CN103012062B - Process for indirectly producing alcohol with synthetic gas and application of process - Google Patents
Process for indirectly producing alcohol with synthetic gas and application of process Download PDFInfo
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- CN103012062B CN103012062B CN201210559809.9A CN201210559809A CN103012062B CN 103012062 B CN103012062 B CN 103012062B CN 201210559809 A CN201210559809 A CN 201210559809A CN 103012062 B CN103012062 B CN 103012062B
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Abstract
The invention relates to a process for indirectly producing alcohol with synthetic gas. The process comprises the steps that the synthetic gas formed by mixing industrial carbon monoxide with hydrogen is taken as a raw material to synthesize methanol; methanol is dehydrated to prepare dimethyl ether; dimethyl ether, carbon monoxide and hydrogen are mixed for carbonylation reaction to prepare methyl acetate; methyl acetate is purified and hydrogenated; a hydrogenated product is purified; and an alcohol product is obtained. An adopted catalyst, the process and a device have the characteristics of high conversion per pass and high effective utilization rate of reaction heat; the load of separating a crude product is reduced greatly; the production flow is shortened; and the production energy consumption is reduced greatly.
Description
Technical field
The present invention relates to technique and application thereof that a kind of synthetic gas produces ethanol indirectly, belong to synthetic gas ethanol field.
Background technology
Ethanol is important basic chemical raw materials, for the manufacture of acetaldehyde, ethene, ethamine, vinyl acetic monomer, acetic acid, monochloroethane etc., and deriving many intermediates of the products such as medicine, dyestuff, coating, spices, synthetic rubber, washing composition, agricultural chemicals, its goods reach more than 300 kinds.Simultaneously in the application of fuel energy industry, because ethanol has, calorific value is low, the latent heat of vaporization is high, the capability of antidetonance is good, oxygen level is high, deposit easily to produce in case at a small amount of water and be separated, and compared with regular gasoline, the features such as burning more completely, CO quantity discharged is low, combustionproperty is similar, are therefore called as 21 century " green energy resource ".The current unstable coming from the non-renewable of oil and oildom, fuel energy safety problem causes increasing concern in the world, applying of alcohol fuel is all actively being carried out in countries in the world, and 60% of ethanol production is used as vehicle fuel in the world.Therefore, greatly develop the energy industry that alcohol fuel, ethanol diesel fuel etc. take alcohol as raw material, become a spotlight of International Fuel energy industry.
At present, fuel ethanol production is mainly raw material with cereal, and Corn Fuel Ethanol has become important power supply source in a lot of country, but due to the rise of provision price, ethanol price constantly rises.At present, the close prices of dehydrated alcohol 8000 yuan/ton, therefore, adopts non-grain operational path to be a very wise selection.
Patent CN1122567C discloses the method for hydrogen and carbon monoxide synthesis direct production ethanol.The method know-why operational path simple, efficiency is higher, easy mass-producing, is desirable synthetic route.But in technological process, 1.4 tons of synthetic gas produce 1 ton of ethanol, and Synthetic holography rate is only 71%, and the by product of synthetic gas ethanol is water, and in synthetic gas, hydrogen about 1/4 is depleted.Product component more complicated, thick product also needs hydrogenation and refinement treatment.And synthetic gas directly alcohol catalysis agent processed exploitation also rest on the lab scale stage at present, and use expensive precious metal (rhodium etc.) catalyzer, there is the problems such as speed of reaction is slow, these are the technical bottlenecks that cannot break through its current and following a very long time.
Patent CN102317412 discloses the method for the biological legal system ethanol of synthetic gas, namely microbial fermentation technology is utilized, ethanol is produced with synthetic gas (comprising the waste gas containing carbon monoxide and hydrogen), because fermentation needs stay for some time, be difficult to realize continuous prodution, current cost is higher, is only in conceptual phase, and large industrialized is still to be tested.
Patent CN101952231 discloses the method for synthetic gas through acetic acid esterified preparation of ethanol by hydrogenating.Synthetic holography is first methyl alcohol by this technique, and then methyl alcohol and synthetic gas carbonylation produce acetic acid, acetic acid again with methyl alcohol or alcohol production acetic ester, last acetic ester generates ethanol at further hydrogenation.This technique adopts the precious metal such as rhodium, iridium in methanol carbohylation process, and equipment adopts expensive zirconium material or Hastelloy, and equipment one-time investment is large, and reaction scheme is long, and plant energy consumption is high.
Synthetic gas is current coal ethanol prevailing technology route through acetic acid preparation of ethanol by hydrogenating operational path.This technique is by synthetic gas CO, CO
2and H
2first be prepared into methyl alcohol, then carbonylation of methanol produces acetic acid, last acetic acid hydrogenation ethanol production.Adopt this technique ton ethanol to consume acetic acid 1.3034t, hydrogen 972.4Nm3 in theory, produce 0.391 ton of water.Current acetic acid price 2600 ~ 3600 yuan/ton, price comparison is cheap, and Production Technology of Acetic Acid is ripe, and therefore acetic acid hydrogenation production ethanol is expected to maximization, mass-producing.But in its operational path, methanol carbohylation process adopts the precious metal such as rhodium, iridium; Acetic acid preparation of ethanol by hydrogenating, utilize platinum/tin catalyst from the technology (patent USP7863489) of the direct and selective production ethanol of acetic acid, hydrogenation process needs two steps to complete, and economy is still to be tested.Technique requires higher to material simultaneously, and output investment ratio is comparatively large, as Production of Acetic Acid by Methanol Carbonylation reactor and acetic acid hydrogenator equipment all adopt expensive zirconium material or Hastelloy.
Summary of the invention
The object of the invention is to the shortcoming overcoming above prior art, a kind of technique and application thereof of indirectly being produced ethanol by synthetic gas are provided.
First the present invention discloses the technique that a kind of synthetic gas produces ethanol indirectly: the first synthetic gas be mixed to form with hydrogen and technical grade carbon monoxide is for Material synthesis methyl alcohol, methyl alcohol dewaters and prepares dme, then dme mixes with carbon monoxide and hydrogen and carries out oxonation and produce ritalin, carry out hydrogenation after ritalin purifying, after hydrogenation products purifying, namely obtain alcohol product.
The technique of described synthetic gas indirect synthesis ethanol, specifically comprises the following steps:
The first step, synthetic gas catalyzes and synthesizes methanol process: passed into from the top of methanol reactor by the synthetic gas that hydrogen and technical grade carbon monoxide are mixed to form, and carries out catalyzing and synthesizing methyl alcohol reaction under the existence of catalst for synthesis of methanol; In described methanol reactor, temperature of reaction is 200 ~ 300 DEG C, and reaction pressure is 3 ~ 12MPa.
