CN104098441A - Technology and device system for producing dimethyl oxalate by high-pressure carbonylation of industrial synthesis gases and producing ethylene glycol through dimethyl oxalate hydrogenation - Google Patents
Technology and device system for producing dimethyl oxalate by high-pressure carbonylation of industrial synthesis gases and producing ethylene glycol through dimethyl oxalate hydrogenation Download PDFInfo
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- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
- C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
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- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
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Abstract
The invention relates to a technology and a device system for producing dimethyl oxalate by high-pressure carbonylation of industrial synthesis gases and producing ethylene glycol through dimethyl oxalate hydrogenation. The technology comprises the following steps: adopting industrial NO, O2 and methanol as raw materials for an esterification reaction to produce methyl nitrite; adopting industrial CO and methyl nitrite for a carbonylation reaction in a plate reactor to produce carbonylation products, which mainly include dimethyl oxalate and dimethyl carbonate; separating the carbonylation products to obtain dimethyl carbonate products; subsequently adding hydrogen into dimethyl oxalate in the plate reactor to produce ethylene glycol products; conducting the coupling recovery treatment on waste acids in the esterification reaction and purge gases in the carbonylation reaction for recycling. The device system comprises an esterification reaction system, a carbonylation reaction system, a coupling recovery system for purge gases and waste acids and a hydrogenation reaction system. The technology has the characteristic that device consumption is remarkably reduced, and particularly the nitric acid waste liquid recycling and purge gas recycling technologies as well as the separation technologies thereof are highly coupled; recycling of the raw materials in reaction waste gases is realized, and the effect is remarkable.
Description
Technical field
The present invention relates to a kind of technique and apparatus system of industrial synthetic gas preparing ethylene glycol, relate in particular to technique and apparatus system thereof that a kind of industrial synthetic gas pressure carbonylation is produced dimethyl oxalate Hydrogenation ethylene glycol.
Background technology
Ethylene glycol is a kind of broad-spectrum chemical, be mainly used in the multiple production fields such as trevira (PET), frostproofer, thanomin and explosive, and as solvent, lubricant and softening agent, used in a large number, and ethylene glycol approaches 95% in the application of PET PET industry.In current industrial, ethylene glycol is produced the main oil ethene that adopts and is obtained oxyethane through gaseous oxidation, then through the route of liquid-phase catalysis hydration preparing ethylene glycol.But along with international oil price in recent years occupies high price for a long time, take ethene and face immense pressure as waste ethylene glycol industrial chain in the world at present.Therefore, adopt synthetic gas preparing ethylene glycol technological line due to low production cost, more and more cause widely and pay close attention to.
In coal-ethylene glycol technological process, mainly adopt at present shell and tube reactor, it is low that ubiquity heat of reaction is moved thermo-efficiency, and utilization coefficient and the packing factor of catalyzer are low, thereby affect reactor throughput.
Patent (publication number CN101462961) provide a kind of technique of producing ethylene glycol with coproduction product dimethyl carbonate, technological process comprises CO and methyl nitrite synthesizing dimethyl oxalate and methylcarbonate process, fractionation by distillation obtains methylcarbonate product process, heavy constituent dimethyl oxalate shortening synthesizing glycol process, also comprises the regenerative response process of methyl nitrite in system.But reactor adopts shell and tube reactor, and the waste gas producing in reaction process and waste liquid are not realized circulation recycling, and plant energy consumption is higher, can not meet the growing environmental protection needs of country.
Patent (publication number CN101830806) discloses the method and apparatus of a kind of co-producing dimethyl carbonate and dimethyl oxalate, patent adopts two oxonation devices, first is methylcarbonate synthesis reactor, second is the reactor of dimethyl oxalate, after methyl nitrite reaction generates, enter respectively two reactors and produce respectively methylcarbonate and dimethyl oxalate, then product carries out separating-purifying, this is from Process Route angle, its essence is only the simple cumulative of two class reactors, cannot really realize the practical significance of DMO coproduction DMC in same device.In patent, integrated artistic flow process is not carried out energy-optimisedly yet, environmental practice necessary in reaction process is not had to announcement yet.Experimentation is not also course of industrialization.
In addition the nitric acid by product producing in the loss of NO and processing reaction process in speeding to let slip journey, is a stubborn problem.Patent CN201210531022.1 discloses a kind of method, and the nitric acid producing is concentrated, and then by part, the circulation gas containing NO reacts with it, produces NO
2, supplement and get back to methyl nitrite regeneration reactor.But containing in the circulation gas of NO, also contain the gases such as a large amount of methyl nitrites and methyl alcohol, these gases also can react with concentrated nitric acid, and product is more complicated, thereby affects device usefulness.
In sum, at present coal-ethylene glycol technique mainly exists that catalyst utilization is low, catalyst loading coefficient is low, and in device, valuable gas can not make full use of, on the contrary contaminate environment, apparatus system heat can not fully be utilized, thus cause society and economic benefit undesirable.
Summary of the invention
The object of the invention is to solve that the raw material availability that current production ethylene glycol technology exists is low, production cost is high, catalyst utilization is low, packing factor is low, facility investment is excessive, single series equipment cannot maximize by adaptive device, high and the device of system consumption is used and can not meet country's problems such as requirement to industrial environment day by day, provide a kind of for improving single series plant capacity, treating tail gas, by-product reclaims and technique and the apparatus system thereof of raw material comprehensive utilization.
The present invention is achieved by the following technical solutions:
Industrial synthetic gas pressure carbonylation is produced an apparatus system for dimethyl oxalate Hydrogenation ethylene glycol, comprises oxonation system, esterification system, speeds to exit and spent acid coupling recovery system and hydrogenation reaction system;
Described oxonation system comprises oxonation device, the first gas-liquid separator, Methanol Wash Column, methanol rectifying tower and DMO rectifying tower; Described oxonation device is provided with its top feed mouth, bottom discharge mouth, bottom refrigerant import and top refrigerant exit; Described the first gas-liquid separator is provided with opening for feed, pneumatic outlet and liquid exit; Described Methanol Wash Column is provided with top opening for feed, underfeed mouth, top exit and outlet at bottom; Described methanol rectifying tower is provided with top opening for feed, underfeed mouth, top exit and outlet at bottom; Described DMO rectifying tower is provided with underfeed mouth, top exit and outlet at bottom;
Described esterification system comprises esterification reaction tower and methanol distillation column; Described esterification reaction tower is provided with its top feed mouth, top opening for feed, a plurality of underfeed mouth, middle part reflux inlet, top exit and outlet at bottom; Described methanol distillation column is provided with middle and lower part opening for feed, underfeed mouth, top exit and outlet at bottom;
The described venting of speeding comprises nitric acid concentration tower, NO recovery tower, MN recovery tower and pressure-variable adsorption tank with spent acid coupling recovery system; Described nitric acid concentration tower is provided with middle part opening for feed, top exit and outlet at bottom; Described NO recovery tower is provided with its top feed mouth, middle part opening for feed, bottom feed mouth, top exit and outlet at bottom; Described MN recovery tower is provided with top opening for feed, underfeed mouth, top exit and outlet at bottom; Described pressure-variable adsorption tank is provided with opening for feed, reclaims gas outlet and the outlet of discharge gas;
Described hydrogenation reaction system comprises and adds Recycle hydrogen compressor, hydrogenator, the second gas-liquid separator, membrane separation apparatus, method separation tower, light constituent rectifying tower and ethylene glycol product tower; The described Recycle hydrogen compressor that adds comprises import and outlet; Described hydrogenator is provided with its top feed mouth, bottom discharge mouth, bottom refrigerant import and top refrigerant exit; Described the second gas-liquid separator is provided with opening for feed, pneumatic outlet and liquid exit; Described membrane separation apparatus is provided with opening for feed, reclaims gas outlet and the outlet of discharge gas; Described method separation tower is provided with middle part opening for feed, the outlet of top non-condensable gas, the outlet of top liquid phase light constituent and the outlet of bottom liquid phases heavy constituent; Described light constituent rectifying tower is provided with underfeed mouth, top exit and outlet at bottom; Described ethylene glycol product tower is provided with underfeed mouth, top exit, top outlet and outlet at bottom;
Its top feed mouth of described oxonation device and CO raw material pipeline and N
2raw material pipeline connects through pipeline; The bottom discharge mouth of described oxonation device is connected through pipeline with the opening for feed of described the first gas-liquid separator; The pneumatic outlet of described the first gas-liquid separator is connected through pipeline with the underfeed mouth of described Methanol Wash Column; The liquid exit of described the first gas-liquid separator is connected through pipeline with the top opening for feed of described methanol rectifying tower; The top exit of described Methanol Wash Column is provided with branch outlet A and branch outlet B, and branch outlet A is connected through pipeline with a underfeed mouth of described esterification reaction tower, and branch outlet B is connected through pipeline with the bottom feed mouth of described NO recovery tower; The outlet at bottom of described Methanol Wash Column is connected through pipeline with the underfeed mouth of described methanol rectifying tower; The top exit of described methanol rectifying tower is connected through pipeline with the top opening for feed of described esterification reaction tower; The outlet at bottom of described methanol rectifying tower is connected through pipeline with the underfeed mouth of described DMO rectifying tower; The outlet at bottom of described DMO rectifying tower is connected through pipeline with its top feed mouth of described hydrogenator, and the top exit of described DMO rectifying tower is DMC products export;
Other underfeed mouth of described esterification reaction tower and NO raw material pipeline and multichannel O
2raw material pipeline connects through pipeline respectively; Its top feed mouth of described esterification reaction tower is connected through pipeline with methanol feedstock pipeline; The outlet at bottom of described esterification reaction tower is provided with branch outlet C and branch outlet D, and branch outlet C is connected through pipeline with the middle part reflux inlet of described esterification reaction tower, and branch outlet D is connected through pipeline with the underfeed mouth of described methanol distillation column; The top exit of described esterification reaction tower is connected through pipeline with its top feed mouth of described oxonation device; The top exit of described methanol distillation column is provided with branch outlet E and branch outlet F, and branch outlet E is connected through pipeline with the top opening for feed of described esterification reaction tower, and branch outlet F is connected through pipeline with the top opening for feed of described MN recovery tower; The outlet at bottom of described methanol distillation column is connected through pipeline with the middle part opening for feed of described nitric acid concentration tower;
The top exit of described nitric acid concentration tower is waste liquid relief outlet; The outlet at bottom of described nitric acid concentration tower is connected through pipeline with the middle part opening for feed of described NO recovery tower; The top exit of described NO recovery tower is connected through pipeline with the underfeed mouth of described MN recovery tower; The outlet at bottom of described NO recovery tower is connected through pipeline with the middle and lower part opening for feed of described methanol distillation column; The top exit of described MN recovery tower is connected through pipeline with the opening for feed of described pressure-variable adsorption tank; The outlet at bottom of described MN recovery tower is connected through pipeline with the top opening for feed of described esterification reaction tower; The recovery gas outlet of described pressure-variable adsorption tank is connected through pipeline with its top feed mouth of described oxonation device; The discharge gas outlet of described pressure-variable adsorption tank is connected through pipeline with retrieving arrangement out-of-bounds;
The described import that adds Recycle hydrogen compressor is connected through pipeline with plant hydrogen raw material pipeline, described in add the outlet of Recycle hydrogen compressor and its top feed mouth of described hydrogenator is connected through pipeline; The bottom discharge mouth of described hydrogenator is connected through pipeline with the opening for feed of described the second gas-liquid separator; The pneumatic outlet of described the second gas-liquid separator is provided with branch outlet G and branch outlet H, branch outlet G with described in add Recycle hydrogen compressor import through pipeline, be connected, branch outlet H is connected through pipeline with the opening for feed of described membrane separation apparatus; The liquid exit of described the second gas-liquid separator is connected through pipeline with the underfeed mouth of described method separation tower; The top non-condensable gas outlet of described method separation tower is connected through pipeline with the opening for feed of described membrane separation apparatus; The top liquid phase light constituent outlet of described method separation tower is provided with branch outlet I and branch outlet J, and branch outlet I is connected through pipeline with the top opening for feed of described Methanol Wash Column, and branch outlet J is connected through pipeline with its top feed mouth of described NO recovery tower; The bottom liquid phases heavy constituent outlet of described method separation tower is connected through pipeline with the underfeed mouth of described light constituent rectifying tower; The top light constituent outlet of described light constituent rectifying tower is connected through pipeline with alcohol retrieving arrangement out-of-bounds; The bottom heavy constituent outlet of described light constituent rectifying tower is connected through pipeline with the underfeed mouth of described ethylene glycol product tower; The top exit of described ethylene glycol product tower and out-of-bounds 1,2-BDO recycling and processing device connects through pipeline; The outlet at bottom of described ethylene glycol product tower is connected through pipeline with recycling and processing device out-of-bounds; The top outlet of described ethylene glycol product tower is ethylene glycol products export; The discharge gas outlet of described membrane separation apparatus is connected through pipeline with retrieving arrangement out-of-bounds, and the recovery gas of described membrane separation apparatus exports and is connected through pipeline with its top feed mouth of described hydrogenator.
Described oxonation device is externally connected with dehydration tower; Described dehydration tower is provided with opening for feed and dry gas outlet; The recovery gas outlet of the top exit of described esterification reaction tower and described pressure-variable adsorption tank is connected through pipeline with the opening for feed of described dehydration tower; The dry gas outlet of described dehydration tower is connected through pipeline with described oxonation device its top feed mouth.
Described dehydration tower is comprised of mole sieve drier A and the mole sieve drier B of two alternate runs and regeneration; Filled with adsorbent in mole sieve drier A and mole sieve drier B; Described sorbent material is selected from 3A molecular sieve, 4A molecular sieve, 5A molecular sieve, 9A molecular sieve and calcium oxide.
The bottom discharge mouth of described oxonation device is connected with outlet interchanger I; Described outlet interchanger I is provided with cold logistics import, cold logistics outlet, thermal material import and hot logistics outlet; Described CO raw material pipeline, N
2the dry gas outlet of raw material pipeline and dehydration tower is connected through pipeline with the cold logistics import of described outlet interchanger I; The cold logistics outlet of described outlet interchanger I is connected through pipeline with its top feed mouth of described oxonation device; The bottom discharge mouth of described oxonation device is connected through pipeline with the hot logistics import of described outlet interchanger I; The hot logistics outlet of described outlet interchanger I is connected through pipeline with the opening for feed of described the first gas-liquid separator.
Described oxonation device is externally connected with drum I; Described drum I is provided with refrigerant import, refrigerant exit, liquid-vapor mixture import and vapour outlet; The refrigerant import of described drum I is connected through pipeline with refrigerant raw material pipeline; The refrigerant exit of described drum I is connected through pipeline with the bottom refrigerant import of described oxonation device; The top refrigerant exit of described oxonation device is connected through pipeline with the liquid-vapor mixture import of described drum I; The vapour outlet of described drum I is connected through pipeline with vapor-recovery system out-of-bounds.
Between the branch outlet A of described Methanol Wash Column and the underfeed mouth of described esterification reaction tower, be connected with carbonylation recycle compressor; Described carbonylation recycle compressor is provided with import and outlet; Described branch outlet A is connected through pipeline with the import of described carbonylation recycle compressor; The outlet of described carbonylation recycle compressor is connected through pipeline with the underfeed mouth of described esterification reaction tower.
Between the bottom feed mouth of the top exit of described NO recovery tower and described MN recovery tower, be connected with compressor; Described compressor is provided with import and outlet; The top exit of described NO recovery tower is connected through pipeline with the import of described compressor; The outlet of described compressor is connected through pipeline with the bottom feed mouth of described MN recovery tower.
The bottom discharge mouth of described hydrogenator is connected with outlet interchanger II; Described outlet interchanger II is provided with cold logistics import, cold logistics outlet, thermal material import and hot logistics outlet; The recovery gas outlet of the outlet at bottom of described DMO rectifying tower, described membrane separation apparatus and described in add the outlet of Recycle hydrogen compressor and the cold logistics import of described outlet interchanger II is connected through pipeline; The cold logistics outlet of described outlet interchanger II is connected through pipeline with its top feed mouth of described hydrogenator; The bottom discharge mouth of described hydrogenator is connected through pipeline with the hot logistics import of described outlet interchanger II; The hot logistics outlet of described outlet interchanger II is connected through pipeline with the opening for feed of described the second gas-liquid separator.
