CN103570492B - The technique of the crude methyl acetate hydrogenation of net product ethanol of by-product and system in a kind of polyvinyl alcohol production process - Google Patents
The technique of the crude methyl acetate hydrogenation of net product ethanol of by-product and system in a kind of polyvinyl alcohol production process Download PDFInfo
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- 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
Abstract
The invention provides technique and the system of the crude methyl acetate hydrogenation of net product ethanol of by-product in a kind of polyvinyl alcohol production process.The technique of the crude methyl acetate hydrogenation of net product ethanol of by-product in described polyvinyl alcohol production process, it comprises: the ritalin of by-product in polyvinyl alcohol production process and the mixture of methyl alcohol and hydrogen are added to reaction unit, makes ritalin and hydrogen carry out reaction and generate ethanol and by-product methyl alcohol; The gas material of hydrogen and the liquid material containing ethanol, methyl alcohol, ritalin, a small amount of water is isolated from the outputting material of described reaction unit; Speed to bleed off partial gas material from the gas material of described hydrogen, most of gas material circulation enters described reaction unit; From described containing recovery of acetic acid methyl esters-methanol azeotropic material and the mixture containing methyl alcohol, ethanol, a small amount of water the liquid material of ethanol, methyl alcohol, ritalin, a small amount of water; Methanol charge and the ethanol material containing a small amount of water is isolated from the mixture of described methyl alcohol, ethanol, a small amount of water; Dehydrated alcohol product is obtained containing being separated the ethanol material of a small amount of water from described.
Description
[technical field]
The present invention relates to technique and the system of the crude methyl acetate hydrogenation of net product ethanol of by-product in a kind of polyvinyl alcohol production process.
[background technology]
Polyvinyl alcohol (Po1yviny1A1coho1, be called for short PVA, structural formula:
) be a kind of high molecular weight water soluble polymer, performance is between plastics and rubber, be mainly used to produce polymer builder, tackiness agent, spinning sizing agent, paper coating and vinylon fiber etc., have a wide range of applications in building, coating, weaving, papermaking, wood working, printing, food, medicine and the industry such as metallurgical, have the title of " economic climate " in the industry.
Polyvinyl alcohol is made up through polymerization alcoholysis of vinyl acetate, and polyvinyl alcohol produces containing a large amount of ritalins and methyl alcohol in alcohol liquid waste solution, usually often produces 1 ton of polyvinyl alcohol by-product about 1.68 tons of ritalins (Methyl Acetate).Because ritalin industry consumption is limited, current most of manufacturer for the recycling of ritalin all first by the alcoholysis liquid (mixture of ritalin and methyl alcohol, be called for short crude methyl acetate product) azeotropic distillation, obtain ritalin and methyl alcohol azeotrope (as, under normal pressure, quality group becomes ritalin 82.3wt%, methyl alcohol 17.7wt%), adopt catalyzing cation exchange resin hydrolysis method to make it be hydrolyzed to acetic acid and methyl alcohol the ritalin of higher degree again, acetic acid is through recycling Posterior circle to vinyl acetate synthesis operation.But the hydrolysis reaction due to ritalin is balanced reaction, equilibrium constant K value very little (0.12 ~ 0.17), per pass conversion is low, and relate to the separation of multicomponent system, cause that equipment in recovery process is many, energy consumption is large, cost is high, polyvinyl alcohol energy consumption of unit product is increased, reduces the economy of polyvinyl alcohol.Manufacturer actively seeks to improve percent hydrolysis, reduce the technological method such as energy consumption always for this reason, as publication number be the Chinese patent application process modification method and apparatus of methyl acetate hydrolysis " in " of CN101130482A, the Chinese patent application " method of methyl acetate hydrolysis " of publication number to be the Chinese patent application " a kind of new hydrolysis coupling process of methyl acetate and specific equipment thereof " of CN101704733A and publication number be CN102190556A all discloses different technical schemes.Although increase through improving methyl acetate hydrolysis rate, the energy consumption of acetic acid recovery workshop section still accounts for 50 ~ 60% of polyvinyl alcohol plant energy consumption.Along with polyvinyl alcohol industrial expansion, the contradiction between the huge energy consumption of hydrolysis recovery of acetic acid methyl esters and the requirement of synergy of expanding production is more and more obvious.