Preferably, in described methanol reactor, temperature of reaction is 225 ~ 265 DEG C, and reaction pressure is 5 ~ 10MPa.
Preferably, the purity of described hydrogen and technical grade carbon monoxide is respectively 99.9V% and 98V%; The mixed volume of described hydrogen and technical grade carbon monoxide, than being 2-3.5:1, is preferably 2.5-3:1.
Preferably, described methanol reactor is fixed-bed reactor or fluidized-bed reactor; Be preferably fixed-bed reactor; Be particularly preferably board-like fixed-bed reactor.
Preferably, described methanol reactor is provided with heat-exchange system; The interchanger turnkey of described methanol reactor draws together methanol reactor outlet interchanger and methanol reactor inlet heat exchanger.
Preferably, after the multistage Continuous Heat Transfer of heat-exchange system of described synthetic gas also through described methanol reactor before entering methanol reactor reaches the beds inlet temperature of described methanol reactor, then enter described methanol reactor and carry out catalyzing and synthesizing methyl alcohol reaction.
Preferably, described catalst for synthesis of methanol is Cu-Zn-Al series catalysts, and the carrier of described catalyzer is Al
2o
3be 10 ~ 30wt%, the activeconstituents of described catalyzer and content are respectively CuO:5 ~ 30wt% and ZnO:10 ~ 70wt%.
Preferably, described in catalyze and synthesize the product of methyl alcohol reaction from the bottom discharge of methanol reactor, after entering the heat exchange of described methanol reactor outlet interchanger, enter in water cooler and be cooled to 30 ~ 50 DEG C further, then enter gas-liquid separator; Supercharging after described gas-liquid separator top gas phase discharge unit non-condensable gas, then mixes with described synthetic gas, and the heat-exchange system heat exchange Posterior circle through described methanol reactor continues reaction to methanol reactor; Described gas-liquid separator bottom liquid phases crude carbinol enters follow-up methyl alcohol rough segmentation or treating process.
Second step, methyl alcohol rough segmentation or treating process: the crude carbinol product synthesized in described methanol reactor is passed into the rough segmentation that methyl alcohol is carried out in flash tank flash separation, or pass into methanol rectification separating technology unit and carry out the refining of methyl alcohol;
Preferably, in described methanol reactor, synthesizing methanol reaction product reduces pressure through reducing valve before passing into flash tank, and then in flash tank, carry out gas-liquid separation, isolated noncondensable gas discharges the external world and recycles, and isolated lime set is crude carbinol.
Preferably, described methanol rectification separating technology unit is two tower rectifying or three-tower rectifications, obtains refined methanol after separation.
3rd step, the reactive distillation processes of dimethyl ether preparation by dehydrating methyl alcohol: described flash tank or the isolated crude carbinol of methanol rectification separating technology unit or refined methanol, after preheater preheats to the bubble point temperature of methyl alcohol, pass into the reactive distillation processes carrying out dimethyl ether preparation by dehydrating methyl alcohol from the bottom of the reactive distillation column that solid super-strong acid filler is housed;
Preferably, the mixed solution of described reactive distillation column tower reactor extraction enters methanol distillation column, methanol distillation column tower reactor is discharged the impurity such as water and is delivered to extraneous process, and the methyl alcohol of methanol distillation column overhead extraction continues to react with described flash tank or the isolated crude carbinol of methanol rectification separating technology unit or refined methanol mixing Posterior circle to reactive distillation column.
Described methanol distillation column is atmospheric distillation tower.
Preferably, the operational condition of described methanol distillation column is tower top temperature 58 ~ 68 DEG C, and bottom temperature is 90 ~ 130 DEG C.
Described bubble point temperature refers to the bubble point temperature of methyl alcohol in described reactive distillation column under reaction zone pressure.
Preferably, described flash tank or the isolated crude carbinol of methanol rectification separating technology unit or refined methanol, after described preheater preheats to bubble point temperature, are introduced in heat insulation tank and store, and then enter in described reactive distillation column and react.
Preferably, the theoretical plate number of described reactive distillation column is 9 ~ 50 pieces, is preferably 30 ~ 50 pieces, is particularly preferably 40 ~ 50 pieces.
Preferably, described reactive distillation column is compression rectification tower, and tower top pressure is 0.5 ~ 1.8MPa, is preferably 0.8 ~ 1.2MPa; Bottom temperature is 100 ~ 300 DEG C, is preferably 160 ~ 260 DEG C.
Preferably, in described reactive distillation column, the temperature of main reaction region is 120 ~ 220 DEG C.
Preferably, in described reactive distillation column, controlling reflux ratio is 0.01 ~ 3.0.
Preferably, in described reactive distillation column, methanol solution hourly space velocity is 2.5 ~ 30h
-1.
Preferably, in described reactive distillation column, unreacted methyl alcohol is drawn through tower top side line, and mix with described flash tank or the isolated crude carbinol of methanol rectification separating technology unit or refined methanol, is circulated to reactive distillation column and continues to react.
Preferably, described tower top side line is positioned at the 1st ~ 5th piece of column plate place of reactive distillation column, is preferably the 1st ~ 2nd piece of column plate place.
Preferably, described reactive distillation column overhead light constituent dme, a small amount of methyl alcohol and water etc. are overflowed by tower top, after multi-stage condensing, most of dme, first alcohol and water and a small amount of impurity are condensed and return in tower, noncondensable gas is honored as a queen through overhead water and is delivered to extraneous recovery system, and all the other enter oxonation device and carry out oxonation.
Preferably, described multi-stage condensing system is three grades of condenser systems, and first step condensing temperature is higher, reduces the light constituent that returns in tower, to improve the stability of dme after rectifying; The second stage is then normal temperature, reclaims dme as far as possible; The third stage will be chilled to lower temperature with refrigerant, to purify dme, reclaims dme further simultaneously.
Described solid super-strong acid filler is the ceramic packing that load has solid super-strong acid; Described solid super-strong acid is the acid type catalyst that in solid acid, strength of acid is the highest, to equipment without any corrosion.Its Hammett function is :-16.02<H
0<-14.520, is equivalent to 10000 times of 100% fluid sulphuric acid.
Preferably, described solid super-strong acid is SO
4 2-/ beta-molecular sieve composite catalyst.
The present invention further discloses its preparation method of described solid super-strong acid filler, comprise the following steps:
(1) by (NH
4)
2s
2o
8be immersed on nano-beta molecular sieve, make nm-class catalyst powder;
(2) add ceramic material and adhesive aid mixes, then mediate, shaping;
(3) namely dry, roasting obtains described solid super-strong acid filler again.