Its top feed mouth of described hydrogenator is connected with the well heater that goes into operation; The described well heater that goes into operation is provided with opening for feed and discharge port; The cold logistics outlet of described outlet interchanger II with described in the go into operation opening for feed of well heater through pipeline, be connected; The discharge port of the described well heater that goes into operation is connected through pipeline with its top feed mouth of described hydrogenator.
Described hydrogenator is externally connected with drum II; Described drum II is provided with refrigerant import, refrigerant exit, liquid-vapor mixture import and vapour outlet; The refrigerant import of described drum II is connected through pipeline with refrigerant raw material pipeline; The refrigerant exit of described drum II is connected through pipeline with the bottom refrigerant import of described hydrogenator; The top refrigerant exit of described hydrogenator is connected through pipeline with the liquid-vapor mixture import of described drum II; The vapour outlet of described drum II is connected through pipeline with vapor-recovery system out-of-bounds.
Described the second gas-liquid separator comprises high-pressure gas-liquid separator and low-pressure gas-liquid separator; Described high-pressure gas-liquid separator is provided with opening for feed, pneumatic outlet and liquid exit; Described low-pressure gas-liquid separator is provided with opening for feed, pneumatic outlet and liquid exit; The hot logistics outlet of described outlet interchanger II is connected through pipeline with the opening for feed of described high-pressure gas-liquid separator; The pneumatic outlet of described high-pressure gas-liquid separator is provided with branch outlet K and branch outlet L, branch outlet K with described in add Recycle hydrogen compressor import through pipeline, be connected, branch outlet L is connected through pipeline with the opening for feed of described low-pressure gas-liquid separator; The liquid exit of described high-pressure gas-liquid separator is connected through pipeline with the middle part opening for feed of described method separation tower; The pneumatic outlet of described low-pressure gas-liquid separator is connected through pipeline with the opening for feed of described membrane separation apparatus; The liquid exit of described low-pressure gas-liquid separator is connected through pipeline with the middle part opening for feed of described method separation tower.
Before the opening for feed of described membrane separation apparatus, be provided with methyl alcohol tourie; Described methyl alcohol tourie is provided with opening for feed and clean gas outlet; The top non-condensable gas outlet of the pneumatic outlet of described low-pressure gas-liquid separator and described method separation tower is connected through pipeline with the opening for feed of described methyl alcohol tourie; The clean gas outlet of described methyl alcohol tourie is connected through pipeline with the opening for feed of described membrane separation apparatus.
Preferably, described oxonation device is plate-type reactor, tubular reactor or tubular type-board-like compound reactor.
Preferably, described oxonation device is board-like fixed bed oxonation device.
Preferably, described board-like fixed bed oxonation Qi center is provided with plate groups lock chamber, in described plate groups lock chamber, is provided with plate groups, and described plate groups lock chamber is also provided with bottom inlet and top exit; The outer wall of described plate groups lock chamber is provided with beds between the inwall of board-like fixed bed oxonation device; In beds, be filled with oxonation catalyzer, described beds is also provided with top entrance and outlet at bottom; Bottom at described board-like fixed bed oxonation device, the bottom refrigerant import of described board-like fixed bed oxonation device is connected through pipeline with the bottom inlet of described plate groups lock chamber, and the outlet at bottom of described beds is connected through pipeline with the bottom discharge mouth of described board-like fixed bed oxonation device; Top at described board-like fixed bed oxonation device, the its top feed mouth of described board-like fixed bed oxonation device is connected through pipeline with the top entrance of described beds, and the top exit of described plate groups lock chamber is connected through pipeline with the top refrigerant exit of described board-like fixed bed oxonation device.
Preferably, described esterification reaction tower is packing tower.
Preferably, described esterification reaction tower is for have column plate-filler mixing column of column plate part and filler filling part simultaneously.
Preferably, described Methanol Wash Column, methanol rectifying tower, methanol distillation column, NO recovery tower, MN recovery tower, DMO rectifying tower and nitric acid concentration tower are packing tower, tray column or bubble-plate column.
Preferably, the filler loading in described packing tower is dumped packing or High Efficient Standard Packing; Described dumped packing be shaped as the shape of a saddle, Raschig ring, Pall ring, wheel shape, rectangular saddle ring, spherical or column; Described High Efficient Standard Packing is ripple packing, grid packing or Impulse packing.
Preferably, described hydrogenator is plate-type reactor, tubular reactor or tubular type-board-like compound reactor.
Preferred, described hydrogenator is board-like fixed bed hydrogenation reactor.
Preferably, the center of described board-like fixed bed hydrogenation reactor is provided with plate groups lock chamber, in described plate groups lock chamber, is provided with plate groups, and described plate groups lock chamber is also provided with bottom inlet and top exit; The outer wall of described plate groups lock chamber is provided with beds between the inwall of board-like fixed bed hydrogenation reactor; In described beds, be filled with catalyst for hydrogenation, described beds is also provided with top entrance and outlet at bottom; Bottom at described board-like fixed bed hydrogenation reactor, the bottom refrigerant import of described board-like fixed bed hydrogenation reactor is connected through pipeline with the bottom inlet of described plate groups lock chamber, and the outlet at bottom of described beds is connected through pipeline with the bottom discharge mouth of described board-like fixed bed hydrogenation reactor; Top at described board-like fixed bed hydrogenation reactor, the its top feed mouth of described board-like fixed bed hydrogenation reactor is connected through pipeline with the top entrance of described beds, and the top exit of described plate groups lock chamber is connected through pipeline with the top refrigerant exit of described board-like fixed bed hydrogenation reactor.
Preferably, described membrane separation apparatus is in parallel or be connected in series and form by 1～100 hollow fiber film assembly.
Industrial synthetic gas pressure carbonylation is produced a technique for dimethyl oxalate Hydrogenation ethylene glycol, for adopting technical grade NO, O
2with methyl alcohol be that raw material generation esterification generates methyl nitrite, then with technical grade CO and methyl nitrite, carry out oxonation and generate the carbonyl compounds that is mainly dimethyl oxalate and methylcarbonate, carbonyl compounds obtains methylcarbonate product after separation, and dimethyl oxalate is through follow-up hydrogenation generating glycol product; And the venting of speeding of the spent acid of esterification and oxonation is through coupling recycling recycle.
Reaction equation is as follows:
Esterification: 4NO+O
2+ 4CH
3oH → 4CH
3oNO+2H
2o;
Oxonation: 2CO+2CH
3oNO → (COOCH
3)
2+ 2NO;
Hydrogenation reaction: (COOCH
3)
2+ 4H
2→ (CH
2oH)
2+ 2CH
3oH;
Total reaction: 4CO+O
2+ 8H
2→ 2 (CH
2oH)
2+ 2H
2o;
Described a kind of industrial synthetic gas pressure carbonylation is produced the technique of dimethyl oxalate Hydrogenation ethylene glycol, specifically comprises the following steps:
(1) in esterification reaction tower, pass into technical grade NO, O
2carry out esterification with methyl alcohol; Esterification column overhead methyl nitrite gas mixture passes into oxonation device and carries out oxonation; Esterification reaction tower tower reactor acidity alcohol solution is partly refluxed to esterification reaction tower, and part passes into methanol distillation column; The methyl alcohol of methanol distillation column recovered overhead is partly circulated to esterification reaction tower recycle, and all the other enter MN recovery tower as washings; Methanol distillation column tower reactor spent acid enters nitric acid concentration tower and carries out concentration;
(2) from methyl nitrite and technical grade CO, the N of esterification reaction tower
2charging enters oxonation device, under oxonation catalyzer exists, oxonation occurs; The temperature of oxonation is 30～200 ℃, and reaction pressure is 1～10MPa, gas hourly space velocity 3000～30000h-
1;
(3) carbonyl compounds enters the first gas-liquid separator generation gas-liquid separation, and gas phase enters Methanol Wash Column, and liquid phase enters methanol rectifying tower; Methanol Wash Column top gaseous phase component is partly circulated to esterification reaction tower, and part enters NO recovery tower as the venting of speeding and recycles; Methanol Wash Column tower bottoms phase component enters methanol rectifying tower and carries out rectifying separation; The methyl alcohol of methanol rectifying tower recovered overhead and methyl nitrite mixture are circulated to esterification reaction tower recycling, and tower reactor heavy constituent enters DMO rectifying tower; DMO rectifying tower tower top obtains DMC product, and tower reactor dimethyl oxalate component enters hydrogenator and carries out hydrogenation reaction;
(4) from the spent acid of methanol distillation column after nitric acid concentration tower concentrate to concentration of nitric acid is 10～68wt%, be circulated to NO recovery tower; In NO recovery tower, concentrated nitric acid, methyl alcohol and esterification regenerative response occurs from the venting of speeding of Methanol Wash Column; NO recovery tower top gaseous phase light constituent enters MN recovery tower, and the nitric acid waste that contains methyl alcohol that tower reactor produces is circulated to methanol distillation column and further recycles; In MN recovery tower, gas-phase feed, after reclaiming methanol wash, enters pressure-variable adsorption tank, and MN recovery tower tower reactor enters esterification reaction tower containing the alcoholic solution circulation of methyl nitrite; The isolated CO of pressure-variable adsorption tank
2be disposed to out-of-bounds and process, the N of recovery
2enter the recycle of oxonation device with CO purified gas;
(5) from the dimethyl oxalate component of DMO tower bottom of rectifying tower, enter hydrogenator with after plant hydrogen after adding Recycle hydrogen compressor pressurization mixes, under hydrogenation catalyst existence, hydrogenation reaction methanol and ethylene glycol etc.; The temperature of hydrogenation reaction is 160～320 ℃, and reaction pressure is 1～10MP, and liquid hourly space velocity is 1～3Kg/Kg.h;
(6) hydrogenation products enters the second gas-liquid separator generation gas-liquid separation, gas phase part through described in add after Recycle hydrogen compressor pressurizes and be circulated to hydrogenator, part enters membrane separation apparatus and return to hydrogenator recycle after recycling, and liquid phase enters the separation of ethylene glycol product tower and obtains ethylene glycol product.
Wherein,
Preferably, described oxonation device is externally connected with dehydration tower; The gas phase reclaiming through pressure-variable adsorption tank and removing after moisture through described dehydration tower from the methyl nitrite gas mixture of esterification column overhead, then enter and in oxonation device, carry out oxonation.
Preferably, described dehydration tower is comprised of mole sieve drier A and the mole sieve drier B of two alternate runs and regeneration; In mole sieve drier A and mole sieve drier B, be filled with sorbent material; Described sorbent material is selected from 3A molecular sieve, 4A molecular sieve, 5A molecular sieve, 9A molecular sieve and calcium oxide.The service temperature of described mole sieve drier A and mole sieve drier B is 40～260 ℃, and pressure is 1～10MPa.Except particularly pointing out, in the present invention, all pressure all refers to gauge pressure.
Preferably, through dehydration tower, process and obtain dry gas, moisture content 0.1～100ppm in dry gas.
Preferably, described oxonation device is externally connected with outlet interchanger I; Technical grade CO, N
2and from the dry gas of dehydration tower, as oxonation raw material, after described outlet interchanger I and oxonation product heat exchange from oxonation device, enter again and in oxonation device, carry out oxonation.
Preferably, the part gaseous component from methanol wash column overhead enters esterification reaction tower after the pressurization of carbonylation recycle compressor again.
Preferably, described NO recovery tower top gaseous phase light constituent enters MN recovery tower after compressor compression supercharging again.
Preferably, described hydrogenator is externally connected with outlet interchanger II; From the dimethyl oxalate component of DMO rectifying tower, from the plant hydrogen of pressurized circulation compressor and circulation gas and from the recovery gas of membrane separation apparatus, as hydrogenation reaction raw material, after described outlet interchanger II and hydrogenation products heat exchange from hydrogenator, enter again and in hydrogenator, carry out hydrogenation reaction.
Preferably, first the liquid phase of described the second gas-liquid separator separates enters method separation tower; The non-condensable gas of method separation tower recovered overhead enters described membrane separation apparatus, and the liquid phase light constituents such as methyl alcohol of method separation tower recovered overhead partly enter the top of described Methanol Wash Column as washings, and part enters NO recovery tower; Method separation tower tower reactor liquid phase heavy constituent enters the further separating-purifying of light constituent rectifying tower; Light constituent rectifying tower tower top light constituent enters out-of-bounds alcohol retrieving arrangement recycling; Light constituent tower bottom of rectifying tower heavy constituent enters described ethylene glycol product tower; Ethylene glycol product column overhead light constituent enters out-of-bounds 1, and 2-BDO recycling and processing device further recycles, and ethylene glycol product tower tower reactor heavy constituent enters out-of-bounds recycling and processing device and carries out subsequent disposal, and the top side line of ethylene glycol product tower is drawn ethylene glycol product.
Preferably, described the second gas-liquid separator comprises high-pressure gas-liquid separator and low-pressure gas-liquid separator; Through the isolated gas phase of high-pressure gas-liquid separator, add Recycle hydrogen compressor described in partly entering, part enters described low-pressure gas-liquid separator; The isolated liquid phase of high-pressure gas-liquid separator enters described method separation tower; Through the isolated gas phase of described low-pressure gas-liquid separator, enter described membrane separation apparatus, through the isolated liquid phase of low-pressure gas-liquid separator, enter described method separation tower.
Preferably, in the isolated gas phase of described high-pressure gas-liquid separator, wherein 0.1～10v% enters low-pressure gas-liquid separator.
Preferably, through the isolated gas phase of described low-pressure gas-liquid separator and from the non-condensable gas of described separating methanol column overhead, after absorbing methyl alcohol, methyl alcohol tourie enters again described membrane separation apparatus.
Preferably, described oxonation device is plate-type reactor, tubular reactor or tubular type-board-like compound reactor.
Preferred, described carbonylation plate-type reactor is board-like fixed bed oxonation device.
Preferably, described board-like fixed bed oxonation Qi center is provided with plate groups lock chamber, in described plate groups lock chamber, is provided with plate groups; The outer wall of described plate groups lock chamber is provided with beds between the inwall of board-like fixed bed oxonation device; In beds, be filled with oxonation catalyzer; Oxonation raw material reaches after beds inlet temperature, enters oxonation occurs in beds from the top of described board-like fixed bed oxonation device; The refrigerant of introducing from outside enters plate groups lock chamber from the bottom of board-like fixed bed oxonation device, and from the Base top contact of described board-like fixed bed oxonation device, counter-current process carries out the reaction heat that oxonation is taken away in heat exchange; Carbonyl compounds from beds bottom is drawn from the bottom of board-like fixed bed oxonation device.
Preferably, described board-like fixed bed oxonation device is externally connected with drum I; The refrigerant of introducing from outside enters drum I, and the refrigerant in drum I enters in the plate groups lock chamber of board-like fixed bed oxonation device and carries out heat exchange with beds, shifts out reaction heat; Refrigerant after heating is liquid-vapor mixture, enters drum I and carries out gas-liquid separation, and the low-pressure saturated steam of generation enters out-of-bounds low-pressure steam recovery system and recycles.
Preferably, described oxonation catalyzer adopts Shanghai Wuzheng Engineering Co., Ltd. commercial catalyst, and catalyzer trade names are DMO-0701T.
Preferably, described esterification reaction tower is packing tower;
Preferably, described esterification reaction tower is for have column plate-filler mixing column of column plate part and filler filling part simultaneously.
Preferably, the number of theoretical plate of described esterification reaction tower is 20～50.It is first block of column plate that described each tower stage number sequential expression is all set tower top, then sequentially by number to tower bottom, arranges.
Preferably, in the charging of described esterification reaction tower, described O
2divide 2～8 tunnels respectively from 16th～50 column plate chargings; Described NO and from the top gaseous phase light constituent of Methanol Wash Column from 18th～50 column plate chargings; Described fresh methanol, from the recovery methyl alcohol of Methanol Recovery column overhead, from the methyl alcohol of methanol rectifying tower recovered overhead and methyl nitrite mixture and from the alcoholic solution containing methyl nitrite of MN recovery tower tower reactor from 1st～5 column plate chargings; Esterification reaction tower tower reactor backflow material is from 10th～25 column plate chargings.