On the other hand, a kind of polyvinyl alcohol by-product alcohol liquid waste solution solution adopts separation of extractive distillation to go out high-purity ritalin as industrial raw material, while attempting to reduce polyvinyl alcohol energy consumption of unit product, alleviates the pressure of commercial synthesis ritalin.The method of current report has the separation method such as solution technique extracting rectifying, extractive distillation with salt, composite salts extraction rectifying, as publication number be the Chinese patent application " the ionic liquid intermittent extraction, distillation and separation method of Data for Methyl Acetate-Methanol mixture " of CN102180791A, publication number is the Chinese patent application " method of two strands of solvent side entry feed separation of extractive distillation method separating methyl acetate and methanol-water and equipment thereof " of CN102120719A.But expand along with the production capacity of ritalin industry, there is problem of excess production capacity in current China ritalin, because consumption structure considerable change does not occur, do not form new demand growth point to support newly-increased production capacity, therefore to increase the too fast contradiction relatively lagged behind with demand outstanding day by day for ritalin production capacity.
From the angle of economy and the utilization of resources, hydrolysis recovery of acetic acid and extracting rectifying extract ritalin and all do not reach best resource reasonable disposition state, if using the crude methyl acetate product of by-product in polyvinyl alcohol production process as raw material, and then other Chemicals of synthesis high added value, then can explore the new way of the rational distribution of resources.
Ethanol is important large Organic chemical products, can be widely used in the industries such as medicine, food, fuel, chemical industry.Current ethanol consumption mainly concentrates on white wine and the large field of alcohol fuel two.In view of ethanol is the desirable free of contamination vehicle fuel of high-octane rating and additive thereof, have stimulated the quick growth in ethanol market greatly.According to European OECD (OECD) statistics, within 2007, global alcohol fuel output reaches 4.1 × 10
7t, comparatively increases 200% in 2000, is equivalent to nearly 3% of global gasoline consumption.Expect global alcohol fuel output in 2012 to double again than 2007.Brazil uses ethanol as automobile fuel or fuel dope for many years always, and in 2011, ethanol is brought up to the height of the strategic energy by the derived prods of general agricultural-food.China implements the popularization of ethanol petrol in multiple province in recent years, successful.Along with the raising of environmental quality requirement, developing alcohol ate and adding alcohol, ether has in the oil become the main outlet improving automobile fuel.
The production method of ethanol mainly contains fermentation method and chemical method.The main raw material of fermentation method is farm crop, obtains ethanol by utilizing the amylofermentation in farm crop; Chemical method mainly adopts the ethene of petroleum cracking gained to be raw material, produces ethanol by ethylene hydration.The current method ethanol production of China mainly adopts fermentation method, account for 96.5% of ethanol total amount, the method production cost is high, production capacity is lower, add the consumption of grain, in recent years China's food shortage and price increase problem become increasingly conspicuous day, make the corn of production ethanol, Ipomoea batatas etc. in short supply, cause the ton on the ground such as Shandong, Henan above alcohol production factory reduce or stop production.The raw materials used ethylene source of ethylene hydration method is in non-reproducible petroleum resources, by the restriction of petroleum resources worsening shortages, and production unit requires to have higher acidproof, withstand voltage properties, working condition and cost are all higher, objectively limit popularization and the development of the method.