Wherein,
(NH
4)
2s
2o
8be immersed in after on nano-beta molecular sieve and also can form SO after roasting
4 2-/ beta-molecular sieve composite catalyst, reason is (NH
4)
2s
2o
8decompose under maturing temperature, NH
4 +in hydration mode out, remaining SO
4 2-/ beta-molecular sieve.
Preferably, the particle diameter of step (1) described nano-beta molecular sieve is 68 ~ 80nm.
Preferably, the mode of step (2) described mixing is spraying or mechanically mixing, is preferably mechanically mixing.
Preferably, step (2) described adhesive aid is selected from Vltra tears, sesbania powder and carboxymethyl cellulose.
Preferably, the ratio of the mixing quality of described catalyst fines, ceramic material and adhesive aid is 45-89.8:10-50:0.2-5, is preferably, 50-85:10-49:1-5.
Preferably, the temperature of step (3) described roasting is 500 ~ 600 DEG C, and the time of roasting is 3 ~ 6h.
Preferably, described solid super-strong acid filler is of a size of 3 ~ 5mm × 3 ~ 5mm, is preferably 5mm × 5mm.
Preferably, average load super acids active centre 0.58 ~ 0.62wt% on described filler particles.
Described solid super-strong acid filler is dumped packing or structured packing; The shape of described dumped packing comprises the shape of a saddle, Raschig ring, Pall ring, wheel shape, rectangular saddle ring, spherical or column.
The shape of described structured packing comprises corrugated plate shape or cellular.
Preferably, described solid super-strong acid filler is for huddling Berl saddles.
In described reactive distillation column, methanol liquid and steam continuous countercurrent on described solid super-strong acid filler contacts the reactive distillation processes carrying out dimethyl ether preparation by dehydrating methyl alcohol.
4th step, oxonation process: be mixed into as oxonation unstripped gas enters oxonation device by the dme of described reactive distillation column overhead extraction and hydrogen, industrial carbon monoxide, carries out oxonation and generates ritalin under carbonylation catalyst exists;
The temperature of reaction of described oxonation is 150 ~ 350 DEG C, is preferably 230 ~ 300 DEG C; Reaction pressure is 1 ~ 8MPa, is preferably 3 ~ 5MPa.
Described oxonation device is fixed-bed reactor or fluidized-bed reactor, is preferably fixed-bed reactor, is particularly preferably board-like fixed-bed reactor.
Described carbonylation catalyst is H-MOR, and coagent and content are CuO 0 ~ 30wt%, CoO 0.1 ~ 10wt%, MoO 0.1 ~ 10wt%, preferably CuO 5 ~ 15wt%, CoO 0.5 ~ 6wt%, Mo
2o
30.5 ~ 8wt%.
Preferably, in described oxonation device, dme, CO and H
2raw materials components mole ratio is 1 ~ 5:50 ~ 90:1 ~ 20.
Preferably, in described oxonation device, liquid mass space time velocity is 0.15 ~ 0.3Kg/Kg.h.
Preferably, described oxonation device is provided with heat-exchange system; The heat-exchange system of described oxonation device comprises oxonation device outlet interchanger and oxonation device inlet heat exchanger.
Preferably, after the multistage Continuous Heat Transfer of heat-exchange system of described oxonation unstripped gas also through described oxonation device before entering oxonation device reaches the beds inlet temperature of described oxonation device, then enter described oxonation device and carry out oxonation.
Preferably, the reaction product of described oxonation is drawn bottom oxonation device, after entering the heat exchange of described oxonation device outlet interchanger, enters water cooler and is cooled to 30-50 DEG C further, then enter gas-liquid separator and carry out gas-liquid separation; Supercharging after described gas-liquid separator top gas phase discharge unit non-condensable gas, then mix with described oxonation unstripped gas, heat-exchange system heat exchange Posterior circle through described oxonation device continues reaction to oxonation device, and described gas-liquid separator bottom liquid enters thick ester tank or directly enters the separation and purification that dme recovery tower carries out oxonation product.
5th step, oxonation product separation treating process: the reaction product of described oxonation is drawn bottom oxonation device, enters the rectifying of dme recovery tower and reclaims dme; The light constituents such as dme recovery tower top extraction dme and a small amount of ritalin, bottom liquid heavy constituent enters the further separating-purifying of ritalin rectifying tower;
Preferably, the operational condition of described dme recovery tower is tower top temperature 58 ~ 70 DEG C, and bottom temperature 100 ~ 150 DEG C, pressure is 0.3 ~ 0.8MPa.
Preferably, the operational condition of described ritalin rectifying tower is tower top temperature 58 ~ 65 DEG C, and bottom temperature 130 ~ 170 DEG C, pressure is normal pressure.
Preferably, the dme of described dme recovery tower top extraction is circulated to described oxonation device continuation reaction.
Preferably, mix with described oxonation unstripped gas after the dme supercharging of described dme recovery tower top extraction, after the heat-exchange system of oxonation device reaches the beds inlet temperature of oxonation device after multistage Continuous Heat Transfer, then enter oxonation device continuation reaction.
6th step, hydrogenation process: enter hydrogenator after the light constituents such as the isolated ritalin in described ritalin rectifying tower top portion and hydrogen are mixed into hydrogenation reaction unstripped gas, carry out hydrogenation reaction in the presence of a hydrogenation catalyst, methanol and ethanol; The temperature of described hydrogenation reaction is 190 ~ 320 DEG C, and reaction pressure is 1 ~ 10MPa.
Preferably, the temperature of described hydrogenation reaction is 210 ~ 280 DEG C, and reaction pressure is 2 ~ 6MPa.
Described hydrogenator is fixed-bed reactor or fluidized-bed reactor, is preferably fixed-bed reactor, is particularly preferably board-like fixed-bed reactor.
The carrier of described hydrogenation catalyst is SiO
2, the activeconstituents of described hydrogenation catalyst and content are respectively CuO:5 ~ 50wt%, ZnO:0 ~ 20wt% and Mo
2o
3: 0 ~ 5wt%.
Preferably, in described hydrogenator, liquid mass space time velocity is 1 ~ 3Kg/Kg.h.
Preferably, described hydrogenator is provided with heat-exchange system; The heat-exchange system of described hydrogenator comprises hydrogenator outlet interchanger and hydrogenator inlet heat exchanger.
Preferably, after the multistage Continuous Heat Transfer of heat-exchange system of described hydrogenation reaction unstripped gas also through described hydrogenator before entering hydrogenator reaches the beds inlet temperature of described hydrogenator, then enter described hydrogenator and carry out hydrogenation reaction.