Preferably, in described esterification reaction tower, O
2, NO and methyl alcohol molar ratio be 0.01～0.8:0.1～3.2:0.8～50.
Preferably, described esterification reaction tower tower top temperature is 30～80 ℃, and tower reactor temperature is 50～200 ℃, and reaction zone temperature is 50～160 ℃, and reaction pressure is 0.5～10MPa.
Preferably, described methanol distillation column, Methanol Wash Column, methanol rectifying tower, nitric acid concentration tower, NO recovery tower, MN recovery tower, DMO rectifying tower are packing tower, tray column or bubble-plate column.
Preferably, the filler loading in described packing tower is dumped packing or High Efficient Standard Packing; Described dumped packing be shaped as the shape of a saddle, Raschig ring, Pall ring, wheel shape, rectangular saddle ring, spherical or column; Described High Efficient Standard Packing is ripple packing, grid packing or Impulse packing.
Preferably, the theoretical plate number of described methanol distillation column is 5～50,40～150 ℃ of tower top temperatures, and tower reactor temperature is 60～230 ℃, tower top pressure is 0.01～2.0MPa.
Preferably, the reflux ratio of described Methanol Recovery column overhead light constituent is 0.1～3.0.
Preferably, in described methanol distillation column recovered overhead methyl alcohol, the part proportion that circulation enters esterification reaction tower is 10～90wt%.
Preferably, the theoretical plate number of described Methanol Wash Column is 10～50, and tower top temperature is 15～70 ℃, and tower reactor temperature is 10～100 ℃, and tower top pressure is 0.9～10MPa.
Preferably, in described Methanol Wash Column top gaseous phase component, described in speed venting accounting be 0.05～5v%.
Preferably, described methanol rectifying tower is extractive distillation column, and theoretical plate number is 10～60, and tower top temperature is 50～150 ℃, and tower reactor temperature is 130～250 ℃, and tower top pressure is 0.01～0.5MPa.
Preferably, the theoretical plate number of described nitric acid concentration tower is 1～30,30～110 ℃ of tower top temperatures, 60～160 ℃ of tower reactor temperature, tower top pressure 0.01～0.3MPa.
Preferably, the reflux ratio of the tower top light constituent of described nitric acid concentration tower is 0.01～3.
Preferably, the theoretical plate number of described NO recovery tower is 5～30, and tower top temperature is 30～120 ℃, and tower reactor temperature is 50～200 ℃, and tower top pressure is 1～10MPa.
Preferably, described in, speed venting from 5th～30 column plate chargings of NO recovery tower; Described concentrate nitric acid is from 1st～10 column plate chargings of NO recovery tower; From the recovery methyl alcohol of separating methanol column overhead from 1st～10 column plate chargings.
Preferably, in described NO recovery tower, mole proportioning of nitric acid, methyl alcohol and the NO in venting that speeds is 1.1～10:2～100:1～5.
Preferably, the theoretical plate number of described MN recovery tower is 10～60, and tower top temperature is 0～50 ℃, and tower reactor temperature is 0～80 ℃, and reaction pressure is 1～10MPa.
Preferably, the theoretical plate number of described DMO rectifying tower is 10～50, and tower top temperature is 80～120 ℃, and tower reactor temperature is 120～200 ℃, normal pressure or decompression operation.
Preferably, described DMO rectifying tower tower top light constituent reflux ratio is 0.1～100.
Preferably, consisting of of the purified gas reclaiming in described pressure-variable adsorption tank: N
2be 60～80v%, CO is 20～40v%; Isolated CO
2gas accounts for 0.1～5v% of air inlet total amount, wherein CO
2concentration be 99.8～99.9v%; Isolated CO
2gas can be through out-of-bounds device processing.
Preferably, described hydrogenator is plate-type reactor, tubular reactor or tubular type-board-like compound reactor.
Preferred, described hydrogenation plate-type reactor is board-like fixed bed hydrogenation reactor.
Preferably, the center of described board-like fixed bed hydrogenation reactor is provided with plate groups lock chamber, in described plate groups lock chamber, is provided with plate groups; The outer wall of described plate groups lock chamber is provided with beds between the inwall of board-like fixed bed hydrogenation reactor; In described beds, be filled with catalyst for hydrogenation; Hydrogenation reaction raw material reaches after beds inlet temperature, enters hydrogenation reaction occurs in beds from the top of described board-like fixed bed hydrogenation reactor; The refrigerant of introducing from outside enters plate groups lock chamber from the bottom of board-like fixed bed hydrogenation reactor, and from the Base top contact of described board-like fixed bed hydrogenation reactor, counter-current process carries out the reaction heat that hydrogenation reaction is taken away in heat exchange; Hydrogenation products from beds bottom is drawn from the bottom of board-like fixed bed hydrogenation reactor.
Preferably, described board-like fixed bed hydrogenation reactor is externally connected with drum II; The refrigerant of introducing from outside enters drum II, and the refrigerant in drum II enters in the plate groups lock chamber of board-like fixed bed hydrogenation reactor and carries out heat exchange with beds, shifts out reaction heat; Refrigerant after heating is liquid-vapor mixture, enters drum II and carries out gas-liquid separation, and the low-pressure saturated steam of generation enters out-of-bounds low-pressure steam recovery system and recycles.
Preferably, described refrigerant is water or thermal oil, is preferably water.
Preferably, described board-like fixed bed hydrogenation reactor is externally connected with the well heater that goes into operation; Go into operation the initial stage, temperature does not reach reaction requirement, and hydrogenation reaction raw material enters the well heater that goes into operation and carries out preheating, and preheating reaches and enters beds after beds temperature in and carry out hydrogenation reaction; Go into operation the initial stage, described in the well heater that goes into operation provide unique thermal source for the hydrogenation reaction in described board-like fixed bed hydrogenation reactor; The thermal source of the described well heater that goes into operation is low-pressure steam.
Preferably, described catalyst for hydrogenation is selected from Shanghai Wuzheng Engineering Co., Ltd. commercial catalyst, and catalyzer trade names are MEG-801T.
Preferably, the theoretical plate number of described method separation tower is 10～40,40～70 ℃ of tower top temperatures, 80～180 ℃ of tower reactor temperature, normal pressure or decompression operation; Described separating methanol column overhead light constituent reflux ratio is 0.1～3.
Preferably, the theoretical plate number of described light constituent rectifying tower is 10～60,58～90 ℃ of tower top temperatures, 70～160 ℃ of tower reactor temperature, absolute pressure of top of the tower 5～50KPa.
Preferably, the tower top light constituent reflux ratio of described light constituent rectifying tower is 1～50.
Preferably, the theoretical plate number of described ethylene glycol product tower is 30～100,100～150 ℃ of the temperature of tower top, and 130～230 ℃ of tower reactor temperature, absolute pressure of top of the tower is 5～50KPa; Described ethylene glycol product column overhead light constituent reflux ratio is 50～120 or total reflux.
Preferably, described membrane separation apparatus is in parallel or be connected in series and form by 1～100 hollow fiber film assembly.
Preferably, the proof pressure of the shell of described membrane separation apparatus is 4.75MPa, maximum differential pressure 1.5MPa (unstripped gas is to infiltration gas); The service temperature of membrane separation apparatus is up to 85 ℃.
Preferably, in the purification gas obtaining through membrane separation apparatus separating-purifying, density of hydrogen is 88～99.00v%, hydrogen recovery rate 90～98.5%.
The ultimate principle of described membrane separation apparatus is to utilize the partial pressure difference of hollow-fibre membrane both sides gas as impellent, by the infiltration-dissolving-steps such as diffusion-parsing, utilizes hollow-fibre membrane different to the selection perviousness of various gases, thereby reaches separated object.Raw material is made the shell side of hollow fiber film assembly leave with rage, and tube side is made in infiltration leave with rage, and tail gas enters next hollow fiber film assembly.Because of H
2on film surface, infiltration rate is CH
4, N
2, tens times of Ar etc., so H
2enter after collecting in every hollow fiber conduit and discharge from membrane separation apparatus bottom, impermeable gas (tail gas) is discharged from the top of hollow fiber film assembly.Hollow fiber film assembly inside is a chipware being comprised of 1000～100000 hollow-fibre membrane fiber tubes, and fibre pipe is to be processed through special by macromolecular material.Unstripped gas is entered by separator side mouth, while contacting with tunica fibrosa fiber tube outside surface along fiber tube bank lateral current downflow gas gas just on fibre wall, dissolve, infiltration and diffusion process, utilize the difference in various gas dissolvings, penetrating power, different types of gas delivery out.
Technique effect of the present invention and advantage are:
Owing to adopting high top pressure operation in carbonylation system and esterification system, the requirement of synthetic gas preparing ethylene glycol process unit to equipment volume that can greatly reduce to maximize, is beneficial to single series device and produces maximization, is beneficial to equipment safety production and reduces facility investment.
Nitric acid waste utilization process and the deflation cycles of speeding are utilized technique height coupling, the waste liquid that produce in device can be contained to the speed raw material of venting of a large amount of nitrogen protoxides, the required methyl nitrite of generation main reaction by circular treatment as recovery.Process combination technological sciences are reasonable, realize the abundant recycle of discharging waste gas and waste liquid by a reactor, economy and environmental protection.
Described methyl nitrite is heat-sensitive substance, especially after higher than certain temperature, with temperature, continue to raise, the decomposition meeting of methyl nitrite constantly aggravates, and the reaction of CO carbonylation coupling dimethyl oxalate processed is strong exothermal reaction, adopt suitable reactor to keep the uniform temperature distribution of bed, controlling reaction hot(test)-spot temperature is the key that prevents the decomposition of methyl nitrite and improve the yield of product, carbonylation plate-type reactor of the present invention is plate-type reactor, realize the reaction of CO carbonylation coupling dimethyl oxalate processed, can make full use of the feature that temperature of reactor is evenly distributed, reach the feature that improves dimethyl oxalate space-time yield recycle reaction heat.Improve simultaneously catalyzer utilization coefficient and reactor volume utilization ratio, increased loaded catalyst, improved reactor throughput.Such reaction characteristics has also obtained same energy conservation and consumption reduction effects in preparing ethylene glycol by using dimethyl oxalate plus hydrogen.
Valuable hydrogen resource has fully been saved in the recovery that hydrogenation workshop section described in technique speeds to exit, and then has reduced unit coal consumption, is conducive to reduce the whole energy consumption of device and disposal of pollutants, has more real meaning.Meanwhile, the speed recovery of venting of the hydrogenation workshop section described in technique, the film separating system adopting reacting system pressure under equal load can reduce 1MPa left and right, and concerning compression system, the reduction of top hole pressure, can save a large amount of power consumptions.Fully save valuable hydrogen resource, and then reduced unit coal consumption, be conducive to reduce the whole energy consumption of device and disposal of pollutants, there is more real meaning.Adopt this film separating system, this is conducive to improve hydrogenation reaction speed, and ethylene glycol day output increased by 10% left and right more originally.
In sum, by adopting high-pressure process flow process and plate-type reactor, effectively solving device maximization bottleneck, reduces facility investment, by reclaiming heat of reaction waste heat, carries out net heat recovery, and unit ethylene glycol production energy consumption reduces, and reduces steam, consumption of cooling-water; By waste gas and waste liquid technique, be coupled, reduce toxic emission, thereby reach the dual purpose of energy-saving and environmental protection.The present invention realizes the abundant reuse of discharging waste gas and waste liquid and device reaction heat, the separated complex energy of tower uses, and improves efficiency of energy utilization, saves energy consumption, has significant industrial application value.The present invention provides guarantee to environmental protection more, higher, the more energy-conservation technical development of efficiency for synthetic gas preparing ethylene glycol technology.Adopt the present invention's feasible and reasonable in economy technically.
Above-mentioned optimization design can improve productive rate significantly, is that any document was not all recorded.And the technological process that the present invention proposes is seen also advantageous particularly from energy consumption angle, the feature with remarkable energy efficient, in conjunction with application useful matter circulation step, particularly nitric acid waste utilization process and the deflation cycles of speeding are utilized the recycling of hydrogen in the coupling of technique height and separating technology and reactor off-gas, and effect is very significant.
Accompanying drawing explanation
A kind of industrial synthetic gas pressure carbonylation of Fig. 1 is produced the apparatus system (part) of dimethyl oxalate Hydrogenation ethylene glycol
A kind of industrial synthetic gas pressure carbonylation of Fig. 2 is produced the apparatus system (part) of dimethyl oxalate Hydrogenation ethylene glycol
Reference numeral:
1, oxonation device; 2, drum I; 3; Outlet interchanger I; 4, the first gas-liquid separators; 5, methanol rectifying tower; 6, DMO rectifying tower; 7, Methanol Wash Column; 8, carbonylation recycle compressor; 9, esterification reaction tower; 10, dehydration tower; 11, methanol distillation column; 12, nitric acid concentration tower; 13, NO recovery tower; 14, compressor; 15, MN recovery tower; 16, pressure-variable adsorption tank; 17, hydrogenator; 18, drum II; 19, well heater goes into operation; 20, outlet interchanger II; 21, high-pressure gas-liquid separator; 22, method separation tower; 23, light constituent rectifying tower; 24, ethylene glycol product tower; 25, add Recycle hydrogen compressor; 26, low-pressure gas-liquid separator; 27, methyl alcohol tourie; 28, membrane separation apparatus.
Embodiment
By specific specific examples, technical scheme of the present invention is described below.Should be understood that one or more method stepss that the present invention mentions do not repel between the step that also has additive method step or clearly mention at these before and after described combination step can also insert additive method step; Should also be understood that these embodiment are only not used in and limit the scope of the invention for the present invention is described.And, except as otherwise noted, the numbering of various method steps is only for differentiating the convenient tool of various method steps, but not for limiting the ordering of various method steps or limiting the enforceable scope of the present invention, the change of its relativeness or adjustment, without essence change technology contents in the situation that, when being also considered as the enforceable category of the present invention.
The experimental technique of unreceipted actual conditions in embodiment below, conventionally according to normal condition, as: chemical industry operation handbook, or the condition of advising according to manufacturer.