Therefore develop non-grain route and Non oil-based route to produce ethanol and become people and pay close attention to and the focus of research, and there is important economic implications.Wherein, part research concentrates on the method that acetic acid direct hydrogenation prepares ethanol, if the patent No. is US4, 405, the United States Patent (USP) " Process for the production of alcohols from carboxylic acids " of 819, the patent No. is US7, 863, the United States Patent (USP) " Direct and selective production of ethanol from acetic acid utilizing a platinumtin catalyst " of 489, publication number is the Chinese patent application " a kind of catalyzer of acetic acid gas phase hydrogenation ethanol production " of CN102228831A, and Authorization Notice No. is that the Chinese patent of CN1027043C " is generated the catalytic hydrogenation catalyst of alcohol and/or ester " by carboxylic acid and acid anhydride thereof.But acetic acid has very strong corrodibility, require very high to the material of equipment, develop acetic acid first through the operational path of lactate synthesis acetic ester repeated hydrogenation synthesizing alcohol for this reason, this route only need utilize corrosion resistant material in the reactor part of acetic acid esterified, can avoid using erosion resistance equipment on a large scale, reduce cost of investment.As publication number be the Chinese patent application " a kind of method of acetic ester preparation of ethanol through hydrogenation " of CN102093162A, publication number is the Chinese patent application " a kind of Catalysts and its preparation method of acetic ester preparation of ethanol by hydrogenating and application " of CN101934228A.Visible, with carboxylicesters (with ritalin and vinyl acetic monomer in the majority) technique of preparation of ethanol through hydrogenation caused certain concern.
[summary of the invention]
An aspect of of the present present invention provides the technique of the crude methyl acetate hydrogenation of net product ethanol of by-product in a kind of polyvinyl alcohol production process, this technique comprises the following steps: the ritalin of by-product in polyvinyl alcohol production process and the mixture of methyl alcohol and hydrogen are added to reaction unit as raw material by (a), make ritalin and hydrogen carry out reaction and generate ethanol and methyl alcohol; B () isolates the gas material of hydrogen and the liquid material containing ethanol, methyl alcohol and ritalin from the outputting material of described reaction unit; C () obtains methyl acetate and methanol azeotropic material and contains the mixture of methyl alcohol and ethanol from described liquid material; And (d) isolates methyl alcohol and ethanol from described mixture.
Further, described technique also comprises: the gas material of at least part of described hydrogen is looped back described reaction unit.
Further, described technique also comprises: at least part of described methyl acetate and methanol azeotropic material is looped back described reaction unit.
Further, described step (b) comprising: the outputting material of described reaction unit is sent into knockout drum, isolates the gas material of hydrogen and the liquid material containing ethanol, methyl alcohol and ritalin.
Further, described step (c) comprising: the described liquid material containing ethanol, methyl alcohol and ritalin is sent into methanol distillation column, and tower top isolates the azeotropic material of methyl acetate and methanol, isolates the mixture containing methyl alcohol and ethanol at the bottom of tower.
Further, also containing water in described mixture, described step (d) comprising: from described mixture, isolate methyl alcohol and moisture ethanol, and separation obtains dehydrated alcohol product from described moisture ethanol.
Further, the described step isolating methyl alcohol and moisture ethanol from mixture comprises: the mixture of described methyl alcohol, ethanol, water is sent into methanol rectifying tower, and tower top isolates methyl alcohol, isolates moisture ethanol at the bottom of tower.
Further, the described step obtaining dehydrated alcohol product that is separated from moisture ethanol comprises: described moisture ethanol is sent into membrane separation apparatus separation and obtain dehydrated alcohol product.
Another aspect of the present invention provides the system of the crude methyl acetate hydrogenation of net product ethanol of by-product in a kind of polyvinyl alcohol production process, and this system comprises reaction unit, gas-liquid separation device and product separation device.In described reception hydrogen and polyvinyl alcohol production process, the ritalin of by-product and the mixture of methyl alcohol are as raw material, and make ritalin wherein and hydrogen carry out reaction to generate ethanol and methyl alcohol.Described gas-liquid separation device isolates the gas material of hydrogen and the liquid material containing ethanol, methyl alcohol and ritalin from the outputting material of described reaction unit.Described product separation device comprises raw materials recovery tower and refining methanol tower, and wherein raw materials recovery tower obtains methyl acetate and methanol azeotropic material and contains the mixture of methyl alcohol and ethanol from described liquid material; Refining methanol tower isolates methyl alcohol and ethanol material from described mixture.
Further, described system also comprises the circulation device isolated gas material of at least part of described gas-liquid separation device being looped back described reaction unit.
Further, described circulation device comprises compressor, is used for compressing it before described gas material is looped back described reaction unit.