Preferably, the reaction product of described hydrogenation reaction is drawn from the bottom of hydrogenator, after the heat exchange of described hydrogenator outlet interchanger, enters water cooler and is cooled to 30-50 DEG C further, then enter gas-liquid separator and carry out gas-liquid separation; Supercharging after described gas-liquid separator top gas phase discharge unit non-condensable gas, then mix with described hydrogenation reaction unstripped gas, heat-exchange system heat exchange Posterior circle through described hydrogenator continues reaction to hydrogenator, and described gas-liquid separator bottom liquid phases enters thick alcohol tank or directly enters methyl acetate recovery tower.
7th step, alcohol product treating process: the reaction product of described hydrogenation reaction is drawn from the bottom of hydrogenator, is introduced into methyl acetate recovery tower, distills out ritalin etc.; The mixed solution that described methyl acetate recovery tower tower reactor is drawn enters the further separating-purifying of alcohol product tower, obtains alcohol product.
Preferably, the tower top temperature of described methyl acetate recovery tower 58 ~ 70 DEG C, bottom temperature 80 ~ 160 DEG C, pressure is normal pressure.
Preferably, the tower top temperature of described alcohol product tower 58 ~ 70 DEG C, bottom temperature 70 ~ 100 DEG C, pressure is normal pressure.
Preferably, the light constituent that described methyl acetate recovery top of tower is drawn is divided into the liquid phase light constituent containing ritalin and the non-condensable gas containing dme and a small amount of ritalin etc. after one or more levels cooling; Described liquid phase light constituent enters described hydrogenator after mixing with described hydrogenation reaction unstripped gas continues to react, and enters described oxonation device continue to react after described non-condensable gas pressurization with described oxonation unstripped gas after mixing.
Preferably, the light constituent such as the described alcohol product column overhead methyl alcohol of drawing and described flash tank or the isolated crude carbinol of methanol rectification separating technology unit or refined methanol are mixed into described reactive distillation column and continue to react.
Technique effect of the present invention and advantage are:
The present invention uses commercial syngas synthesizing methanol, then Catalytic dehydration of methanol reactive distillation generates dme, then h-mordenite (H-MOR) is used, Dimethyl ether carbonylation is made to generate ritalin (MA), and then make the ritalin of generation repeated hydrogenation on copper-based catalysts, generate ethanol and methyl alcohol, the technological process that methanol loop uses.Wherein, dme technique unit adopts the method for catalytic distillation, realize the combination of the mode of catalyzed reaction and separation coupling, save facility investment and separating energy consumption, simplify flow process, effectively utilize reaction heat, timely separated product is conducive to Dehydration of methanol and balances and the generation suppressing side reaction; Due to the existence of Dehydration of methanol, be more conducive to boiling point close to or reaction system in the separation of azeotrope, per pass conversion is high, and significantly reduce the load of thick product separation, shorten Production Flow Chart, production energy consumption also significantly reduces; Dimethyl ether carbonylation ritalin technique unit, catalyzer is conventional non-precious metal catalyst, and reaction conditions is gentle, and reaction mass corrodibility is little, low equipment investment, and technology mode is novel, and production efficiency is high; Ritalin preparation of ethanol by hydrogenating technique unit technological reaction mild condition, be separated easily, energy consumption is low, less investment, energy consumption are low, catalyzer is conventional copper based composite catalyst and cost is lower.Meanwhile, because the corrodibility of its raw material and product is more weak, can adopt carbon steel material, investment cost reduces greatly.Adopt this process operation process cost cheap, especially in technological process, involved catalyzer is common non-precious metal catalyst, and comparatively other operational path generally uses noble metal catalyst to have clear superiority.It is estimated, this technological equipment investment is only the 1/2 even lower of acetic acid direct hydrogenation ethanol, and its production cost, lower than standard biologic fermentation legal system ethanol technology, is the operational path of most possible industrialization at present.Seriously superfluous for the current Domestic DME production capacity of solution, the serious inversion phenomenon of production and marketing price is significant.
The present invention adopt catalyzer, because per pass conversion is high, selectivity is good, simplify intermediate fractionation process.Technical process arranges and has taken into full account heat releasing unit and the coupling with hot cell, greatly can reduce comprehensive energy consumption.Facility investment is few, environmental friendliness, and preparation technology is simple, economical and practical.
Accompanying drawing explanation
A kind of synthetic gas of Fig. 1 is indirectly produced ethanol schema and is divided Fig. 1
A kind of synthetic gas of Fig. 2 is indirectly produced ethanol schema and is divided Fig. 2
A kind of synthetic gas of Fig. 3 is indirectly produced ethanol schema and is divided Fig. 3
Reference numeral:
A methanol reactor; B methanol reactor inlet heat exchanger; C methanol reactor outlet interchanger; D water cooler; E gas-liquid separator; F flash tank; G preheater; H reactive distillation column; I methanol distillation column; J oxonation device; K oxonation device inlet heat exchanger; L oxonation device outlet interchanger; M water cooler; N gas-liquid separator; O dme recovery tower; P ritalin rectifying tower; Q hydrogenator; R hydrogenator inlet heat exchanger; S hydrogenator outlet interchanger; T water cooler; U gas-liquid separator; V methyl acetate recovery tower; W alcohol product tower.
Embodiment
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can do any change or amendment to the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after having read the content that the present invention tells about.
The experimental technique of unreceipted actual conditions in embodiment below, usually conveniently condition, as: chemical industry operation handbook, or according to the condition that manufacturer advises.