As shown in Figure 1 and Figure 2, a kind of industrial synthetic gas pressure carbonylation is produced the apparatus system of dimethyl oxalate Hydrogenation ethylene glycol, comprises oxonation system, esterification system, the spent acid of speeding to exit coupling recovery system and hydrogenation reaction system;
Described oxonation system comprises oxonation device 1, the first gas-liquid separator 4, Methanol Wash Column 7, methanol rectifying tower 5 and DMO rectifying tower 6; Described oxonation device 1 is provided with its top feed mouth, bottom discharge mouth, bottom refrigerant import and top refrigerant exit; Described the first gas-liquid separator 4 is provided with opening for feed, pneumatic outlet and liquid exit; Described Methanol Wash Column 7 is provided with top opening for feed, underfeed mouth, top exit and outlet at bottom; Described methanol rectifying tower 5 is provided with top opening for feed, underfeed mouth, top exit and outlet at bottom; Described DMO rectifying tower 6 is provided with underfeed mouth, top exit and outlet at bottom;
Described esterification system comprises esterification reaction tower 9 and methanol distillation column 11; Described esterification reaction tower 9 is provided with its top feed mouth, top opening for feed, a plurality of underfeed mouth, middle part reflux inlet, top exit and outlet at bottom; Described methanol distillation column 11 is provided with middle and lower part opening for feed, underfeed mouth, top exit and outlet at bottom;
The described venting of speeding comprises nitric acid concentration tower 12, NO recovery tower 13, MN recovery tower 15 and pressure-variable adsorption tank 16 with spent acid coupling recovery system; Described nitric acid concentration tower 12 is provided with middle part opening for feed, top exit and outlet at bottom; Described NO recovery tower 13 is provided with its top feed mouth, middle part opening for feed, bottom feed mouth, top exit and outlet at bottom; Described MN recovery tower 15 is provided with top opening for feed, underfeed mouth, top exit and outlet at bottom; Described pressure-variable adsorption tank 16 is provided with opening for feed, reclaims gas outlet and the outlet of discharge gas;
Described hydrogenation reaction system comprises and adds Recycle hydrogen compressor 14, hydrogenator 17, the second gas-liquid separator, membrane separation apparatus 28, method separation tower 22, light constituent rectifying tower 23 and ethylene glycol product tower 24; The described Recycle hydrogen compressor 14 that adds comprises import and outlet; Described hydrogenation plate answers device 17 to be provided with its top feed mouth, bottom discharge mouth, bottom refrigerant import and top refrigerant exit; Described the second gas-liquid separator is provided with opening for feed, pneumatic outlet and liquid exit; Described membrane separation apparatus 28 is provided with opening for feed, reclaims gas outlet and the outlet of discharge gas; Described method separation tower 22 is provided with middle part opening for feed, the outlet of top non-condensable gas, the outlet of top liquid phase light constituent and the outlet of bottom liquid phases heavy constituent; Described light constituent rectifying tower 23 is provided with underfeed mouth, top exit and outlet at bottom; Described ethylene glycol product tower 24 is provided with underfeed mouth, top exit, top outlet and outlet at bottom;
Its top feed mouth of described oxonation device 1 and CO raw material pipeline and N
2raw material pipeline connects through pipeline; The bottom discharge mouth of described oxonation device 1 is connected through pipeline with the opening for feed of described the first gas-liquid separator 4; The pneumatic outlet of described the first gas-liquid separator 4 is connected through pipeline with the underfeed mouth of described Methanol Wash Column 7; The liquid exit of described the first gas-liquid separator 4 is connected through pipeline with the top opening for feed of described methanol rectifying tower 5; The top exit of described Methanol Wash Column 7 is provided with branch outlet A and branch outlet B, and branch outlet A is connected through pipeline with a underfeed mouth of described esterification reaction tower 9, and branch outlet B is connected through pipeline with the bottom feed mouth of described NO recovery tower 13; The outlet at bottom of described Methanol Wash Column 7 is connected through pipeline with the underfeed mouth of described methanol rectifying tower 5; The top exit of described methanol rectifying tower 5 is connected through pipeline with the top opening for feed of described esterification reaction tower 9; The outlet at bottom of described methanol rectifying tower 5 is connected through pipeline with the underfeed mouth of described DMO rectifying tower 6; The outlet at bottom of described DMO rectifying tower 6 is connected through pipeline with its top feed mouth of described hydrogenator 17, and the top exit of described DMO rectifying tower 6 is DMC products export;
Other underfeed mouth of described esterification reaction tower 9 and NO raw material pipeline and multichannel O
2raw material pipeline connects through pipeline respectively; Its top feed mouth of described esterification reaction tower 9 is connected through pipeline with methanol feedstock pipeline; The outlet at bottom of described esterification reaction tower 9 is provided with branch outlet C and branch outlet D, and branch outlet C is connected through pipeline with the middle part reflux inlet of described esterification reaction tower 9, and branch outlet D is connected through pipeline with the underfeed mouth of described methanol distillation column 11; The top exit of described esterification reaction tower 9 is connected through pipeline with its top feed mouth of described oxonation device 1; The top exit of described methanol distillation column 11 is provided with branch outlet E and branch outlet F, and branch outlet E is connected through pipeline with the top opening for feed of described esterification reaction tower 9, and branch outlet F is connected through pipeline with the top opening for feed of described MN recovery tower 15; The outlet at bottom of described methanol distillation column 11 is connected through pipeline with the middle part opening for feed of described nitric acid concentration tower 12;
The top exit of described nitric acid concentration tower 12 is waste liquid relief outlet; The outlet at bottom of described nitric acid concentration tower 12 is connected through pipeline with the middle part opening for feed of described NO recovery tower 13; The top exit of described NO recovery tower 13 is connected through pipeline with the underfeed mouth of described MN recovery tower 15; The outlet at bottom of described NO recovery tower 13 is connected through pipeline with the middle and lower part opening for feed of described methanol distillation column 11; The top exit of described MN recovery tower 15 is connected through pipeline with the opening for feed of described pressure-variable adsorption tank 16; The outlet at bottom of described MN recovery tower 15 is connected through pipeline with the top opening for feed of described esterification reaction tower 9; The recovery gas outlet of described pressure-variable adsorption tank 16 is connected through pipeline with its top feed mouth of described carbonylation plate-type reactor 1; The discharge gas outlet of described pressure-variable adsorption tank 16 is connected through pipeline with retrieving arrangement out-of-bounds;
The described import that adds Recycle hydrogen compressor 14 is connected through pipeline with plant hydrogen raw material pipeline, described in add the outlet of Recycle hydrogen compressor 14 and its top feed mouth of described hydrogenator 17 is connected through pipeline; The bottom discharge mouth of described hydrogenator 17 is connected through pipeline with the opening for feed of described the second gas-liquid separator; The pneumatic outlet of described the second gas-liquid separator is provided with branch outlet G and branch outlet H, branch outlet G with described in add Recycle hydrogen compressor 14 import through pipeline, be connected, branch outlet H is connected through pipeline with the opening for feed of described membrane separation apparatus 28; The liquid exit of described the second gas-liquid separator is connected through pipeline with the underfeed mouth of described method separation tower 22; The top non-condensable gas outlet of described method separation tower 22 is connected through pipeline with the opening for feed of described membrane separation apparatus 28; The top liquid phase light constituent outlet of described method separation tower 22 is provided with branch outlet I and branch outlet J, and branch outlet I is connected through pipeline with the top opening for feed of described Methanol Wash Column 7, and branch outlet J is connected through pipeline with its top feed mouth of described NO recovery tower 13; The bottom liquid phases heavy constituent outlet of described method separation tower 22 is connected through pipeline with the underfeed mouth of described light constituent rectifying tower 23; The top light constituent outlet of described light constituent rectifying tower 23 is connected through pipeline with alcohol retrieving arrangement out-of-bounds; The bottom heavy constituent outlet of described light constituent rectifying tower 23 is connected through pipeline with the underfeed mouth of described ethylene glycol product tower 24; The top exit of described ethylene glycol product tower 24 and out-of-bounds 1,2-BDO recycling and processing device connects through pipeline; The outlet at bottom of described ethylene glycol product tower 24 is connected through pipeline with recycling and processing device out-of-bounds; The top outlet of described ethylene glycol product tower 24 is ethylene glycol products export; The discharge gas outlet of described membrane separation apparatus 28 is connected through pipeline with retrieving arrangement out-of-bounds, and the recovery gas of described membrane separation apparatus 28 exports and is connected through pipeline with its top feed mouth of described hydrogenator 17.
As preferred embodiment a kind of, described oxonation device 1 is externally connected with dehydration tower 10; Described dehydration tower 10 is provided with opening for feed and dry gas outlet; The recovery gas outlet of the top exit of described esterification reaction tower 9 and described pressure-variable adsorption tank 16 is connected through pipeline with the opening for feed of described dehydration tower 10; The dry gas outlet of described dehydration tower 10 is connected through pipeline with described oxonation device 1 its top feed mouth.
Described dehydration tower is comprised of mole sieve drier A and the mole sieve drier B of two alternate runs and regeneration; Filled with adsorbent in mole sieve drier A and mole sieve drier B.
As preferred embodiment a kind of, the bottom discharge mouth of described oxonation device 1 is connected with outlet interchanger I 3; Described outlet interchanger I 3 is provided with cold logistics import, cold logistics outlet, thermal material import and hot logistics outlet; Described CO raw material pipeline, N
2the dry gas outlet of raw material pipeline and dehydration tower 10 is connected through pipeline with the cold logistics import of described outlet interchanger I 3; The cold logistics outlet of described outlet interchanger I 3 is connected through pipeline with its top feed mouth of described oxonation device 1; The bottom discharge mouth of described oxonation device 1 is connected through pipeline with the hot logistics import of described outlet interchanger I 3; The hot logistics outlet of described outlet interchanger I 3 is connected through pipeline with the opening for feed of described the first gas-liquid separator 4.
As preferred embodiment a kind of, described oxonation device 1 is externally connected with drum I 2; Described drum I 2 is provided with refrigerant import, refrigerant exit, liquid-vapor mixture import and vapour outlet; The refrigerant import of described drum I 2 is connected through pipeline with refrigerant raw material pipeline; The refrigerant exit of described drum I 2 is connected through pipeline with the bottom refrigerant import of described carbonylation plate-type reactor 1; The top refrigerant exit of described oxonation device 1 is connected through pipeline with the liquid-vapor mixture import of described drum I 2; The vapour outlet of described drum I 2 is connected through pipeline with vapor-recovery system out-of-bounds.
As preferred embodiment a kind of, between the branch outlet A of described Methanol Wash Column 7 and the underfeed mouth of described esterification reaction tower 9, be connected with carbonylation recycle compressor 8; Described carbonylation recycle compressor 8 is provided with import and outlet; Described branch outlet A is connected through pipeline with the import of described carbonylation recycle compressor 8; The outlet of described carbonylation recycle compressor 8 is connected through pipeline with the underfeed mouth of described esterification reaction tower 9.
As preferred embodiment a kind of, the bottom feed mouth of the top exit of described NO recovery tower 13 and described MN recovery tower 15 is connected with compressor 14; Described compressor 14 is provided with import and outlet; The top exit of described NO recovery tower 13 is connected through pipeline with the import of described compressor 14; The outlet of described compressor is connected through pipeline with the bottom feed mouth of described MN recovery tower 15.
As preferred embodiment a kind of, the bottom discharge mouth of described hydrogenator 17 is connected with outlet interchanger II 20; Described outlet interchanger II 20 is provided with cold logistics import, cold logistics outlet, thermal material import and hot logistics outlet; The recovery gas outlet of the outlet at bottom of described DMO rectifying tower 6, described membrane separation apparatus 28 and described in add the outlet of Recycle hydrogen compressor 25 and the cold logistics import of described outlet interchanger II 20 is connected through pipeline; The cold logistics outlet of described outlet interchanger II 20 is connected through pipeline with its top feed mouth of described hydrogenator 17; The bottom discharge mouth of described hydrogenator 17 is connected through pipeline with the hot logistics import of described outlet interchanger II 20; The hot logistics outlet of described outlet interchanger II 20 is connected through pipeline with the opening for feed of described the second gas-liquid separator.
As preferred embodiment a kind of, its top feed mouth of described hydrogenator 17 is connected with the well heater 19 that goes into operation; The described well heater 19 that goes into operation is provided with opening for feed and discharge port; The cold logistics outlet of described outlet interchanger II 20 with described in the go into operation opening for feed of well heater 19 through pipeline, be connected; The discharge port of the described well heater that goes into operation is connected through pipeline with its top feed mouth of described hydrogenator 17.
As preferred embodiment a kind of, described hydrogenator 17 is externally connected with drum II 18; Described drum II 18 is provided with refrigerant import, refrigerant exit, liquid-vapor mixture import and vapour outlet; The refrigerant import of described drum II 18 is connected through pipeline with refrigerant raw material pipeline; The refrigerant exit of described drum II 18 is connected through pipeline with the bottom refrigerant import of described hydrogenator 17; The top refrigerant exit of described hydrogenator 17 is connected through pipeline with the liquid-vapor mixture import of described drum II 18; The vapour outlet of described drum II 18 is connected through pipeline with vapor-recovery system out-of-bounds.
As preferred embodiment a kind of, described the second gas-liquid separator comprises high-pressure gas-liquid separator 21 and low-pressure gas-liquid separator 26; Described high-pressure gas-liquid separator 21 is provided with opening for feed, pneumatic outlet and liquid exit; Described low-pressure gas-liquid separator 26 is provided with opening for feed, pneumatic outlet and liquid exit; The bottom discharge mouth of described hydrogenator 17 is connected through pipeline with the opening for feed of described high-pressure gas-liquid separator 21; The pneumatic outlet of described high-pressure gas-liquid separator 21 is provided with branch outlet K and branch outlet L, branch outlet K with described in add Recycle hydrogen compressor 25 import through pipeline, be connected, branch outlet L is connected through pipeline with the opening for feed of described low-pressure gas-liquid separator 26; The liquid exit of described high-pressure gas-liquid separator 21 is connected through pipeline with the middle part opening for feed of described method separation tower 22; The pneumatic outlet of described low-pressure gas-liquid separator 26 is connected through pipeline with the opening for feed of described membrane separation apparatus 28; The liquid exit of described low-pressure gas-liquid separator 26 is connected through pipeline with the middle part opening for feed of described method separation tower 22.
As preferred embodiment a kind of, before the opening for feed of described membrane separation apparatus 28, be provided with methyl alcohol tourie 27; Described methyl alcohol tourie 27 is provided with opening for feed and clean gas outlet; The top non-condensable gas outlet of the pneumatic outlet of described low-pressure gas-liquid separator 26 and described method separation tower 22 is connected through pipeline with the opening for feed of described methyl alcohol tourie 27; The clean gas outlet of described methyl alcohol tourie 27 is connected through pipeline with the opening for feed of described membrane separation apparatus 28.
Described oxonation device 1 can be plate-type reactor, tubular reactor or tubular type-board-like compound reactor;
As preferred embodiment a kind of, described oxonation device 1 is board-like fixed bed oxonation device;
Described board-like fixed bed oxonation Qi center is provided with plate groups lock chamber, in described plate groups lock chamber, is provided with plate groups, and described plate groups lock chamber is also provided with bottom inlet and top exit; The outer wall of described plate groups lock chamber is provided with beds between the inwall of board-like fixed bed oxonation device; In beds, be filled with oxonation catalyzer, described beds is also provided with top entrance and outlet at bottom; Bottom at described board-like fixed bed oxonation device, the bottom refrigerant import of described board-like fixed bed oxonation device is connected through pipeline with the bottom inlet of described plate groups lock chamber, and the outlet at bottom of described beds is connected through pipeline with the bottom discharge mouth of described board-like fixed bed oxonation device; Top at described board-like fixed bed oxonation device, the its top feed mouth of described board-like fixed bed oxonation device is connected through pipeline with the top entrance of described beds, and the top exit of described plate groups lock chamber is connected through pipeline with the top refrigerant exit of described board-like fixed bed oxonation device.
As preferred embodiment a kind of, described esterification reaction tower 9 is packing tower;
As a kind of embodiment being more preferably, described esterification reaction tower 9 is for have column plate-filler mixing column of column plate part and filler filling part simultaneously.
As preferred embodiment a kind of, described Methanol Wash Column 7, methanol rectifying tower 5, methanol distillation column 11, NO recovery tower 13, MN recovery tower 15, DMO rectifying tower 6 and nitric acid concentration tower 12 are packing tower, tray column or bubble-plate column.
As preferred embodiment a kind of, the filler loading in described packing tower is dumped packing or High Efficient Standard Packing; Described dumped packing be shaped as the shape of a saddle, Raschig ring, Pall ring, wheel shape, rectangular saddle ring, spherical or column; Described High Efficient Standard Packing is ripple packing, grid packing, Impulse packing.。
Described hydrogenation plate-type reactor 17 can be plate-type reactor, tubular reactor or tubular type-board-like compound reactor;
As preferred embodiment a kind of, described hydrogenator 17 is board-like fixed bed hydrogenation reactor;
The center of described board-like fixed bed hydrogenation reactor is provided with plate groups lock chamber, in described plate groups lock chamber, is provided with plate groups, and described plate groups lock chamber is also provided with bottom inlet and top exit; The outer wall of described plate groups lock chamber is provided with beds between the inwall of board-like fixed bed hydrogenation reactor; In described beds, be filled with catalyst for hydrogenation, described beds is also provided with top entrance and outlet at bottom; Bottom at described board-like fixed bed hydrogenation reactor, the bottom refrigerant import of described board-like fixed bed hydrogenation reactor is connected through pipeline with the bottom inlet of described plate groups lock chamber, and the outlet at bottom of described beds is connected through pipeline with the bottom discharge mouth of described board-like fixed bed hydrogenation reactor; Top at described board-like fixed bed hydrogenation reactor, the its top feed mouth of described board-like fixed bed hydrogenation reactor is connected through pipeline with the top entrance of described beds, and the top exit of described plate groups lock chamber is connected through pipeline with the top refrigerant exit of described board-like fixed bed hydrogenation reactor.