Further, described system also comprises the circulation device at least part of methyl acetate and methanol azeotropic material obtained from described raw materials recovery tower being looped back described reaction unit.
Further, described ethanol material is moisture ethanol, and described product separation device also comprises film water trap, can be separated and obtain dehydrated alcohol product from described moisture ethanol.
Further, described reaction unit comprises mixing tank, reactor and discharging water cooler.Wherein said mixing tank is used for receiving, the ritalin of by-product and the mixture of methyl alcohol in mixing pre-hot hydrogen and polyvinyl alcohol production process; Described reactor is used for receiving from the material of described mixing tank, and makes ritalin wherein and hydrogen carry out reaction to generate ethanol and methyl alcohol; Described discharging water cooler, the material cooling being used for described reactor to export is rear sends into described gas-liquid separation device.
Further, described reaction unit comprises fixed-bed reactor.
Further, described fixed-bed reactor are two-part insulation fix bed reactor, the intersegmental interchangeable heat drop temperature of described two section reactor.
Further, described fixed-bed reactor comprise the insulation fix bed reactor of two or more series connection, and described two or more insulation fix bed reactor inter-stage is provided with heat exchange heat sink.
Further, described fixed-bed reactor are isothermal fixed-bed reactor.
Further, described isothermal fixed-bed reactor are shell-and-tube reactor or built-in coil reactor.
Further, the bielement nano O composite metallic oxide catalyst comprising copper and aluminium is mounted with in described fixed-bed reactor.
Further, be mounted with in described fixed-bed reactor and comprise copper, the ternary of aluminium and one or more transition metal or alkaline earth metal oxide or the above nano composite metal oxide of ternary.
Compared with prior art, the present invention has the following advantages:
1. the present invention utilizes the crude methyl acetate product of by-product in polyvinyl alcohol production process as raw material direct hydrogenation synthesizing alcohol, provide a kind of novel process of alcohol production, to avoid in direct acetic acid synthesized methyl esters process corrodibility strong, invest the shortcomings such as high, liquid waste disposal is difficult; In addition the traditional fermentation process mainly adopted with China is prepared compared with ethanol, and ethanol production process of the present invention is not by the impact of provision price fluctuating factor.
2. the invention solves the problem of outlet of the ritalin of by-product in polyvinyl alcohol production process, expanded ritalin derived product chain, the Chemicals dehydrated alcohol of synthesis high added value.This avoids in hydrolyzed pva recovery process on the one hand, and equipment is many, energy consumption is large, cost is high, the shortcoming that polyvinyl alcohol energy consumption of unit product is high; It also avoid on the other hand extracting rectifying and extract the contradiction of ritalin as industrial raw material and China's ritalin production capacity surplus.
3. catalyst stability of the present invention is good, has higher activity and selectivity, and reaction conditions is gentle, substantially increases the economy of ritalin preparation of ethanol by hydrogenating technique.
4. present invention process is simple, and with low cost, flexible operation, meets energy-conservation chemical industry requirement, be beneficial to industrial mass production requirement.
[accompanying drawing explanation]
Fig. 1 is system and the process flow diagram of the crude methyl acetate hydrogenation of net product ethanol being by-product in a kind of polyvinyl alcohol production process.
Fig. 2 is system and the process flow diagram of embodiment one and embodiment two.
Fig. 3 is system and the process flow diagram of embodiment three.
[embodiment]
Fig. 1 shows the technical process schematic diagram of the crude methyl acetate hydrogenation of net product ethanol of by-product in a kind of polyvinyl alcohol (PVA) production process, and it comprises: make ritalin and carbinol mixture and hydrogen reaction generate ethanol and methyl alcohol reaction unit 110, from the outputting material of described reaction unit 110, isolate the gas-liquid separation device 120 of gas and liquid material, from the liquid material that described gas-liquid separation device 120 exports, isolate the product separation device 130 of major product ethanol, byproduct methyl alcohol and unreacted ritalin.