As shown in Figure 1-2, a kind of synthetic gas provided by the present invention technical process of indirectly preparing ethanol is as follows:
From the CO of the pipeline 1 and H of pipeline 2
2enter pipeline 3 after converging, and enter pipeline 4 after mixing with the circulation gas from pipeline 8.Gas mixture in pipeline 4 is successively after methanol reactor outlet interchanger C and methanol reactor inlet heat exchanger B Continuous Heat Transfer, passed into by the top of pipeline 5 from methanol reactor A, carry out catalyzing and synthesizing methyl alcohol reaction, after its reaction product is entered and is carried out heat exchange with the gas mixture from pipeline 4 by pipeline 6 in methanol reactor outlet interchanger C, enter water cooler D through pipeline 7 and after being cooled to specified temperature, entering gas-liquid separator E and carry out gas-liquid separation.The discharging of gas-liquid separator E top gas phase by supercharging after pipeline 9 discharge unit non-condensable gas, is circulated to pipeline 4 through pipeline 8, and bottom liquid phases crude carbinol then after reducing valve decompression, carries out liquid phase separation at flash tank F by pipeline 10; The non-condensable gas such as methane, hydrogen be separated through flash tank F speeds to be put into extraneous recycling by pipeline 48; Liquid phase crude carbinol is then flowed out by pipeline 11, and enter pipeline 12 after converging with the methyl alcohol reclaimed from pipeline 45 and pipeline 18, then through preheater G be preheated to converge with the methyl alcohol of to be drawn by the tower top side line 14 of reactive distillation column H after bubble point temperature after to pass into the bottom of reactive distillation column H through pipeline 13, in the reactive distillation column H that solid super-strong acid filler is housed, carry out the reactive distillation processes of dimethyl ether preparation by dehydrating methyl alcohol; The major part backflow after three grades of condensations of reactive distillation column H tower top dme, a small amount of light constituent such as methyl alcohol and water returns in tower, and noncondensable gas is honored as a queen through overhead water and is delivered to extraneous recovery system through pipeline 15, and all the other enter pipeline 16.Unreacted methyl alcohol drawn by the tower top side line 14 of reactive distillation column H.The heavy constituents such as reactive distillation column H tower reactor methyl alcohol, water enter methanol distillation column I by pipeline 17 and carry out Methanol Recovery.The impurity such as the methyl alcohol that methanol distillation column I tower top is drawn imports pipeline 12 through pipeline 18 after condensation extraction, the water that methanol distillation column I tower reactor is discharged deliver to extraneous process.From the CO of the pipeline 49 and H of pipeline 47
2be mixed into pipeline 21, the component such as the dme from pipeline 16 and the recovery dme from pipeline 43 and pipeline 29 enters pipeline 20 after converging, and with CO and H from pipeline 21
2mixing raw material gas and from pipeline 26 circulation gas mixing after, oxonation device outlet interchanger L is entered through piping 22, enter the further heat exchange of oxonation device inlet heat exchanger K from pipeline 23, enter oxonation device J after reaching oxonation device J beds inlet temperature and carry out oxonation.Oxonation product enters oxonation device outlet interchanger L and oxonation raw material heat exchange by pipeline 24, then enters after water cooler M cools further through pipeline 25, enters gas-liquid separator N and carry out gas-liquid separation.The discharging of gas-liquid separator N top gas phase is by supercharging after pipeline 27 discharge unit non-condensable gas, and be circulated to pipeline 22 through pipeline 26, the thick ester of bottom liquid phases enters dme recovery tower O through pipeline 28 and purify.The light constituents such as dme recovery tower O tower top dme and a small amount of ritalin, after extraction supercharging, be circulated to pipeline 20 by pipeline 29, the heavy constituent that tower reactor extraction contains a small amount of heteroacid etc. enters ritalin rectifying tower P through pipeline 30 and purifies further.The heavy constituent that the extraction of ritalin rectifying tower P tower reactor contains the heteroacid such as acetic acid is discharged to by pipeline 31 and out-of-bounds recycles, the ritalin light constituent that overhead extraction contains a small amount of methyl alcohol enters pipeline 32, then pipeline 33 is mixed into the ritalin circulation gas from pipeline 42, then with from pipeline 34 hydrogen and be mixed into hydrogenation reaction unstripped gas from the circulation gas of pipeline 39 and enter pipeline 35, after hydrogenator outlet interchanger S and hydrogenator inlet heat exchanger R two-stage Continuous Heat Transfer reach hydrogenator beds inlet temperature, row hydrogenation reaction is carried out from its top feed of hydrogenator Q.Hydrogenation reaction product is drawn bottom hydrogenator Q, enters after hydrogenator outlet interchanger S heat exchange through pipeline 37, is entered enter gas-liquid separator U after water cooler T is cooled to specified temperature and carry out gas-liquid separation by pipeline 38.Gas-liquid separator U top gas phase by after a part of non-condensable gas of the outer row of pipeline 40 through compressor boost, be then circulated to pipeline 35 through pipeline 39; Gas-liquid separator U bottom liquid phases then enters methyl acetate recovery tower V through pipeline 41 and carries out rectifying.The light constituent of methyl acetate recovery tower V overhead extraction is through condensation, and the non-condensable gas containing dme and a small amount of ritalin etc. is circulated to pipeline 20 through pipeline 43, is circulated to pipeline 33 after lime set extraction through pipeline 42.Enter alcohol product tower W through pipeline 44 after the extraction of methyl acetate recovery tower V tower reactor heavy constituent to purify further; The light constituents such as the methyl alcohol of alcohol product tower W overhead extraction are circulated to pipeline 12 through pipeline 45, and tower reactor is then discharged qualified alcohol product and delivered to alcohol product storage tank.
As another preferred embodiment, above-mentioned flash tank F can be replaced methanol rectification separating technology unit, two tower rectifying or the three-tower rectifications namely connected successively by pipeline, as shown in Figure 3.
Embodiment 1
In the present embodiment with reference to the device shown in accompanying drawing 1-2 and each reaction component of flow setting.
Methanol reactor A is board-like fixed-bed reactor, internal diameter 40mm, and height 1800mm, in-built Cu-Zn-Al system catalst for synthesis of methanol (consists of CuO 15wt%, ZnO 65wt% and Al
2o
320wt%); Reaction zone temperature is 225 ~ 265 DEG C, and reaction pressure is 5MPa;
Industry carbon monoxide (purity is 98V%) and H
2(purity is 99.9V%) by volume 2.7:1 is mixed into synthetic gas, carry out catalyzing and synthesizing methyl alcohol reaction from the tower top charging of methanol reactor A after methanol reactor outlet interchanger C and methanol reactor inlet heat exchanger B Continuous Heat Transfer reach the beds inlet temperature 195 DEG C of methanol reactor A, bottom reaction product discharging, after methanol reactor outlet interchanger C and raw material of synthetic gas carry out heat exchange, enters after water cooler D is cooled to 30-50 DEG C and enters gas-liquid separator E; Gas-liquid separator E top gas phase (composition: hydrogen 77.49V%, CO 9V%, CO
21.74V%, nitrogen 9.99V%, other gas 1.78V%) discharge a small amount of non-condensable gas after supercharging and raw material of synthetic gas mixed cycle use; Out the consisting of of lime set bottom gas-liquid separator E: methyl alcohol 90.77wt%, water 8.78wt%, CO
20.4wt%, other 0.05wt%.
Bottom gas-liquid separator E, lime set imports to flash tank F(internal diameter 32mm after reducing valve decompression, height 1500mm) in, carry out liquid phase separation, gas phase non-condensable gas is discharged into extraneous uniform effluent, liquid phase (composition: methyl alcohol 90.77wt%, water 8.78wt%, other component 0.45wt%) bubble point temperature (under 0.8MPa) that is heated to methyl alcohol through preheater G enters in heat insulation tank and stores, and then carries out reaction of preparing dimethyl ether from methanol by dehydration from the 43rd piece of column plate charging of reactive distillation column H.