As preferred embodiment a kind of, described membrane separation apparatus 28 is in parallel or be connected in series and form by 1～100 hollow fiber film assembly.
As shown in Figure 1 and Figure 2, the technical process that a kind of industrial synthetic gas pressure carbonylation provided by the present invention is produced dimethyl oxalate Hydrogenation ethylene glycol is as follows:
From the NO of pipeline 18, from the fresh methanol of pipeline 26 and the O of minute 2～8 tunnel chargings
2in esterification reaction tower 9, carry out gas-liquid counter current contact esterification occurs, the MN gas mixture that tower top generates converges and by pipeline 24, enters dehydration tower 10 and carry out processed through pipeline 23 with from the recovery gas phase of the pressure-variable adsorption tank of pipeline 39, the dry gas after dehydration through pipeline 25 with from the CO of pipeline 1 and the N of pipeline 2
2after mixing, as oxonation unstripped gas, enter pipeline 3.Tower reactor in esterification reaction tower 9 is the acid waste liquid that contains a large amount of methyl alcohol, except being back to esterification reaction tower 9 by a certain amount of by pipeline 20, all the other acid waste liquids by pipeline 21 with from the methyl alcohol acid waste liquid of pipeline 33, enter methanol distillation column 11 simultaneously and carry out Methanol Recovery; The methyl alcohol light constituent that methanol distillation column 11 tower tops produce is shunted after piping 28, except a part is entered in MN recovery tower 15 and is done washings by pipeline 29, other parts are with the fresh methanol from pipeline 26, the alcohol source by pipeline 22 as esterification reaction tower 9; The acid-bearing wastewater that methanol distillation column 11 tower reactors produce enters nitric acid concentration tower 12 by pipeline 27 and carries out nitric acid concentrate.
From the oxonation raw material of pipeline 3 through outlet interchanger I 3 with from the oxonation product heat exchange of oxonation device 1 bottom discharge, from the top of oxonation device 1, enter beds and carry out oxonation; From the Purified Water outside system, by pipeline 8, enter in drum I 2 simultaneously, refrigerant in drum I 2 from oxonation device 1 bottom, enters plate groups lock chamber by pipeline 9 and beds carries out heat exchange, shift out the heat that reaction produces, refrigerant after heating is liquid-vapor mixture, from the Base top contact of oxonation device 1, enter drum I 2 and carry out gas-liquid separation, the low-pressure saturated steam of generation enters out-of-bounds low-pressure steam recovery system by pipeline 7 and recycles.Oxonation product enters the first gas-liquid separator 4 gas-liquid separation occurs after 3 heat exchange of outlet interchanger I, the gaseous component that contains most of DMC (methylcarbonate) enters Methanol Wash Column 7 through pipeline 11, and with recovery methyl alcohol counter current contact from pipeline 57; The methyl alcohol washing lotion that the first gas-liquid separator 4 tower reactor DMO heavy constituents contain MN (methyl nitrite), DMC and DMO (dimethyl oxalate) in pipeline 10 and Methanol Wash Column 7 tower reactors enters methanol rectifying tower 5 through pipeline 12, two bursts of logistics counter current contact, carry out extracting and separating; The gas phase light constituent major part of Methanol Wash Column 7 tower tops enters esterification reaction tower 9 recycles by carbonylation recycle compressor 8 through pipeline 17, and small part enters NO recovery tower 13 as the venting of speeding through piping 32 and recycles; The methyl alcohol of methanol rectifying tower 5 recovered overhead and methyl nitrite mixture are circulated to esterification reaction tower 9 recyclings by pipeline 14, and tower reactor heavy constituent enters DMO rectifying tower 6 by pipeline 13; DMO rectifying tower 6 tower tops obtain DMC product, and tower reactor dimethyl oxalate component enters pipeline 15 as the raw material of hydrogenation reaction.
Nitric acid concentration tower 12 tower tops are mainly acid-bearing wastewater and are drained into and outside battery limit (BL), carried out environmental protection treatment by pipeline 30, at the bottom of tower the concentrated nitric acid of concentrate through pipeline 31 enter NO recovery tower 13 as acid source and from the recovery methyl alcohol of pipeline 57 with from pipeline 32 speed exit counter current contact generation esterification regenerative response to reclaim the NO speeding in venting; The nitric acid waste that NO recovery tower 13 tower reactors contain methyl alcohol enters into methanol distillation column 11 recovery that circulates by pipeline 33, and the light constituent containing MN that tower top generates enters MN recovery tower 15 after compressor 14 superchargings.In MN recovery tower 15 with from the recovery methyl alcohol counter current contact of pipeline 29, wash away MN wherein, and through piping 36, enter esterification reaction tower 9 from tower reactor, top gaseous phase light constituent enters pressure-variable adsorption tank 16 by pipeline 37, through pressure-variable adsorption, removes CO
2after containing the gas mixture of CO, by pipeline 39, enter dehydration tower 10, and the CO removing
2gas can be used as to be disposed to outside battery limit (BL) and processes.
From the plant hydrogen of pipeline 54 with from the circulation gas of pipeline 53, mix after adding Recycle hydrogen compressor 25 pressurizations and enter pipeline 55, then with dimethyl oxalate component from pipeline 15 and mix as hydrogenation reaction raw material from the recover hydrogen of pipeline 68, from pipeline 40, enter outlet interchanger II 20, carry out heat exchange with the hydrogenation reaction product of drawing from hydrogenator 17 bottoms, then from the tower top of hydrogenator 17, enter beds and carry out catalytic hydrogenation reaction; Meanwhile, from the Purified Water outside system, by pipeline 48, enter drum II 18, refrigerant in drum II 18 from the bottom of hydrogenator 17, enters plate groups lock chamber by pipeline 49 and beds carries out heat exchange, shift out the heat that reaction produces, refrigerant after heating is liquid-vapor mixture, from the Base top contact of hydrogenator 17, enter drum II 18 and carry out gas-liquid separation, the low-pressure saturated steam of generation enters out-of-bounds low-pressure steam recovery system by pipeline 47 and recycles.Hydrogenation reaction product enters high-pressure gas-liquid separator 21 from pipeline 44 and carries out gas-liquid separation after heat exchange, gas phase part is most of after piping 51 to enter pipeline 53 as circulation gas and circulates, and remains a part of gas and by pipeline 52, enters low-pressure gas-liquid separator 26 and carry out gas-liquid separation; Liquid Phase Methanol in low-pressure gas-liquid separator 26 flows out by pipeline 64, gas phase part enters methyl alcohol tourie 27 by pipeline 66 after converging by pipeline 65 with from the non-condensable gas of pipeline 58 and carries out further methanol removal, gas after de-liquid enters membrane separation apparatus 28 from pipeline 67, through the recycling of film system, except sub-fraction CO
2, CO and CH
4deng condensing not, from pipeline 69, speed to put most of H reclaiming
2after supercharging, enter pipeline 68 recycles.
The thick product of liquid phase ethylene glycol of separating from high-pressure gas-liquid separator 21 flows out from pipeline 50, through with from pipeline 64 Liquid Phase Methanols, converge after enter method separation tower 22; Method separation tower 22 tower tops are speeded to put a certain amount of not condensing by pipeline 58 and are reclaimed, and tower top liquid phase light constituent enters pipeline 57, and the tower bottoms piping 56 that communicates enters and in light constituent rectifying tower 23, carries out separation; The light constituents such as light constituent rectifying tower 23 tower top light constituent ethanol, methyl glycolate enter alcohol retrieving arrangement outside battery limit (BL) by pipeline 60 and reclaim, tower reactor polyol blends is entered in ethylene glycol product tower 24 and is further purified by pipeline 59, wherein mainly containing 1, the mixing light constituent of 2-BDO, ethylene glycol further recycles by pipeline 63, the ethylene glycol of tower body top side line output is by pipeline 62 as product extraction, and tower reactor is that the mixture that contains a small amount of ethylene glycol and ethylene glycol polycondensate enters outside battery limit (BL) and processes.
The driving initial stage, the use 19 pairs of hydrogenation reaction raw materials of well heater that go into operation heat, thermal source adopts low-pressure steam, enters pipeline 45 through the well heater 19 that goes into operation, be preheated to bed temperature in and by pipeline 46 and pipeline 42, from the top of hydrogenator 17, enter beds and carry out hydrogenation reaction from the hydrogenating materials of pipeline 40.
Utilize above-mentioned technical process to carry out industrial example as follows:
Tower top light constituent from Methanol Wash Column (forms: MN:5.22v%, CO:22.12v%, N
2: 58.5v%, NO:11.14v%, CO
2: 0.63v%, methyl alcohol 1.57v%, other: 0.82v%) and after mixing from NO outside battery limit (BL), enter esterification reaction tower 9 (theoretical plate number 25, tower plate structure is packing tower for internal diameter 50mm, height 2600mm) from the 25th column plate charging, O
2divide 3 tunnels from the 22nd, the 23rd and the 25th block of column plate, to enter esterification reaction tower 9 respectively, with the methyl alcohol reclaiming from methanol rectifying tower 5 of fresh methanol from the 1st column plate charging of tower top and the recovery methyl alcohol mixed liquor from methanol distillation column 11, the 5th charging and methyl nitrite mixture and from the alcoholic solution containing methyl nitrite of MN recovery tower 15 tower reactors and carry out gas-liquid counter current from the tower reactor phegma of the 10th charging in tower and contact, there is esterification (O wherein
2, NO and methyl alcohol mole proportioning be: 0.1:0.6:50).Esterification reaction tower 9 tower top temperatures are 50 ℃, and tower reactor temperature is 93 ℃, and reaction zone temperature is 70 ± 10 ℃, and reaction pressure is 2MPa.Esterification reaction tower 9 tower reactor dischargings (forming: methyl alcohol: 71.8wt%, MN:8.0wt%, other heavy constituent 20.2wt% such as the acid that reaction generates and water) enter methanol distillation column 11 recyclings after extraction.Esterification reaction tower 9 top gaseous phase components (form: MN:10.05v%, CO:26.42v%, N
2: 55.88v%, NO:5.2v%, CO
2: 0.60v%, methyl alcohol 1.57v%, other: 0.28v%) enter dehydration tower 10 dehydrations.After the dehydration of dehydration tower 10 (sorbent material is 4A molecular sieve, service temperature: 43 ℃: pressure: 1.9MPa, two mole sieve drier A and mole sieve drier B alternate run and regeneration), obtain the dry gas that water content is 60ppm.
The useless alcohol liquid of acid that contains of esterification reaction tower 9 tower reactors enters methanol distillation column 11 (internal diameter 50mm, height 2100mm, 20 of theoretical plate numbers, in-built High Efficient Standard Packing, 120 ℃ of tower top temperatures, column bottom temperature is 140 ℃, tower top pressure 0.7MPa, the reflux ratio 1.2 of tower top light constituent, tower top is the light constituent (component: methyl alcohol: 90wt% containing methyl alcohol, MN:8wt%, H
2o:2wt%) part (accounting 75wt%) is converged with supplementary fresh methanol, enters the top of esterification reaction tower 9, and residue is as the washings in MN recovery tower 15; Methanol distillation column 11 tower reactor acid-bearing wastewaters enter nitric acid concentration tower 12 and carry out nitric acid concentrate.
Oxonation device 1 (height is 2000mm for board-like fixed-bed reactor, internal diameter: 320mm), center is provided with plate groups lock chamber, is provided with 3 groups of plates in plate groups lock chamber, every group of 3 plates; The outer wall of plate groups lock chamber is provided with beds between oxonation device 1 inwall, interior filling carbonylation reaction under high pressure catalyzer (Shanghai Wuzheng Engineering Co., Ltd. commercial catalyst, catalyzer trade names are DMO-0701T).From the dry gas of dehydration tower 10 and dehydrogenation as oxonation raw material, process postindustrial level CO (99v%) and mix by after outlet interchanger I 3 and the heat exchange of oxonation product as the nitrogen of inertia source of the gas, be preheated to 95 ℃, first from the top of oxonation device 1, enter, then through radial flow mode, enter beds and carry out oxonation (130 ℃ of beds hot(test)-spot temperatures, reaction pressure is 1.8MPa, and gas hourly space velocity is 10000h
-1); Carbonyl compounds enters the first gas-liquid separator 4 after then entering 3 heat exchange of outlet interchanger, at this, carries out gas-liquid separation.
Described oxonation device 1 plate groups lock chamber refrigerant is water medium.From the Purified Water outside system, enter drum I 2 and supplement water inlet, water in drum I enters plate groups lock chamber and beds in oxonation device 1 and carries out heat exchange, shift out the heat that reaction produces, water after heating is liquid-vapor mixture, enter drum and carry out gas-liquid separation, the low-pressure saturated steam of generation is sent to low-pressure steam pipe network outside battery limit (BL) and recycles.
The liquid phase that the first gas-liquid separator 4 is drawn (methyl alcohol: 1.16wt%, DMC:0.45wt%, DMO:97.6wt%, other 0.79wt%) enters and in methanol rectifying tower 5, carries out separation as extraction agent; The gas mixture phase component containing DMC of drawing enters Methanol Wash Column 7 (internal diameter: 50mm, height is 3200mm, number of theoretical plate is 30, in-built High Efficient Standard Packing, tower top temperature is 28.1 ℃, tower reactor temperature is 39.8 ℃, tower top pressure is 1.5MPa) by reclaiming methyl alcohol (content 99.9wt%) counter current contact with method separation tower 22, by the DMC in gas mixture and DMO wash-out, the gas phase light constituent major part at Methanol Wash Column 7 tops enters esterification reaction tower 9 by carbonylation recycle compressor 8, and the oxynitride that oxonation is generated carries out recycle; Small part non-condensable gas (gas accounting 0.5v%) enters NO recovery tower 13 as the venting of speeding and recycles; Methanol Wash Column 7 tower reactor liquid phases enter carries out separation in methanol rectifying tower 5.
Methanol rectifying tower 5 (internal diameter: 50mm, height is 2600mm, extractive distillation column, number of theoretical plate is 25, in-built High Efficient Standard Packing, and tower top temperature is 73.12 ℃, tower reactor temperature is 185.0 ℃, tower top pressure is 0.1MPa) light constituent (methyl alcohol: 88.2wt%, MN:11.8wt%) of tower top enters esterification reaction tower 9 as one of alcohol source, in tower reactor, contains
The heavy constituent of DMC and DMO enters DMO rectifying tower 6 and carries out separated.
DMO rectifying tower 6 (internal diameter: 50mm, height is 3000mm, number of theoretical plate is 28, in-built High Efficient Standard Packing, 103 ℃ of tower top temperatures, 180 ℃ of tower reactor temperature, atmospheric operation, reflux ratio 50), tower top DMC collects (DMC product purity is 99.41wt%) as product; Tower reactor heavy constituent (DMO purity is 99.9wt%) is all as the raw material of hydrogenation workshop section.
Described nitric acid concentration tower 12 (internal diameter 32mm, height 850mm, 8 of theoretical plate numbers, in-built High Efficient Standard Packing, 64 ℃ of tower top temperatures, tower reactor temperature is 87 ℃, tower top pressure 0.15MPa, reflux ratio 0.05), in, tower top is mainly acid-bearing wastewater and drains into and outside battery limit (BL), carry out environmental protection treatment, tower reactor concentrate produces the concentrated nitric acid that concentration is 68wt%, as the acid source of NO recovery tower 13.