Send into from the mixture of the ritalin obtained after azeotropic distillation in polyvinyl alcohol production process and methyl alcohol and hydrogen in reaction unit 101 as raw material, make it react under catalyst action and generate ethanol and methyl alcohol.Wherein, the expression formula of described reaction is:
CH
3COOCH
3+2H
2＝C
2H
5OH+CH
3OH
The ethanol that described reaction generates and methyl alcohol can may generate ethane and H with hydrogen reaction further respectively by the impact of temperature
2o, methane and water, the expression formula of described reaction is as follows:
C
2H
5OH+H
2＝CH
3CH
3+H
2O
CH
3OH+H
2＝CH
4+H
2O
Therefore, the outputting material of described reaction unit 110 at least comprises ethanol, methyl alcohol, hydrogen, ritalin, selectively, comprises ethanol, methyl alcohol, hydrogen, ritalin, ethane, methane, water.Described outputting material is sent in gas-liquid separation device 120 isolate containing major product ethanol, byproduct methyl alcohol, unreacted ritalin liquid material and at least comprise the gas material of hydrogen, wherein, the isolated gas material major part of described gas-liquid separation device 110 is back to reaction unit 110, and small part is drained as periodic off-gases.In described gas-liquid separation device 120, isolated liquid material enters product separation device 130, isolates alcohol product.In one embodiment, described product separation device 130 comprises raw materials recovery tower 131, refining methanol tower 132 and film water trap 133.Liquid material isolated in described gas-liquid separation device 120 is sent into raw materials recovery tower 131, and tower top isolates methyl acetate and methanol azeotrope, isolates the mixture of methyl alcohol, ethanol, a small amount of water at the bottom of tower; The mixture of described methyl alcohol, ethanol, a small amount of water is sent into refining methanol tower 132, and tower top isolates byproduct methyl alcohol, isolates the ethanol containing a small amount of water at the bottom of tower; The described ethanol containing a small amount of water is sent in film water trap 133 and isolates major product dehydrated alcohol.
In one embodiment, described reaction unit 110 comprises reactor.In one embodiment, described reactor is fixed-bed reactor.Described fixed-bed reactor can be two-part insulation fix bed reactors, the intersegmental interchangeable heat drop temperature of wherein said two section reactor; Described fixed-bed reactor also can be the insulation fix bed reactors of two or more series connection, and wherein said two or more insulation fix bed reactor inter-stage can arrange heat exchange heat sink; Described fixed-bed reactor can also be isothermal fixed-bed reactor, and further, described isothermal fixed-bed reactor can be shell-and-tube reactor or built-in coil reactor.
In one embodiment, catalyzer is mounted with in described fixed-bed reactor.In one embodiment, the catalyzer loaded in described fixed-bed reactor is solid nano O composite metallic oxide catalyst, and it can be by transition metal oxide CuO and IIIa family metal oxide Al
2o
3the bielement nano complex metal oxides formed, or by transition metal oxide CuO and IIIa family metal oxide Al
2o
3and the nano composite metal oxide more than ternary that formed of one or more other transition metal oxides or alkaline earth metal oxide or ternary.
Described gas-liquid separation device 120 can be a knockout drum.
Described film water trap can be a kind of mineral membrane water trap, further, can be molecular screen membrane water trap.
In one embodiment, can reaction be regulated to generate the ratio of ethanol, ethane, methane by the component and/or processing condition regulating catalyzer.
Melt below and describe more details so that fully understand the present invention in conjunction with the embodiments; but the present invention can also adopt other alternate manners being different from embodiment described here to implement; therefore the present invention is not by the restriction of following public embodiment; every embodiment is done according to technical spirit of the present invention any simple modification, equivalent variations and modification, all still belong to the technology of the present invention and rights protection category.
Embodiment one
As shown in Figure 2, in embodiment one, in a kind of polyvinyl alcohol production process, the system of the crude methyl acetate hydrogenation of net product ethanol of by-product comprises: mixing tank 211, reactor 212, discharging water cooler 213, knockout drum 221, compressor 222, raw materials recovery tower 231, refining methanol tower 232, film water trap 233.