Described reactive distillation column H(internal diameter 40mm, height 4000mm) be compression rectification tower, interior filling 50 pieces of theoretical plate height huddle saddle-shape solid super-strong acid filler; Described solid super-strong acid filler is self-made fill: be first by (NH4)
2s
2o
8be immersed on nano-beta molecular sieve that particle diameter is 60-80nm, make catalyst nano level powder (particle diameter is 68 ~ 80nm), adopt mechanically mixing mode by the 60:35:5 mixing in mass ratio of described catalyst nano level powder, ceramic material and adhesive aid (Vltra tears or sesbania powder), then mediate, after shaping, drying, roasting 4h at 550 DEG C and obtaining, it is of a size of 5mm × 5mm, filler particles average load super acids active centre 0.6wt%.
In reactive distillation column H, the liquid of methyl alcohol and steam huddle counter current contact on saddle-shape solid super-strong acid filler described, and filler occurs dewatering preparing dimethy ether reaction, and reaction zone temperature is 120 DEG C ~ 220 DEG C, and pressure is 1.5MPa, and methanol solution hourly space velocity is 4.5h
-1, reflux ratio is 2.5; Unreacted methyl alcohol is drawn from the tower top side line being positioned at the 2nd block of column plate, with the liquid-phase mixing from flash tank F, is circulated to reactive distillation column H and continues reaction; Top gaseous phase adopts three grades of condensations, and (first step condensing temperature is 40 DEG C, second stage condensing temperature is normal temperature, the third stage is chilled to-26 DEG C with ethylene glycol refrigerant), noncondensable gas is honored as a queen through overhead water and is delivered to extraneous recovery system, oxonation device J is entered after tower top discharging (composition: dme 99.9wt%, other 0.1wt%) goes out tower; Reactive distillation column H tower reactor discharging (composition: methyl alcohol 71.8wt%, other heavy constituents 28.2% such as the water that reaction generates) enters methanol distillation column I(atmospheric distillation tower after extraction: internal diameter 32mm, height 3000mm); Methanol distillation column I tower reactor is discharged the impurity such as water and is delivered to extraneous process, and methyl alcohol and the liquid-phase mixing from flash tank F of methanol distillation column I overhead extraction, be circulated to reactive distillation column H and continue reaction.
Described oxonation device J is board-like fixed-bed reactor, internal diameter 40mm, height 1800mm, interior filling oxonation catalyzer (H-MOR 90wt%, coagent composition CuO9wt%, CoO 0.5wt%, Mo
2o
30.5wt%), reaction zone temperature 230 ~ 300 DEG C, reaction pressure is 5MPa.
After the discharging of reactive distillation column H tower top is pressurized to 5MPa, and from the CO of carbon monoxide house steward (purity is 98v%) and the H of hydrogen manifold
2(purity is 99.9v%) mixing, after oxonation device outlet interchanger L and oxonation device inlet heat exchanger K Continuous Heat Transfer, reaches beds inlet temperature and enters the oxonation that oxonation device J carries out dme and CO; Dme, CO and H in tower
2raw materials components mole ratio is 1:60:15, and in tower, liquid mass space time velocity is 0.2Kg/Kg.h; Oxonation product is drawn after oxonation device outlet interchanger L and cold raw material carry out heat exchange at the bottom of tower, enters after water cooler M is cooled to 30 ~ 50 DEG C and enters gas-liquid separator N; From gas-liquid separator N top gas phase out (composition: 76v% carbon monoxide, 19.5v% hydrogen, 2.5v% nitrogen, 1.2v% dme, 0.5v% methane, 0.3v% other) supercharging after the noncondensable gas of discharge 0.05%, mix with from the discharging of reactive distillation column H tower top and follow V ring and continue to react to oxonation device J; Bottom gas-liquid separator N, out lime set consists of: ritalin 78.2wt%, dme 16.3wt%, methyl alcohol 1.2wt%, heteroacid 3.4wt%, other 0.9wt%.
Bottom gas-liquid separator N, lime set out imports to dme recovery tower O(internal diameter 32mm, height 3000mm, tower top temperature about 65 DEG C, and column bottom temperature is 120 DEG C, and tower reactor pressure is 0.6MPa); The light constituent pressurization Posterior circle such as the dme that dme recovery tower O tower top steams continue reaction to oxonation device J, (the composition: ritalin 94.6wt% of heavy constituent at the bottom of tower, heteroacid 5.4wt%) enter into ritalin rectifying tower P(internal diameter 32mm, height 3000mm, tower top temperature 65 DEG C, bottom temperature 140 DEG C, pressure is normal pressure) carry out rectifying; Draw at the bottom of ritalin rectifying tower P tower and deliver to extraneous recycling containing the polynary heteroacid of heavy constituent, tower top discharging consists of: ritalin 99.5wt%, other 0.5wt%.
The discharging of ritalin rectifying tower P tower top is after being pressurized to 3MPa, mix with the hydrogen (purity is 99.9%) from hydrogen manifold, after hydrogenator outlet interchanger S and hydrogenator inlet heat exchanger R Continuous Heat Transfer, from the board-like fixed-bed reactor of hydrogenator Q(, internal diameter 40mm, height 1800mm) its top feed, hydrogenation catalyst (composition: CuO 32wt%, ZnO 15wt%, Mo
2o
33wt%, SiO
2under existence 50wt%), carry out hydrogenation reaction, reaction zone temperature is 190 ~ 250 DEG C, and reaction pressure is 3MPa, and liquid hourly space velocity is 3Kg/kg.h.
Hydrogenation reaction product is drawn after hydrogenator outlet interchanger S and cold raw material carry out heat exchange bottom hydrogenator Q, enters water cooler T and is cooled to 30 ~ 50 DEG C, then enter gas-liquid separator U; From gas-liquid separator U top gas phase out, (volume forms: hydrogen 99v%, methane 0.05v%, nitrogen 0.02v%, carbon monoxide 0.02v%, other 0.91v%) discharge supercharging after the non-condensable gas of 0.05%, continue to react to hydrogenator Q with hydrogenation reaction unstripped gas mixed cycle; Bottom gas-liquid separator U, lime set quality group out becomes: ethanol 59.3wt%, methyl alcohol 38.2wt%, ritalin 1.1wt%, vinyl acetic monomer 0.9wt%, other 0.5wt%.
Bottom gas-liquid separator U, lime set out imports to methyl acetate recovery tower V(atmospheric distillation tower, internal diameter 32mm, height 3000mm, tower top temperature about 65 DEG C, and column bottom temperature is 120 DEG C); The discharging of methyl acetate recovery tower V top gaseous phase is after condensation, and the non-condensable gases such as dme are circulated to oxonation device J to be continued to utilize, and ritalin lime set continues reaction through supercharging Posterior circle to hydrogenator Q; Liquid phase (weight consists of: methyl alcohol 38.9wt%, ethanol 60.8wt%, other 0.3wt%) at the bottom of methyl acetate recovery tower V tower, enter into alcohol product tower W(atmospheric distillation tower, internal diameter 32mm, height 3000mm, tower top temperature 64 DEG C, column bottom temperature is 85 DEG C) carry out rectifying; Alcohol product tower W tower top discharging (composition: methyl alcohol 98.5wt%, other 1.5wt%) is circulated to reactive distillation column H and continues reaction; Discharging at the bottom of alcohol product tower W tower is the process of alcohol products of purity >=92.1% (V/V).