NO recovery tower 13 (internal diameter: 32mm, height is 2100mm, number of theoretical plate is 20, in-built High Efficient Standard Packing, tower top temperature is 50 ℃, and tower reactor temperature is 100 ℃, and tower top pressure is 1.4MPa) in, the described venting of speeding from Methanol Wash Column 7 is from the 20th column plate charging, from the recovery methyl alcohol (99.9wt%) from method separation tower 22 of the 1st column plate charging with from the concentrated nitric acid counter current contact generation esterification regenerative response from nitric acid concentration tower 12 of the 8th column plate charging.HNO in the described venting of speeding in NO, concentrate nitric acid
3, methyl alcohol mol ratio be 1:2.5:20.The tower top light constituent of NO recovery tower 13 (forms: CO:21.1v%, CO
2: 0.6v%, MN:20.8v%, N
2: 55.7v%, methyl alcohol: 1.8v%) enter MN recovery tower 15 through compressor 14 superchargings; The 3rd block of column plate that NO recovery tower 13 tower reactor heavy constituents enter (forming: methyl alcohol 71.8wt%, other heavy constituent 28.2wt% such as the acid that reaction generates and water) methanol distillation column 11 reclaims.
MN recovery tower 15 (internal diameter: 32mm, height is 3200mm, number of theoretical plate is 30, in-built High Efficient Standard Packing, tower top temperature is 30.8 ℃, tower reactor temperature is 41.3 ℃, tower top pressure is 2MPa) in charging with from the recovery methyl alcohol counter current contact that comes from methanol distillation column 11 of the 1st column plate charging, absorb a large amount of MN in air inlet, remaining gas (forms: CO:27.3v%, CO
2: 0.8v%, N
2: 71.9v%) from tower top, enter pressure-variable adsorption tank 16, the material in tower reactor (forms: the 5th block of column plate that methyl alcohol: 79.3mol%, MN:20.7mol%) enters esterification reaction tower 9 recycled.The top gaseous phase of described MN recovery tower 15 is through pressure-variable adsorption tank 16 pressure-variable adsorptions, purified gas (N
2: 72v%, CO:28v%) enter after dehydration tower 10 is processed and enter oxonation device 1, and 0.95v% gas (is formed: CO
2for 99.8v%) be disposed to outside battery limit (BL) and process.
Hydrogenator 17 (height is 900mm for board-like fixed bed hydrogenation reactor, internal diameter: 325mm), center is provided with plate groups lock chamber, is provided with three groups of plates in plate groups lock chamber, every group of 3 plates; The outer wall of plate groups lock chamber is provided with beds between hydrogenator inwall, the in-built catalyst for hydrogenation of filling out: Shanghai Wuzheng Engineering Co., Ltd. commercial catalyst, catalyzer trade names are MEG-801T).
Technical grade H
2(purity is 99.9v%) and (form: hydrogen 96v% from the circulation gas of high-pressure gas-liquid separator 21, methane 0.05v%, nitrogen 0.02v%, carbon monoxide 0.02v%, methyl alcohol 3v%, other 0.91v%) the outlet interchanger II 20 that enters hydrogenation plate-type reactor 17 after converging with dimethyl oxalate (99.9%wt) from DMO rectifying tower 6 tower reactors after adding Recycle hydrogen compressor 25 compression is preheated to after 175 ℃, first from the top of hydrogenator 17, enter, then through radial flow mode, enter beds and carry out hydrogenation reaction (190 ℃ of beds hot(test)-spot temperatures, reaction pressure is 3.0MPa, liquid hourly space velocity is 2.8Kg/Kg.h), hydrogenation products enters high-pressure gas-liquid separator 21 from 20 heat exchange of the laggard inlet/outlet interchanger of bottom discharge II, at this, carries out gas-liquid separation.
Go into operation the initial stage, enter the well heater 19 that goes into operation carry out preheating through the material of outlet interchanger II 20, the gas after preheating reaches and enters beds after beds temperature in and carry out hydrogenation reaction as unstripped gas.
Hydrogenator 17 plate groups lock chamber refrigerants are water medium.From the Purified Water outside system, enter drum II 18 and supplement water inlet, water in drum II 18 enters plate groups lock chamber and beds in hydrogenator 17 and carries out heat exchange, shift out the heat that reaction produces, water after heating is liquid-vapor mixture, enter drum II and carry out gas-liquid separation, the low-pressure saturated steam of generation is sent to low-pressure steam pipe network outside battery limit (BL) and recycles.
Hydrogenation products is after high-pressure gas-liquid separator 21 separation, gas phase major part enters and adds Recycle hydrogen compressor 25 as circulation gas, residue non-condensable gas (gas accounting 1.2v%) enters low-pressure gas-liquid separator 26, the liquid phase that high-pressure gas-liquid separator 21 is drawn (methyl alcohol: 50.1wt%, ethylene glycol: 48.55wt%, methyl glycolate: 0.06wt%, ethanol: 0.39wt%, BDO:0.12wt%, other 0.78wt%) enter and in method separation tower 22, carry out separation.The liquid phase of low-pressure gas-liquid separator 26 separation enters carries out separation in method separation tower 22, gas phase is through methyl alcohol tourie 27 (internal diameter 160mm, height 900mm) after further methanol removal, gas phase wherein (forms: hydrogen 97v%, methane 0.15v%, nitrogen 0.06v%, carbon monoxide 0.27v%, other 2.52v%) enter membrane separation apparatus 28 and recycle.Hydrogen after membrane separation apparatus separation (purity is 99.9v%) enters hydrogenation plate-type reactor 17 after the preheating of outlet interchanger II, only has the non-condensable gases such as small part methane rich to discharge and out-of-bounds reclaim again as the venting of speeding.
Method separation tower 22 (internal diameter: 50mm, height is 2600mm, number of theoretical plate is 25, in-built High Efficient Standard Packing, tower top temperature is 50.82 ℃, tower reactor temperature is 171 ℃, absolute pressure of top of the tower is 90kPa) in, material is the 12nd column plate place charging, tower top non-condensable gas enters after methyl alcohol tourie 27 is processed and enters membrane separation apparatus 28, trim the top of column, than 1.6, enters respectively Methanol Wash Column 7 and NO recovery tower 13 after tower top discharging (methyl alcohol of 99.9wt%, other low boiling point component of 0.1wt%) extraction; Method separation tower 22 tower reactor heavy constituents (forming: 96wt% ethylene glycol, 0.12wt% methyl glycolate, 2.68wt%1.2-BDO, 0.8wt% ethanol, other component of 0.4wt%) enter light constituent rectifying tower 23.
Light constituent rectifying tower 23 (internal diameter: 50mm, height is 4000mm, number of theoretical plate is 40, in-built High Efficient Standard Packing, 83.8 ℃ of tower top temperatures, 146.9 ℃ of tower reactor temperature, absolute pressure of top of the tower 16kPa, trim the top of column is than 50), tower top is drawn the thick product of ethanol (98wt% ethanol, 2wt% methyl glycolate) and is delivered to and outside battery limit (BL), carry out collection and treatment; (97.9wt% ethylene glycol, 2.1wt%1.2-BDO) in ethylene glycol product tower 24 for tower reactor heavy constituent.
Ethylene glycol product tower 24 (internal diameter 50mm, height 6500mm, 60 of tower number of theoretical plates, in-built High Efficient Standard Packing, 130 ℃ of tower top temperatures, tower reactor temperature is 170.1 ℃, absolute pressure of top of the tower 5kPa) in, trim the top of column is than 98, and (component: 1,2-BDO is 19.79wt% to overhead extraction; Ethylene glycol is 80wt%, other 0.21wt%) to battery limit (BL), as byproduct, reclaim, tower reactor carries out processing outside battery limit (BL) for containing a small amount of ethylene glycol and ethylene glycol polycondensate, and the 5th column plate place of ethylene glycol product tower 24 tower body side line be extraction the finished product ethylene glycol (content is 99.99wt%).
Above-described embodiment is exemplary illustration principle of the present invention and effect only, but not for limiting the present invention.Any person skilled in the art scholar all can, under spirit of the present invention and category, modify or change above-described embodiment.Therefore, in all affiliated technical fields, have and conventionally know that the knowledgeable, not departing from all equivalence modifications that complete under disclosed spirit and technological thought or changing, must be contained by claim of the present invention.
Claims (42)
1. industrial synthetic gas pressure carbonylation is produced a technique for dimethyl oxalate Hydrogenation ethylene glycol, specifically comprises the following steps:
(1) in esterification reaction tower (9), pass into technical grade NO, O
2carry out esterification with methyl alcohol; Esterification reaction tower (9) tower top methyl nitrite gas mixture passes into oxonation device (1) and carries out oxonation; Esterification reaction tower (9) tower reactor acidity alcohol solution is partly refluxed to esterification reaction tower (9), and part passes into methanol distillation column (11); The methyl alcohol of methanol distillation column (11) recovered overhead is partly circulated to esterification reaction tower (9) recycle, and all the other enter MN recovery tower (15) as washings; Methanol distillation column (11) tower reactor spent acid enters nitric acid concentration tower (12) and carries out concentration;
(2) from methyl nitrite and technical grade CO, the N of esterification reaction tower
2charging enters oxonation device (1), under oxonation catalyzer exists, oxonation occurs; The temperature of oxonation is 30～200 ℃, and reaction pressure is 1～10MPa, gas hourly space velocity 3000～30000h
-1;
(3) carbonyl compounds enters the first gas-liquid separator (4) generation gas-liquid separation, and gas phase enters Methanol Wash Column (7), and liquid phase enters methanol rectifying tower (5); Methanol Wash Column (7) top gaseous phase component is partly circulated to esterification reaction tower (9), and part enters NO recovery tower (13) as the venting of speeding and recycles; Methanol Wash Column (7) tower bottoms phase component enters methanol rectifying tower (5) and carries out rectifying separation; The methyl alcohol of methanol rectifying tower (5) recovered overhead and methyl nitrite mixture are circulated to esterification reaction tower (9) recycling, and tower reactor heavy constituent enters DMO rectifying tower (6); DMO rectifying tower (6) tower top obtains DMC product, and tower reactor dimethyl oxalate component enters hydrogenator (17) and carries out hydrogenation reaction;
(4) from the spent acid of methanol distillation column (11) after nitric acid concentration tower (12) concentrate is 10～68wt% to concentration of nitric acid, be circulated to NO recovery tower (13); In NO recovery tower (13), concentrated nitric acid, methyl alcohol and esterification regenerative response occurs from the venting of speeding of Methanol Wash Column (7); NO recovery tower (13) top gaseous phase light constituent enters MN recovery tower (15), and the nitric acid waste that contains methyl alcohol that tower reactor produces is circulated to methanol distillation column (11) and further recycles; In MN recovery tower (15), gas-phase feed, after reclaiming methanol wash, enters pressure-variable adsorption tank (16), and MN recovery tower (15) tower reactor enters esterification reaction tower (9) containing the alcoholic solution circulation of methyl nitrite; The isolated CO of pressure-variable adsorption tank (16)
2be disposed to out-of-bounds and process, the N of recovery
2enter oxonation device (1) recycle with CO purified gas;
(5) from the dimethyl oxalate component of DMO rectifying tower (6) tower reactor, enter hydrogenator (17) with after plant hydrogen after adding Recycle hydrogen compressor (25) pressurization mixes, under hydrogenation catalyst exists, hydrogenation reaction methanol and ethylene glycol etc.; Hydrogenation reaction temperature is 160～320 ℃, and reaction pressure is 1～10MP, and liquid hourly space velocity is 1～3Kg/Kg.h;
(6) hydrogenation products enters the second gas-liquid separator generation gas-liquid separation, gas phase part through described in add after Recycle hydrogen compressor (25) pressurizes and be circulated to hydrogenator (17), part enters membrane separation apparatus (28) and return to hydrogenator (17) recycle after recycling, and liquid phase enters ethylene glycol product tower (24) separation and obtains ethylene glycol product.
2. the technique that a kind of industrial synthetic gas pressure carbonylation as claimed in claim 1 is produced dimethyl oxalate Hydrogenation ethylene glycol, is characterized in that, also comprises any one in following characteristics or multinomial:
(1) described oxonation device (1) is externally connected with dehydration tower (10); The gas phase reclaiming through pressure-variable adsorption tank (16) and removing after moisture through described dehydration tower (10) from the methyl nitrite gas mixture of esterification reaction tower (9) tower top, then enter in oxonation device (1) and carry out oxonation;
(2) described oxonation device (1) is externally connected with outlet interchanger I (3); Technical grade CO, N
2and after described outlet interchanger I (3) and the oxonation product heat exchange from oxonation device (1), enter again in oxonation device (1) and carry out oxonation as oxonation raw material from the dry gas of dehydration tower (10);
(3) the part gaseous component from Methanol Wash Column (7) tower top enters esterification reaction tower (9) after carbonylation recycle compressor (8) pressurization again;
(4) described hydrogenator (17) is externally connected with outlet interchanger II (20); From the dimethyl oxalate component of DMO rectifying tower (6), enter again in hydrogenator (17) and carry out hydrogenation reaction after described outlet interchanger II (20) and hydrogenation products heat exchange from hydrogenator (17) as hydrogenation reaction raw material from the plant hydrogen of pressurized circulation compressor and circulation gas and from the recovery gas of membrane separation apparatus (28);
(5) described NO recovery tower (13) top gaseous phase light constituent enters MN recovery tower (15) after compressor (14) compression supercharging again;
(6) first the liquid phase of described the second gas-liquid separator separates enters method separation tower (22); The non-condensable gas of method separation tower (22) recovered overhead enters described membrane separation apparatus (28), the top that the liquid phase light constituents such as methyl alcohol of method separation tower (22) recovered overhead partly enter described Methanol Wash Column (7) is as washings, and part enters NO recovery tower (13); Method separation tower (22) tower reactor liquid phase heavy constituent enters further separating-purifying of light constituent rectifying tower (23); Light constituent rectifying tower (23) tower top light constituent enters out-of-bounds alcohol retrieving arrangement recycling; Light constituent rectifying tower (23) tower reactor heavy constituent enters described ethylene glycol product tower (24); Ethylene glycol product tower (24) tower top light constituent enters out-of-bounds 1,2-BDO recycling and processing device further recycles, ethylene glycol product tower (24) tower reactor heavy constituent enters out-of-bounds recycling and processing device and carries out subsequent disposal, and the top side line of ethylene glycol product tower (24) is drawn ethylene glycol product.
3. the technique that a kind of industrial synthetic gas pressure carbonylation as claimed in claim 2 is produced dimethyl oxalate Hydrogenation ethylene glycol, is characterized in that, described dehydration tower is comprised of mole sieve drier A and the mole sieve drier B of two alternate runs and regeneration; In mole sieve drier A and mole sieve drier B, be filled with sorbent material; Described sorbent material is selected from 3A molecular sieve, 4A molecular sieve, 5A molecular sieve, 9A molecular sieve and calcium oxide; The service temperature of described mole sieve drier A and mole sieve drier B is 40～260 ℃, and pressure is 1～10MPa; Through dehydration tower (10), process and obtain dry gas, moisture content 0.1～100ppm in dry gas.
4. the technique that a kind of industrial synthetic gas pressure carbonylation as claimed in claim 2 is produced dimethyl oxalate Hydrogenation ethylene glycol, is characterized in that, described the second gas-liquid separator comprises high-pressure gas-liquid separator (21) and low-pressure gas-liquid separator (26); Through the isolated gas phase of high-pressure gas-liquid separator (21), add Recycle hydrogen compressor (25) described in partly entering, part enters described low-pressure gas-liquid separator (26); The isolated liquid phase of high-pressure gas-liquid separator (21) enters described method separation tower (22); Through the isolated gas phase of described low-pressure gas-liquid separator (26), enter described membrane separation apparatus (28), through the isolated liquid phase of low-pressure gas-liquid separator (26), enter described method separation tower (22).
5. the technique that a kind of industrial synthetic gas pressure carbonylation as claimed in claim 4 is produced dimethyl oxalate Hydrogenation ethylene glycol, is characterized in that, in the isolated gas phase of described high-pressure gas-liquid separator, wherein 0.1～10v% enters low-pressure gas-liquid separator.
6. the technique that a kind of industrial synthetic gas pressure carbonylation as claimed in claim 4 is produced dimethyl oxalate Hydrogenation ethylene glycol, it is characterized in that, through the isolated gas phase of described low-pressure gas-liquid separator (26) and from the non-condensable gas of described method separation tower (22) tower top, after methyl alcohol tourie (27) absorbs methyl alcohol, enter again described membrane separation apparatus (28).