The technological process of embodiment one is as follows:
By hydrogen be (10 ~ 100) in molar ratio from the ritalin of by-product in polyvinyl alcohol production process and the mixture of methyl alcohol: 1, or be (20 ~ 75) further: 1, or be further (25 ~ 60): the ratio of 1 sends into mixing tank 211, sends in reactor 212 react with the gas returned and ritalin material after preheating.Described reactor 212 is isothermal fixed-bed reactor, is mounted with solid nano O composite metallic oxide catalyst in it.Described solid nano O composite metallic oxide catalyst is by transition metal oxide CuO and IIIa family metal oxide Al
2o
3the bielement nano complex metal oxides formed, or by transition metal oxide CuO and IIIa family metal oxide Al
2o
3and one or more other transition metal oxides, alkaline earth metal oxide formed ternary or ternary more than nano composite metal oxide.The reaction conditions of described reactor 212 is: temperature of reaction between 170 ~ 260 DEG C, or further between 180 ~ 250 DEG C, or further between 190 ~ 230 DEG C; Reaction pressure between 2.0 ~ 10.0MPa (A), or further between 2.0 ~ 6.0MPa (A), or further between 2.0 ~ 5.0MPa (A); The liquid hourly space velocity of reaction raw materials is at 0.2 ~ 5.0h
-1between, or further at 0.2 ~ 2.0h
-1between, or further at 0.2 ~ 1.0h
-1between.Under the cited reaction conditions, ritalin and hydrogen react under catalyst action, and mainly generate ethanol and by-product methyl alcohol, wherein the transformation efficiency of ritalin is 80 ~ 99wt%, or is 85 ~ 99wt% further, or is further 90 ~ 99wt%; The selectivity of ethanol is 90 ~ 99.5wt%, or is 95 ~ 99.5wt% further, or is further 98 ~ 99.5wt%.
The outputting material of reactor 212 comprises ethanol, methyl alcohol, hydrogen, ritalin, a small amount of water etc., and wherein ethanol content is 25 ~ 40wt%, or is 25 ~ 35wt% further, or is further 25 ~ 32wt%.This outputting material is sent into condenser 213 to be cooled to temperature required, then sends into knockout drum 221 and carries out gas-liquid separation.The Gaseous materials of main hydrogen that what described knockout drum 221 top exported is, major part wherein returns mixing tank 211 through gas compressor 222 supercharging Posterior circle, and small part is drained as periodic off-gases; What export bottom described knockout drum 221 is the liquid material containing ethanol, methyl alcohol, ritalin, a small amount of water, incoming stock recovery tower 231.
The tower top outputting material of described raw materials recovery tower 231 is mainly ritalin and methanol azeotrope, send into after supercharging mixing tank 211 then further dereaction device 212 react; Outputting material at the bottom of the tower of described raw materials recovery tower 231 is mainly the mixing solutions of ethanol, methyl alcohol, ritalin, a small amount of water, enters refining methanol tower 232.
The tower top outputting material of described refining methanol tower 232 is mainly methanol solution; Outputting material at the bottom of the tower of described refining methanol tower 232 is the ethanol liquid containing a small amount of water, and it enters film water trap 233 and obtain dehydrated alcohol product after dehydration after cooling.
Described technique can pass through thermal coupling, utilizes remaining used heat rationally and effectively, reduces production cost further.Such as, the outputting material of reactor 212 needs cooling, and polyvinyl alcohol technique is transported to the ritalin of mixing tank 211 and the mixture of methyl alcohol, the tower top of raw materials recovery tower 231 is transported to the hydrogen that the methyl acetate and methanol azeotrope of mixing tank 211 and knockout drum 221 top turn back to mixing tank 211 and all needs preheating, can give the mixed material preheating of described mixing tank 211 with the outputting material of reactor 212, its insufficient section is supplemented by live steam and provides heat.In addition, the reaction that ritalin and hydrogen generate ethanol and methyl alcohol is a thermopositive reaction, is necessary temperature of reaction to be controlled, prescribed value (this prescribed value is different with the performance of catalyzer), therefore to need reaction heat to shift out.Reclaim described reaction heat and can solve heat problem in technique needed for self for generation of steam, such as, available described reaction heat is supplied raw materials steam needed for recovery tower 231 reboiler, methanol rectifying tower 232 reboiler, the object reaching save energy, reduce environmental pollution, reduce production cost.