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 without prejudice under spirit of the present invention and category, can modify above-described embodiment or changes.Therefore, have in all art usually know the knowledgeable do not depart from complete under disclosed spirit and technological thought all equivalence modify or change, must be contained by claim of the present invention.
Claims (25)
1. synthetic gas produces a technique for ethanol indirectly, it is characterized in that, comprises the following steps:
(1) synthetic gas that hydrogen and technical grade carbon monoxide are mixed to form is passed into from the top of methanol reactor, carry out catalyzing and synthesizing methyl alcohol reaction under the existence of catalst for synthesis of methanol; In described methanol reactor, temperature of reaction is 200 ~ 300 DEG C, and reaction pressure is 3 ~ 12MPa;
(2) synthesizing methanol reaction product in described methanol reactor is passed into the rough segmentation that methyl alcohol is carried out in flash tank flash separation, or pass into methanol rectification separating technology unit and carry out the refining of methyl alcohol;
(3) described flash tank or the isolated crude carbinol of methanol rectification separating technology unit or refined methanol are after preheater preheats to the bubble point temperature of methyl alcohol, pass into the reactive distillation processes carrying out dimethyl ether preparation by dehydrating methyl alcohol from the bottom of the reactive distillation column that solid super-strong acid filler is housed;
(4) dme of described reactive distillation column overhead extraction and hydrogen, industrial carbon monoxide are mixed into oxonation unstripped gas and enter oxonation device, under carbonylation catalyst exists, carry out oxonation generate ritalin;
(5) reaction product of described oxonation is drawn bottom oxonation device, enters the rectifying of dme recovery tower and reclaims dme; The top extraction of dme recovery tower contains the light constituent of dme and a small amount of ritalin, and bottom liquid heavy constituent enters the further separating-purifying of ritalin rectifying tower;
(6) enter hydrogenator after isolated for described ritalin rectifying tower top portion light constituent containing ritalin and hydrogen being mixed into hydrogenation reaction unstripped gas, carry out hydrogenation reaction in the presence of a hydrogenation catalyst, methanol and ethanol; The temperature of described hydrogenation reaction is 190 ~ 320 DEG C, and reaction pressure is 1 ~ 10MPa;
(7) reaction product of described hydrogenation reaction is drawn from the bottom of hydrogenator, enters methyl acetate recovery tower, reclaims the light constituent containing ritalin; Described methyl acetate recovery tower tower bottoms body weight component enters the further separating-purifying of alcohol product tower, obtains alcohol product;
In step (3), described solid super-strong acid filler is the ceramic packing that load has solid super-strong acid; Described solid super-strong acid is SO
4 2-/ beta-molecular sieve composite catalyst; Described solid super-strong acid filler is obtained by following steps: first, by (NH
4)
2s
2o
8be immersed on nano-beta molecular sieve, make nm-class catalyst powder; Then add ceramic material and adhesive aid mixes, then mediate, shaping; Namely dry, roasting obtains described solid super-strong acid filler again;
In step (4), described carbonylation catalyst is H-MOR, and coagent and content are CuO 0 ~ 30wt%, CoO 0.1 ~ 10wt%, Mo
2o
30.1 ~ 10wt%.
2. technique as claimed in claim 1, it is characterized in that, in step (1), the purity of described hydrogen and technical grade carbon monoxide is respectively 99.9V% and 98V%; The mixed volume of described hydrogen and technical grade carbon monoxide is than being 2-3.5:1.
3. technique as claimed in claim 1, it is characterized in that, in step (1), described methanol reactor is provided with heat-exchange system, the interchanger turnkey of described methanol reactor draws together methanol reactor outlet interchanger and methanol reactor inlet heat exchanger, after the multistage Continuous Heat Transfer of heat-exchange system of described synthetic gas also through described methanol reactor before entering methanol reactor reaches the beds inlet temperature of described methanol reactor, then enter described methanol reactor and carry out catalyzing and synthesizing methyl alcohol reaction.
4. technique as claimed in claim 1, it is characterized in that, in step (1), the described bottom discharge of product from methanol reactor catalyzing and synthesizing methyl alcohol reaction, after entering the heat exchange of described methanol reactor outlet interchanger, enter in water cooler and be cooled to 30 ~ 50 DEG C further, then enter gas-liquid separator and carry out gas-liquid separation; Supercharging after described gas-liquid separator top gas phase discharge unit non-condensable gas, then mixes with described synthetic gas, and the heat-exchange system heat exchange Posterior circle through described methanol reactor continues reaction to methanol reactor; Described gas-liquid separator bottom liquid phases crude carbinol enters follow-up methyl alcohol rough segmentation or treating process.
5. technique as claimed in claim 1, it is characterized in that, in step (1), described catalst for synthesis of methanol is Cu-Zn-Al series catalysts, and the carrier of described catalyzer is Al
2o
3be 10 ~ 30w t%, the activeconstituents of described catalyzer and content are respectively CuO:5 ~ 30wt% and ZnO:10 ~ 70wt%.
6. technique as claimed in claim 1, it is characterized in that, in step (2), in described methanol reactor, synthesizing methanol reaction product reduces pressure through reducing valve before passing into flash tank, then in flash tank, gas-liquid separation is carried out, isolated noncondensable gas discharges the external world and recycles, and isolated lime set is crude carbinol.
7. technique as claimed in claim 1, it is characterized in that, in step (2), described methanol rectification separating technology unit is two tower rectifying or three-tower rectifications, obtains refined methanol after separation.
8. technique as claimed in claim 1, it is characterized in that, in step (3), described reactive distillation column theoretical plate number is 9 ~ 50 pieces, tower top pressure is 0.5 ~ 1.8MPa, and bottom temperature is 100 ~ 300 DEG C, and the temperature of main reaction region is 120 ~ 220 DEG C, control of reflux ratio is 0.01 ~ 3.0, and methanol solution hourly space velocity is 2.5 ~ 30h
-1.
9. technique as claimed in claim 1, it is characterized in that, in step (3), the mixed solution of described reactive distillation column tower reactor extraction enters methanol distillation column, the methanol distillation column tower reactor impurity of discharging containing water delivers to extraneous process, and the methyl alcohol of methanol distillation column overhead extraction continues to react with described flash tank or the isolated crude carbinol of methanol rectification separating technology unit or refined methanol mixing Posterior circle to reactive distillation column.