7. the technique that a kind of industrial synthetic gas pressure carbonylation as claimed in claim 1 is produced dimethyl oxalate Hydrogenation ethylene glycol, is characterized in that, also comprises any one in following characteristics or two:
(1) described oxonation device is plate-type reactor, tubular reactor or tubular type-board-like compound reactor;
(2) described hydrogenator is plate-type reactor, tubular reactor or tubular type-board-like compound reactor.
8. the technique that a kind of industrial synthetic gas pressure carbonylation as claimed in claim 7 is produced dimethyl oxalate Hydrogenation ethylene glycol, is characterized in that, also comprises any one in following characteristics or two:
(1) described oxonation device (1) is board-like fixed bed oxonation device; Described board-like fixed bed oxonation Qi center is provided with plate groups lock chamber, in described plate groups lock chamber, is provided with plate groups; The outer wall of described plate groups lock chamber is provided with beds between the inwall of board-like fixed bed oxonation device; In beds, be filled with oxonation catalyzer; Oxonation raw material reaches after beds inlet temperature, enters oxonation occurs in beds from the top of described board-like fixed bed oxonation device; The refrigerant of introducing from outside enters plate groups lock chamber from the bottom of board-like fixed bed oxonation device, and from the Base top contact of described board-like fixed bed oxonation device, counter-current process carries out the reaction heat that oxonation is taken away in heat exchange; Carbonyl compounds from beds bottom is drawn from the bottom of board-like fixed bed oxonation device;
(2) described hydrogenator (17) is board-like fixed bed hydrogenation reactor; The center of described board-like fixed bed hydrogenation reactor is provided with plate groups lock chamber, in described plate groups lock chamber, is provided with plate groups; The outer wall of described plate groups lock chamber is provided with beds between the inwall of board-like fixed bed hydrogenation reactor; In described beds, be filled with catalyst for hydrogenation; Hydrogenation reaction raw material reaches after beds inlet temperature, enters hydrogenation reaction occurs in beds from the top of described board-like fixed bed hydrogenation reactor; The refrigerant of introducing from outside enters plate groups lock chamber from the bottom of board-like fixed bed hydrogenation reactor, and from the Base top contact of described board-like fixed bed hydrogenation reactor, counter-current process carries out the reaction heat that hydrogenation reaction is taken away in heat exchange; Hydrogenation products from beds bottom is drawn from the bottom of board-like fixed bed hydrogenation reactor.
9. the technique that a kind of industrial synthetic gas pressure carbonylation as claimed in claim 8 is produced dimethyl oxalate Hydrogenation ethylene glycol, is characterized in that, described board-like fixed bed oxonation device is externally connected with drum I (2); The refrigerant of introducing from outside enters drum I (2), and the refrigerant in drum I (2) enters in the plate groups lock chamber of board-like fixed bed oxonation device and carries out heat exchange with beds, shifts out reaction heat; Refrigerant after heating is liquid-vapor mixture, enters drum I (2) and carries out gas-liquid separation, and the low-pressure saturated steam of generation enters out-of-bounds low-pressure steam recovery system and recycles; Described board-like fixed bed hydrogenation reactor is externally connected with drum II (18); The refrigerant of introducing from outside enters drum II (18), and the refrigerant in drum II (18) enters in the plate groups lock chamber of board-like fixed bed hydrogenation reactor and carries out heat exchange with beds, shifts out reaction heat; Refrigerant after heating is liquid-vapor mixture, enters drum II (18) and carries out gas-liquid separation, and the low-pressure saturated steam of generation enters out-of-bounds low-pressure steam recovery system and recycles.
10. the technique that a kind of industrial synthetic gas pressure carbonylation as claimed in claim 8 is produced dimethyl oxalate Hydrogenation ethylene glycol, is characterized in that, described board-like fixed bed hydrogenation reactor is externally connected with the well heater that goes into operation (19); Go into operation the initial stage, hydrogenation reaction raw material enters the well heater that goes into operation (19) from outlet interchanger II (20) out and carries out preheating, and preheating reaches and enters beds after beds temperature in and carry out hydrogenation reaction; Go into operation the initial stage, described in the well heater (19) that goes into operation provide unique thermal source for the hydrogenation reaction in described board-like fixed bed hydrogenation reactor; The thermal source of the described well heater that goes into operation (19) is low-pressure steam.
The technique that 11. a kind of industrial synthetic gas pressure carbonylations as claimed in claim 1 are produced dimethyl oxalate Hydrogenation ethylene glycol, is characterized in that, the number of theoretical plate of described esterification reaction tower (9) is 20～50; In the charging of described esterification reaction tower (9), described O
2divide 2～8 tunnels respectively from 16th～50 column plate chargings; Described NO and from the top gaseous phase light constituent of Methanol Wash Column (7) from 18th～50 column plate chargings; Described fresh methanol, from the recovery methyl alcohol of methanol distillation column (11) tower top, from the methyl alcohol of the recovered overhead of methanol rectifying tower (5) and methyl nitrite mixture and from the alcoholic solution containing methyl nitrite of MN recovery tower (15) tower reactor from 1st～5 column plate chargings; Esterification reaction tower (9) tower reactor backflow material is from 10th～25 column plate chargings;
In described esterification reaction tower (9), O
2, NO and methyl alcohol molar ratio be 0.01～0.8:0.1～3.2:0.8～50; Described esterification reaction tower (9) tower top temperature is 30～80 ℃, and tower reactor temperature is 50～200 ℃, and reaction zone temperature is 50～160 ℃, and reaction pressure is 0.5～10MPa.
The technique that 12. a kind of industrial synthetic gas pressure carbonylations as claimed in claim 1 are produced dimethyl oxalate Hydrogenation ethylene glycol, it is characterized in that, the tower theoretical plate number of described methanol distillation column (11) is 5～50,40～150 ℃ of tower top temperatures, tower reactor temperature is 60～230 ℃, and tower top pressure is 0.1～2.0MPa; The reflux ratio of described methanol distillation column (11) tower top light constituent is 0.1～3.0; In described methanol distillation column recovered overhead methyl alcohol, the part proportion that circulation enters esterification reaction tower is 10～90wt%.
The technique that 13. a kind of industrial synthetic gas pressure carbonylations as claimed in claim 1 are produced dimethyl oxalate Hydrogenation ethylene glycol, it is characterized in that, the theoretical plate number of described Methanol Wash Column (7) is 10～50, tower top temperature is 15～70 ℃, tower reactor temperature is 10～100 ℃, and tower top pressure is 0.9～10MPa; In described Methanol Wash Column top gaseous phase component, described in speed venting accounting be 0.05～5v%.
The technique that 14. a kind of industrial synthetic gas pressure carbonylations as claimed in claim 1 are produced dimethyl oxalate Hydrogenation ethylene glycol, it is characterized in that, methanol rectifying tower (5) is extractive distillation column, theoretical plate number is 10～60, tower top temperature is 50～150 ℃, tower reactor temperature is 130～250 ℃, and tower top pressure is 0.01～0.5MPa.
The technique that 15. a kind of industrial synthetic gas pressure carbonylations as claimed in claim 1 are produced dimethyl oxalate Hydrogenation ethylene glycol, it is characterized in that, the theoretical plate number of described nitric acid concentration tower (12) is 1～30,30～110 ℃ of tower top temperatures, 60～160 ℃ of tower reactor temperature, tower top pressure 0.01～0.3MPa; The reflux ratio of the tower top light constituent of described nitric acid concentration tower (12) is 0.01～3.
The technique that 16. a kind of industrial synthetic gas pressure carbonylations as claimed in claim 1 are produced dimethyl oxalate Hydrogenation ethylene glycol, it is characterized in that, the theoretical plate number of described NO recovery tower (13) is 5～30, tower top temperature is 30～120 ℃, tower reactor temperature is 50～200 ℃, and tower top pressure is 1～10MPa; Described 5th～30 piece column plate chargings of venting from NO recovery tower (13) of speeding; Described concentrate nitric acid is from 1st～10 column plate chargings of NO recovery tower (13); From the recovery methyl alcohol of method separation tower (22) tower top from 1st～10 column plate chargings; In described NO recovery tower (13), mole proportioning of nitric acid, methyl alcohol and the NO in venting that speeds is 1.1～10:2～100:1～5.
The technique that 17. a kind of industrial synthetic gas pressure carbonylations as claimed in claim 1 are produced dimethyl oxalate Hydrogenation ethylene glycol, it is characterized in that, the theoretical plate number of described MN recovery tower (15) is 10～60, tower top temperature is 0～50 ℃, tower reactor temperature is 0～80 ℃, and reaction pressure is 1～10MPa.
The technique that 18. a kind of industrial synthetic gas pressure carbonylations as claimed in claim 1 are produced dimethyl oxalate Hydrogenation ethylene glycol, it is characterized in that, the theoretical plate number of described DMO rectifying tower (6) is 10～50, tower top temperature is 80～120 ℃, tower reactor temperature is 120～200 ℃, normal pressure or decompression operation; Described DMO rectifying tower (6) tower top light constituent reflux ratio is 0.1～100.
The technique that 19. a kind of industrial synthetic gas pressure carbonylations as claimed in claim 2 are produced dimethyl oxalate Hydrogenation ethylene glycol, it is characterized in that, the theoretical plate number of described method separation tower (22) is 10～40,40～70 ℃ of tower top temperatures, 80～180 ℃ of tower reactor temperature, normal pressure or decompression operation; Described separating methanol column overhead light constituent reflux ratio is 0.1～3.
The technique that 20. a kind of industrial synthetic gas pressure carbonylations as claimed in claim 2 are produced dimethyl oxalate Hydrogenation ethylene glycol, it is characterized in that, the theoretical plate number of described light constituent rectifying tower (23) is 10～60,58～90 ℃ of tower top temperatures, 70～160 ℃ of tower reactor temperature, absolute pressure of top of the tower is 5～50KPa; The tower top light constituent reflux ratio of described light constituent rectifying tower (23) is 1～50.
The technique that 21. a kind of industrial synthetic gas pressure carbonylations as claimed in claim 2 are produced dimethyl oxalate Hydrogenation ethylene glycol, it is characterized in that, the theoretical plate number of described ethylene glycol product tower (24) is 30～100,100～150 ℃ of the temperature of tower top, 130～230 ℃ of tower reactor temperature, absolute pressure of top of the tower is 5～50KPa; Described ethylene glycol product column overhead light constituent reflux ratio is 50～200 or total reflux.
The technique that 22. a kind of industrial synthetic gas pressure carbonylations as claimed in claim 1 are produced dimethyl oxalates Hydrogenation ethylene glycol, is characterized in that, the consisting of of the purified gas reclaiming in described pressure-variable adsorption tank: N
2be 60～80v%, CO is 20～40v%; Isolated CO
2gas accounts for 0.1～5v% of air inlet total amount, wherein CO
2concentration be 99.8～99.9v%.
The technique that 23. a kind of industrial synthetic gas pressure carbonylations as claimed in claim 2 are produced dimethyl oxalates Hydrogenation ethylene glycol, is characterized in that, described membrane separation apparatus (28) is in parallel or be connected in series and form by a plurality of hollow fiber film assemblies; In the purification gas obtaining through described membrane separation apparatus (28) separating-purifying, density of hydrogen is 88～99.99v%, hydrogen recovery rate 90～98.5%.
24. 1 kinds of industrial synthetic gas pressure carbonylations are produced the apparatus system of dimethyl oxalate Hydrogenation ethylene glycol, it is characterized in that, comprise oxonation system, esterification system, speed to exit and spent acid coupling recovery system and hydrogenation reaction system;
Described oxonation system comprises oxonation device (1), the first gas-liquid separator (4), Methanol Wash Column (7), methanol rectifying tower (5) and DMO rectifying tower (6); Described oxonation device (1) is provided with its top feed mouth, bottom discharge mouth, bottom refrigerant import and top refrigerant exit; Described the first gas-liquid separator (4) is provided with opening for feed, pneumatic outlet and liquid exit; Described Methanol Wash Column (7) is provided with top opening for feed, underfeed mouth, top exit and outlet at bottom; Described methanol rectifying tower (5) is provided with top opening for feed, underfeed mouth, top exit and outlet at bottom; Described DMO rectifying tower (6) is provided with underfeed mouth, top exit and outlet at bottom;
Described esterification system comprises esterification reaction tower (9) and methanol distillation column (11); Described esterification reaction tower (9) is provided with its top feed mouth, top opening for feed, a plurality of underfeed mouth, middle part reflux inlet, top exit and outlet at bottom; Described methanol distillation column (11) is provided with middle and lower part opening for feed, underfeed mouth, top exit and outlet at bottom;
The described venting of speeding comprises nitric acid concentration tower (12), NO recovery tower (13), MN recovery tower (15) and pressure-variable adsorption tank (16) with spent acid coupling recovery system; Described nitric acid concentration tower (12) is provided with middle part opening for feed, top exit and outlet at bottom; Described NO recovery tower (13) is provided with its top feed mouth, middle part opening for feed, bottom feed mouth, top exit and outlet at bottom; Described MN recovery tower (15) is provided with top opening for feed, underfeed mouth, top exit and outlet at bottom; Described pressure-variable adsorption tank (16) is provided with opening for feed, reclaims gas outlet and the outlet of discharge gas;
Described hydrogenation reaction system comprises and adds Recycle hydrogen compressor (14), hydrogenator (17), the second gas-liquid separator, membrane separation apparatus (28), method separation tower (22), light constituent rectifying tower (23) and ethylene glycol product tower (24); The described Recycle hydrogen compressor (14) that adds comprises import and outlet; Described hydrogenator (17) is provided with its top feed mouth, bottom discharge mouth, bottom refrigerant import and top refrigerant exit; Described the second gas-liquid separator is provided with opening for feed, pneumatic outlet and liquid exit; Described membrane separation apparatus (28) is provided with opening for feed, reclaims gas outlet and the outlet of discharge gas; Described method separation tower (22) is provided with middle part opening for feed, the outlet of top non-condensable gas, the outlet of top liquid phase light constituent and the outlet of bottom liquid phases heavy constituent; Described light constituent rectifying tower (23) is provided with underfeed mouth, top exit and outlet at bottom; Described ethylene glycol product tower (24) is provided with underfeed mouth, top exit, top outlet and outlet at bottom;
Its top feed mouth of described oxonation device (1) and CO raw material pipeline and N
2raw material pipeline connects through pipeline; The bottom discharge mouth of described oxonation device (1) is connected through pipeline with the opening for feed of described the first gas-liquid separator (4); The pneumatic outlet of described the first gas-liquid separator (4) is connected through pipeline with the underfeed mouth of described Methanol Wash Column (7); The liquid exit of described the first gas-liquid separator (4) is connected through pipeline with the top opening for feed of described methanol rectifying tower (5); The top exit of described Methanol Wash Column (7) is provided with branch outlet A and branch outlet B, branch outlet A is connected through pipeline with a underfeed mouth of described esterification reaction tower (9), and branch outlet B is connected through pipeline with the bottom feed mouth of described NO recovery tower (13); The outlet at bottom of described Methanol Wash Column (7) is connected through pipeline with the underfeed mouth of described methanol rectifying tower (5); The top exit of described methanol rectifying tower (5) is connected through pipeline with the top opening for feed of described esterification reaction tower (9); The outlet at bottom of described methanol rectifying tower (5) is connected through pipeline with the underfeed mouth of described DMO rectifying tower (6); The outlet at bottom of described DMO rectifying tower (6) is connected through pipeline with its top feed mouth of described hydrogenator (17), and the top exit of described DMO rectifying tower (6) is DMC products export;
Other underfeed mouth of described esterification reaction tower (9) and NO raw material pipeline and multichannel O
2raw material pipeline connects through pipeline respectively; Its top feed mouth of described esterification reaction tower (9) is connected through pipeline with methanol feedstock pipeline; The outlet at bottom of described esterification reaction tower (9) is provided with branch outlet C and branch outlet D, branch outlet C is connected through pipeline with the middle part reflux inlet of described esterification reaction tower (9), and branch outlet D is connected through pipeline with the underfeed mouth of described methanol distillation column (11); The top exit of described esterification reaction tower (9) is connected through pipeline with its top feed mouth of described oxonation device (1); The top exit of described methanol distillation column (11) is provided with branch outlet E and branch outlet F, branch outlet E is connected through pipeline with the top opening for feed of described esterification reaction tower (9), and branch outlet F is connected through pipeline with the top opening for feed of described MN recovery tower (15); The outlet at bottom of described methanol distillation column (11) is connected through pipeline with the middle part opening for feed of described nitric acid concentration tower (12);
The top exit of described nitric acid concentration tower (12) is waste liquid relief outlet; The outlet at bottom of described nitric acid concentration tower (12) is connected through pipeline with the middle part opening for feed of described NO recovery tower (13); The top exit of described NO recovery tower (13) is connected through pipeline with the underfeed mouth of described MN recovery tower (15); The outlet at bottom of described NO recovery tower (13) is connected through pipeline with the middle and lower part opening for feed of described methanol distillation column (11); The top exit of described MN recovery tower (15) is connected through pipeline with the opening for feed of described pressure-variable adsorption tank (16); The outlet at bottom of described MN recovery tower (15) is connected through pipeline with the top opening for feed of described esterification reaction tower (9); The recovery gas outlet of described pressure-variable adsorption tank (16) is connected through pipeline with its top feed mouth of described oxonation device (1); The discharge gas outlet of described pressure-variable adsorption tank (16) is connected through pipeline with retrieving arrangement out-of-bounds;
The described import that adds Recycle hydrogen compressor (14) is connected through pipeline with plant hydrogen raw material pipeline, described in add Recycle hydrogen compressor (14) outlet be connected through pipeline with its top feed mouth of described hydrogenator (17); The bottom discharge mouth of described hydrogenator (17) is connected through pipeline with the opening for feed of described the second gas-liquid separator; The pneumatic outlet of described the second gas-liquid separator is provided with branch outlet G and branch outlet H, branch outlet G with described in add Recycle hydrogen compressor (14) import through pipeline, be connected, branch outlet H is connected through pipeline with the opening for feed of described membrane separation apparatus (28); The liquid exit of described the second gas-liquid separator is connected through pipeline with the underfeed mouth of described method separation tower (22); The top non-condensable gas outlet of described method separation tower (22) is connected through pipeline with the opening for feed of described membrane separation apparatus (28); The top liquid phase light constituent outlet of described method separation tower (22) is provided with branch outlet I and branch outlet J, branch outlet I is connected through pipeline with the top opening for feed of described Methanol Wash Column (7), and branch outlet J is connected through pipeline with its top feed mouth of described NO recovery tower (13); The bottom liquid phases heavy constituent outlet of described method separation tower (22) is connected through pipeline with the underfeed mouth of described light constituent rectifying tower (23); The top light constituent outlet of described light constituent rectifying tower (23) is connected through pipeline with alcohol retrieving arrangement out-of-bounds; The bottom heavy constituent outlet of described light constituent rectifying tower (23) is connected through pipeline with the underfeed mouth of described ethylene glycol product tower (24); The top exit of described ethylene glycol product tower (24) and out-of-bounds 1,2-BDO recycling and processing device connects through pipeline; The outlet at bottom of described ethylene glycol product tower (24) is connected through pipeline with recycling and processing device out-of-bounds; The top outlet of described ethylene glycol product tower (24) is ethylene glycol products export; The discharge gas outlet of described membrane separation apparatus (28) is connected through pipeline with retrieving arrangement out-of-bounds, and the recovery gas of described membrane separation apparatus (28) exports and is connected through pipeline with its top feed mouth of described hydrogenator (17).