The methyl alcohol that described refining methanol tower 232 tower top obtains not only can be used as methanol product, also can deliver to the alcoholysis workshop section of polyvinyl alcohol, generates polyvinyl alcohol as raw material and polyvinyl acetate (PVA).
Embodiment two
The present embodiment have employed the system identical with embodiment one, that is, system as shown in Figure 2, is described the technological process in the present embodiment below with reference to Fig. 2.The present embodiment technological process is as follows:
By hydrogen be (10 ~ 100) in molar ratio from the ritalin of by-product in polyvinyl alcohol production process and the mixture of methyl alcohol: 1, or be (30 ~ 80) further: 1, or be further (40 ~ 70): the ratio of 1 sends into mixing tank 211, sends in reactor 212 react with the gas returned and ritalin material after preheating.Described reactor 212 is isothermal fixed-bed reactor, is mounted with solid nano O composite metallic oxide catalyst in it.Described solid nano O composite metallic oxide catalyst is by transition metal oxide CuO and IIIa family metal oxide Al
2o
3the bielement nano complex metal oxides formed, or by transition metal oxide CuO and IIIa family metal oxide Al
2o
3and one or more other transition metal oxides, alkaline earth metal oxide formed ternary or ternary more than nano composite metal oxide.The reaction conditions of described reactor 212 is: temperature of reaction between 170 ~ 260 DEG C, or further between 180 ~ 250 DEG C, or further between 190 ~ 230 DEG C; Reaction pressure between 2.0 ~ 10.0MPa (A), or further between 2.0 ~ 6.0MPa (A), or further between 2.0 ~ 5.0MPa (A); The liquid hourly space velocity of reaction raw materials is at 0.2 ~ 5.0h
-1between, or further at 0.5 ~ 2.0h
-1between, or further at 0.8 ~ 1.0h
-1between.Under the cited reaction conditions, ritalin and hydrogen react under catalyst action, and mainly generate ethanol and by-product methyl alcohol, wherein the transformation efficiency of ritalin is 80 ~ 99wt%, or is 85 ~ 99wt% further, or is further 90 ~ 99wt%; The selectivity of ethanol is 90 ~ 99.5wt%, or is 95 ~ 99.5wt% further, or is further 98 ~ 99.5wt%.
The outputting material of reactor 212 comprises ethanol, methyl alcohol, hydrogen, ritalin, ethane, methane, a small amount of water etc., and wherein ethanol content is 20 ~ 40wt%, or is 20 ~ 35wt% further, or is further 20 ~ 30wt%.This outputting material is sent into condenser 213 to be cooled to temperature required, then sends into knockout drum 221 and carries out gas-liquid separation.The Gaseous materials of main hydrogen that what described knockout drum 221 top exported is, major part wherein returns mixing tank 211 through gas compressor 222 supercharging Posterior circle, and small part is drained as periodic off-gases; What export bottom described knockout drum 221 is the liquid material containing ethanol, methyl alcohol, ritalin, a small amount of water, incoming stock recovery tower 231.
The tower top outputting material of described raw materials recovery tower 231 is mainly ritalin and methanol azeotrope, send into after supercharging mixing tank 211 then further dereaction device 212 react; Outputting material at the bottom of the tower of described raw materials recovery tower 231 is mainly the mixing solutions of ethanol, methyl alcohol, ritalin, a small amount of water, enters refining methanol tower 232.
The tower top outputting material of described refining methanol tower 232 is mainly methanol solution; Outputting material at the bottom of the tower of described refining methanol tower 232 is the ethanol liquid containing a small amount of water, and it enters film water trap 233 and obtain dehydrated alcohol product after dehydration after cooling.