10. technique as claimed in claim 1, it is characterized in that, in step (3), in described reactive distillation column, unreacted methyl alcohol is drawn through tower top side line, and mix with described flash tank or the isolated crude carbinol of methanol rectification separating technology unit or refined methanol, be circulated to reactive distillation column and continue reaction; Described tower top side line is positioned at the 1st ~ 5th piece of column plate place of reactive distillation column.
11. techniques as claimed in claim 1, it is characterized in that, in step (3), described reactive distillation column overhead light constituent contains dme, a small amount of methyl alcohol and water and is overflowed by tower top, after multi-stage condensing, most of dme, first alcohol and water and a small amount of impurity are condensed and return in tower, noncondensable gas is honored as a queen through overhead water and is delivered to extraneous recovery system, and all the other enter oxonation device and carry out oxonation.
12. techniques as claimed in claim 1, is characterized in that, the particle diameter of described nano-beta molecular sieve is 68 ~ 80nm; Described adhesive aid is selected from Vltra tears, sesbania powder and carboxymethyl cellulose; The temperature of described roasting is 500 ~ 600 DEG C, and the time of roasting is 3 ~ 6h; Average load super acids active centre 0.58 ~ 0.62wt% on described filler particles; Described solid super-strong acid filler is of a size of 3 ~ 5mm × 3 ~ 5mm.
13. technique as claimed in claim 1, it is characterized in that, in step (4), described oxonation device is fixed-bed reactor or fluidized-bed reactor; The temperature of described oxonation is 150 ~ 350 DEG C, and reaction pressure is 1 ~ 8Mpa; In described oxonation device, dme, CO and H
2raw materials components mole ratio is 1 ~ 5:50 ~ 90:1 ~ 20; In described oxonation device, liquid mass space time velocity is 0.15 ~ 0.3Kg/Kg.h.
14. techniques as claimed in claim 1, is characterized in that, in step (4), described oxonation device is provided with heat-exchange system; The heat-exchange system of described oxonation device comprises oxonation device outlet interchanger and oxonation device inlet heat exchanger; After the multistage Continuous Heat Transfer of heat-exchange system of described oxonation unstripped gas also through described oxonation device before entering oxonation device reaches the beds inlet temperature of described oxonation device, then enter described oxonation device and carry out oxonation.
15. techniques as claimed in claim 14, it is characterized in that, in step (4), the reaction product of described oxonation is drawn bottom oxonation device, after entering the heat exchange of described oxonation device outlet interchanger, enter water cooler and be cooled to 30-50 DEG C further, then enter gas-liquid separator and carry out gas-liquid separation; Supercharging after described gas-liquid separator top gas phase discharge unit non-condensable gas, then mix with described oxonation unstripped gas, heat-exchange system heat exchange Posterior circle through described oxonation device continues reaction to oxonation device, and described gas-liquid separator bottom liquid enters thick ester tank or directly enters the separation and purification that dme recovery tower carries out oxonation product.
16. techniques as claimed in claim 1, is characterized in that, in step (5), the operational condition of described dme recovery tower is tower top temperature 58 ~ 70 DEG C, bottom temperature 100 ~ 150 DEG C, and pressure is 0.3 ~ 0.8MPa; The operational condition of described ritalin rectifying tower is tower top temperature 58 ~ 65 DEG C, and bottom temperature 130 ~ 170 DEG C, pressure is normal pressure.
17. techniques as claimed in claim 1, it is characterized in that, in step (5), mix with described oxonation unstripped gas after the dme supercharging of described dme recovery tower top extraction, after the heat-exchange system of oxonation device reaches the beds inlet temperature of oxonation device after multistage Continuous Heat Transfer, then enter oxonation device continuation reaction.
18. techniques as claimed in claim 1, is characterized in that, in step (6), described hydrogenator is fixed-bed reactor or fluidized-bed reactor; In described hydrogenator, liquid mass space time velocity is 1 ~ 3Kg/Kg.h.
19. techniques as claimed in claim 1, is characterized in that, in step (6), the carrier of described hydrogenation catalyst is SiO
2, the activeconstituents of described hydrogenation catalyst and content are respectively CuO:5 ~ 50wt%, ZnO:0 ~ 20wt% and Mo
2o
3: 0 ~ 5wt%.
20. techniques as claimed in claim 1, it is characterized in that, in step (6), described hydrogenator is provided with heat-exchange system; The heat-exchange system of described hydrogenator comprises hydrogenator outlet interchanger and hydrogenator inlet heat exchanger; After the multistage Continuous Heat Transfer of heat-exchange system of described hydrogenation reaction unstripped gas also through described hydrogenator before entering hydrogenator reaches the beds inlet temperature of described hydrogenator, then enter described hydrogenator and carry out hydrogenation reaction.
21. techniques as claimed in claim 20, it is characterized in that, in step (6), the reaction product of described hydrogenation reaction is drawn from the bottom of hydrogenator, after the heat exchange of described hydrogenator outlet interchanger, enter water cooler and be cooled to 30-50 DEG C further, then enter gas-liquid separator and carry out gas-liquid separation; Supercharging after described gas-liquid separator top gas phase discharge unit non-condensable gas, then mix with described hydrogenation reaction unstripped gas, heat-exchange system heat exchange Posterior circle through described hydrogenator continues reaction to hydrogenator, and described gas-liquid separator bottom liquid phases enters thick alcohol tank or directly enters methyl acetate recovery tower.
22. techniques as claimed in claim 1, is characterized in that, in step (7), and the tower top temperature of described methyl acetate recovery tower 58 ~ 70 DEG C, bottom temperature 80 ~ 160 DEG C, pressure is normal pressure; The tower top temperature of described alcohol product tower 58 ~ 70 DEG C, bottom temperature 70 ~ 100 DEG C, pressure is normal pressure.
23. techniques as claimed in claim 1, it is characterized in that, in step (7), the light constituent that described methyl acetate recovery top of tower is drawn is divided into the liquid phase light constituent containing ritalin and contains the non-condensable gas of dme and a small amount of ritalin after one or more levels cooling; Described liquid phase light constituent enters described hydrogenator after mixing with described hydrogenation reaction unstripped gas continues to react, and enters described oxonation device continue to react after described non-condensable gas pressurization with described oxonation unstripped gas after mixing.
24. techniques as claimed in claim 1, it is characterized in that, in step (7), the light constituent containing methyl alcohol that described alcohol product column overhead is drawn and described flash tank or the isolated crude carbinol of methanol rectification separating technology unit or refined methanol are mixed into described reactive distillation column to be continued to react.
25. as arbitrary in claim 1-24 as described in technique produced the application in ethanol by synthetic gas.
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