25. a kind of industrial synthetic gas pressure carbonylations as claimed in claim 24 are produced the apparatus system of dimethyl oxalate Hydrogenation ethylene glycol, it is characterized in that, described oxonation device (1) is externally connected with dehydration tower (10); Described dehydration tower (10) is provided with opening for feed and dry gas outlet; The recovery gas outlet of the top exit of described esterification reaction tower (9) and described pressure-variable adsorption tank (16) is connected through pipeline with the opening for feed of described dehydration tower (10); The dry gas outlet of described dehydration tower (10) is connected through pipeline with described oxonation device (1) its top feed mouth.
26. a kind of industrial synthetic gas pressure carbonylations as claimed in claim 25 are produced the apparatus system of dimethyl oxalate Hydrogenation ethylene glycol, it is characterized in that, described dehydration tower is comprised of mole sieve drier A and the mole sieve drier B of two alternate runs and regeneration; Filled with adsorbent in mole sieve drier A and mole sieve drier B.
27. a kind of industrial synthetic gas pressure carbonylations as claimed in claim 25 are produced the apparatus system of dimethyl oxalate Hydrogenation ethylene glycol, it is characterized in that, the bottom discharge mouth of described oxonation device (1) is connected with outlet interchanger I (3); Described outlet interchanger I (3) is provided with cold logistics import, cold logistics outlet, thermal material import and hot logistics outlet; Described CO raw material pipeline, N
2the dry gas outlet of raw material pipeline and dehydration tower (10) is connected through pipeline with the cold logistics import of described outlet interchanger I (3); The cold logistics outlet of described outlet interchanger I (3) is connected through pipeline with its top feed mouth of described oxonation device (1); The bottom discharge mouth of described oxonation device (1) is connected through pipeline with the hot logistics import of described outlet interchanger I (3); The hot logistics outlet of described outlet interchanger I (3) is connected through pipeline with the opening for feed of described the first gas-liquid separator (4).
28. a kind of industrial synthetic gas pressure carbonylations as claimed in claim 27 are produced the apparatus system of dimethyl oxalate Hydrogenation ethylene glycol, it is characterized in that, described oxonation device (1) is externally connected with drum I (2); Described drum I (2) is provided with refrigerant import, refrigerant exit, liquid-vapor mixture import and vapour outlet; The refrigerant import of described drum I (2) is connected through pipeline with refrigerant raw material pipeline; The refrigerant exit of described drum I (2) is connected through pipeline with the bottom refrigerant import of described oxonation device (1); The top refrigerant exit of described oxonation device (1) is connected through pipeline with the liquid-vapor mixture import of described drum I (2); The vapour outlet of described drum I (2) is connected through pipeline with vapor-recovery system out-of-bounds.
29. a kind of industrial synthetic gas pressure carbonylations as claimed in claim 28 are produced the apparatus system of dimethyl oxalate Hydrogenation ethylene glycol, it is characterized in that, between the branch outlet A of described Methanol Wash Column (7) and the underfeed mouth of described esterification reaction tower (9), be connected with carbonylation recycle compressor (8); Described carbonylation recycle compressor (8) is provided with import and outlet; Described branch outlet A is connected through pipeline with the import of described carbonylation recycle compressor (8); The outlet of described carbonylation recycle compressor (8) is connected through pipeline with the underfeed mouth of described esterification reaction tower (9).
30. a kind of industrial synthetic gas pressure carbonylations as claimed in claim 29 are produced the apparatus system of dimethyl oxalate Hydrogenation ethylene glycol, it is characterized in that, the bottom feed mouth of the top exit of described NO recovery tower (13) and described MN recovery tower (15) is connected with compressor (14); Described compressor (14) is provided with import and outlet; The top exit of described NO recovery tower (13) is connected through pipeline with the import of described compressor (14); The outlet of described compressor is connected through pipeline with the bottom feed mouth of described MN recovery tower (15).
31. a kind of industrial synthetic gas pressure carbonylations as claimed in claim 30 are produced the apparatus system of dimethyl oxalate Hydrogenation ethylene glycol, it is characterized in that, the bottom discharge mouth of described hydrogenator (17) is connected with outlet interchanger II (20); Described outlet interchanger II (20) is provided with cold logistics import, cold logistics outlet, thermal material import and hot logistics outlet; The recovery gas outlet of the outlet at bottom of described DMO rectifying tower (6), described membrane separation apparatus (28) and described in add the outlet of Recycle hydrogen compressor (25) and the cold logistics import of described outlet interchanger II (20) is connected through pipeline; The cold logistics outlet of described outlet interchanger II (20) is connected through pipeline with its top feed mouth of described hydrogenator (17); The bottom discharge mouth of described hydrogenator (17) is connected through pipeline with the hot logistics import of described outlet interchanger II (20); The hot logistics outlet of described outlet interchanger II (20) is connected through pipeline with the opening for feed of described the second gas-liquid separator.
32. a kind of industrial synthetic gas pressure carbonylations as claimed in claim 31 are produced the apparatus system of dimethyl oxalate Hydrogenation ethylene glycol, it is characterized in that, its top feed mouth of described hydrogenator (17) is connected with the well heater that goes into operation (19); The described well heater that goes into operation (19) is provided with opening for feed and discharge port; The cold logistics outlet of described outlet interchanger II (20) with described in the go into operation opening for feed of well heater (19) through pipeline, be connected; The discharge port of the described well heater that goes into operation is connected through pipeline with its top feed mouth of described hydrogenator (17).
33. a kind of industrial synthetic gas pressure carbonylations as claimed in claim 32 are produced the apparatus system of dimethyl oxalate Hydrogenation ethylene glycol, it is characterized in that, described hydrogenator (17) is externally connected with drum II (18); Described drum II (18) is provided with refrigerant import, refrigerant exit, liquid-vapor mixture import and vapour outlet; The refrigerant import of described drum II (18) is connected through pipeline with refrigerant raw material pipeline; The refrigerant exit of described drum II (18) is connected through pipeline with the bottom refrigerant import of described hydrogenator (17); The top refrigerant exit of described hydrogenator (17) is connected through pipeline with the liquid-vapor mixture import of described drum II (18); The vapour outlet of described drum II (18) is connected through pipeline with vapor-recovery system out-of-bounds.
34. a kind of industrial synthetic gas pressure carbonylations as claimed in claim 33 are produced the apparatus system of dimethyl oxalate Hydrogenation ethylene glycol, it is characterized in that, described the second gas-liquid separator comprises high-pressure gas-liquid separator (21) and low-pressure gas-liquid separator (26); Described high-pressure gas-liquid separator (21) is provided with opening for feed, pneumatic outlet and liquid exit; Described low-pressure gas-liquid separator (26) is provided with opening for feed, pneumatic outlet and liquid exit; The bottom discharge mouth of described hydrogenator (17) is connected through pipeline with the opening for feed of described high-pressure gas-liquid separator (21); The pneumatic outlet of described high-pressure gas-liquid separator (21) is provided with branch outlet K and branch outlet L, branch outlet K with described in add Recycle hydrogen compressor (25) import through pipeline, be connected, branch outlet L is connected through pipeline with the opening for feed of described low-pressure gas-liquid separator (26); The liquid exit of described high-pressure gas-liquid separator (21) is connected through pipeline with the middle part opening for feed of described method separation tower (22); The pneumatic outlet of described low-pressure gas-liquid separator (26) is connected through pipeline with the opening for feed of described membrane separation apparatus (28); The liquid exit of described low-pressure gas-liquid separator (26) is connected through pipeline with the middle part opening for feed of described method separation tower (22).
35. a kind of industrial synthetic gas pressure carbonylations as claimed in claim 31 are produced the apparatus system of dimethyl oxalate Hydrogenation ethylene glycol, it is characterized in that, are provided with methyl alcohol tourie (27) before the opening for feed of described membrane separation apparatus (28); Described methyl alcohol tourie (27) is provided with opening for feed and clean gas outlet; The top non-condensable gas outlet of the pneumatic outlet of described low-pressure gas-liquid separator (26) and described method separation tower (22) is connected through pipeline with the opening for feed of described methyl alcohol tourie (27); The clean gas outlet of described methyl alcohol tourie (27) is connected through pipeline with the opening for feed of described membrane separation apparatus (28).
36. a kind of industrial synthetic gas pressure carbonylations as claimed in claim 24 are produced the apparatus system of dimethyl oxalate Hydrogenation ethylene glycol, it is characterized in that, described oxonation device (1) is plate-type reactor, tubular reactor or tubular type-board-like compound reactor.
37. a kind of industrial synthetic gas pressure carbonylations as claimed in claim 36 are produced the apparatus system of dimethyl oxalate Hydrogenation ethylene glycol, it is characterized in that, described oxonation device (1) is board-like fixed bed oxonation device; Described board-like fixed bed oxonation Qi center is provided with plate groups lock chamber, in described plate groups lock chamber, is provided with plate groups, and described plate groups lock chamber is also provided with bottom inlet and top exit; The outer wall of described plate groups lock chamber is provided with beds between the inwall of board-like fixed bed oxonation device; In beds, be filled with oxonation catalyzer, described beds is also provided with top entrance and outlet at bottom; Bottom at described board-like fixed bed oxonation device, the bottom refrigerant import of described board-like fixed bed oxonation device is connected through pipeline with the bottom inlet of described plate groups lock chamber, and the outlet at bottom of described beds is connected through pipeline with the bottom discharge mouth of described board-like fixed bed oxonation device; Top at described board-like fixed bed oxonation device, the its top feed mouth of described board-like fixed bed oxonation device is connected through pipeline with the top entrance of described beds, and the top exit of described plate groups lock chamber is connected through pipeline with the top refrigerant exit of described board-like fixed bed oxonation device.
38. a kind of industrial synthetic gas pressure carbonylations as claimed in claim 24 are produced the apparatus system of dimethyl oxalate Hydrogenation ethylene glycol, it is characterized in that, described esterification reaction tower (9) is packing tower or column plate-filler mixing column simultaneously with column plate part and filler filling part.
39. a kind of industrial synthetic gas pressure carbonylations as claimed in claim 24 are produced the apparatus system of dimethyl oxalate Hydrogenation ethylene glycol, it is characterized in that, described Methanol Wash Column (7), methanol rectifying tower (5), methanol distillation column (11), NO recovery tower (13), MN recovery tower (15), DMO rectifying tower (6) and nitric acid concentration tower (12) are packing tower, tray column or bubble-plate column.
40. a kind of industrial synthetic gas pressure carbonylations as claimed in claim 24 are produced the apparatus system of dimethyl oxalate Hydrogenation ethylene glycol, it is characterized in that, described hydrogenator (17) is plate bed reactor, tubular reactor or board-like-tubular type combined reactor.
41. a kind of industrial synthetic gas pressure carbonylations as claimed in claim 35 are produced the apparatus system of dimethyl oxalate Hydrogenation ethylene glycol, it is characterized in that, described hydrogenator (17) is board-like fixed bed hydrogenation reactor; The center of described board-like fixed bed hydrogenation reactor is provided with plate groups lock chamber, in described plate groups lock chamber, is provided with plate groups, and described plate groups lock chamber is also provided with bottom inlet and top exit; The outer wall of described plate groups lock chamber is provided with beds between the inwall of board-like fixed bed hydrogenation reactor; In described beds, be filled with catalyst for hydrogenation, described beds is also provided with top entrance and outlet at bottom; Bottom at described board-like fixed bed hydrogenation reactor, the bottom refrigerant import of described board-like fixed bed hydrogenation reactor is connected through pipeline with the bottom inlet of described plate groups lock chamber, and the outlet at bottom of described beds is connected through pipeline with the bottom discharge mouth of described board-like fixed bed hydrogenation reactor; Top at described board-like fixed bed hydrogenation reactor, the its top feed mouth of described board-like fixed bed hydrogenation reactor is connected through pipeline with the top entrance of described beds, and the top exit of described plate groups lock chamber is connected through pipeline with the top refrigerant exit of described board-like fixed bed hydrogenation reactor.
42. a kind of industrial synthetic gas pressure carbonylations as claimed in claim 24 are produced the apparatus system of dimethyl oxalates Hydrogenation ethylene glycol, it is characterized in that, described membrane separation apparatus (28) is in parallel or be connected in series and form by 1～100 hollow fiber film assembly.
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| CN201410353158.7A CN104098441B (en) | 2014-06-05 | 2014-07-23 | Commercial syngas mesohigh carbonylation produces dimethyl oxalate and the technique of Hydrogenation ethylene glycol and apparatus system |
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| CN201410353158.7A Active CN104098441B (en) | 2014-06-05 | 2014-07-23 | Commercial syngas mesohigh carbonylation produces dimethyl oxalate and the technique of Hydrogenation ethylene glycol and apparatus system |
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