Described technique can pass through thermal coupling, utilizes remaining used heat rationally and effectively, reduces production cost further.Such as, the outputting material of reactor 212 needs cooling, and polyvinyl alcohol technique is transported to the ritalin of mixing tank 211 and the mixture of methyl alcohol, the tower top of raw materials recovery tower 231 is transported to the hydrogen that the methyl acetate and methanol azeotrope of mixing tank 211 and knockout drum 221 top turn back to mixing tank 211 and all needs preheating, can give the mixed material preheating of described mixing tank 211 with the outputting material of reactor 212, its insufficient section is supplemented by live steam and provides heat.In addition, the reaction that ritalin and hydrogen generate ethanol and methyl alcohol is a thermopositive reaction, is necessary temperature of reaction to be controlled, prescribed value (this prescribed value is different with the performance of catalyzer), therefore to need reaction heat to shift out.Reclaim described reaction heat and can solve heat problem in technique needed for self for the production of steam, such as, available described reaction heat is supplied raw materials steam needed for recovery tower 231 reboiler, methanol rectifying tower 232 reboiler, the object reaching save energy, reduce environmental pollution, reduce production cost.
The methyl alcohol that described refining methanol tower 232 tower top obtains not only can be used as methanol product, also can deliver to the alcoholysis workshop section of polyvinyl alcohol, generates polyvinyl alcohol as raw material and polyvinyl acetate (PVA).
Embodiment three
As shown in Figure 3, in the polyvinyl alcohol production process adopted in embodiment three, the system of the crude methyl acetate hydrogenation of net product ethanol of by-product is roughly the same with embodiment one, difference is: described reactor 312 is two-part insulation fix bed reactor, its intersegmental interchangeable heat drop temperature.The present embodiment technological process is as follows:
By hydrogen be (10 ~ 100) in molar ratio from the ritalin of by-product in polyvinyl alcohol production process and the mixture of methyl alcohol: 1, or be (20 ~ 75) further: 1, or be further (25 ~ 60): the ratio of 1 sends into mixing tank 311, sends in reactor 312 react with the gas returned and ritalin material after preheating.Described reactor 312 is a two-part insulation fix bed reactor, its intersegmental interchangeable heat drop temperature.Solid nano O composite metallic oxide catalyst is mounted with in described reactor.Described solid nano O composite metallic oxide catalyst is by transition metal oxide CuO and IIIa family metal oxide Al
2o
3the bielement nano complex metal oxides formed, or by transition metal oxide CuO and IIIa family metal oxide Al
2o
3and one or more other transition metal oxides, alkaline earth metal oxide formed ternary or ternary more than nano composite metal oxide.The reaction conditions of described reactor 312 is: temperature of reaction between 170 ~ 260 DEG C, or further between 180 ~ 250 DEG C, or further between 190 ~ 230 DEG C; Reaction pressure between 2.0 ~ 10.0MPa (A), or further between 2.0 ~ 6.0MPa (A), or further between 2.0 ~ 5.0MPa (A); The liquid hourly space velocity of reaction raw materials is at 0.2 ~ 5.0h
-1between, or further at 0.2 ~ 2.0h
-1between, or further at 0.2 ~ 1.0h
-1between.Under the cited reaction conditions, ritalin and hydrogen react under catalyst action, and mainly generate ethanol and by-product methyl alcohol, wherein the transformation efficiency of ritalin is 80 ~ 99wt%, or is 85 ~ 99wt% further, or is further 90 ~ 99wt%; The selectivity of ethanol is 90 ~ 99.5wt%, or is 95 ~ 99.5wt% further, or is further 98 ~ 99.5wt%.
The outputting material of reactor 312 comprises ethanol, methyl alcohol, hydrogen, ritalin, a small amount of water etc., and wherein ethanol content is 25 ~ 40wt%, or is 25 ~ 35wt% further, or is further 25 ~ 32wt%.This outputting material is sent into condenser 313 to be cooled to temperature required, then sends into knockout drum 321 and carries out gas-liquid separation.The Gaseous materials of main hydrogen that what described knockout drum 321 top exported is, major part wherein returns mixing tank 311 through gas compressor 322 supercharging Posterior circle, and small part is drained as periodic off-gases; What export bottom described knockout drum 321 is the liquid material containing ethanol, methyl alcohol, ritalin, a small amount of water, incoming stock recovery tower 331.
The tower top outputting material of described raw materials recovery tower 331 is mainly ritalin and methanol azeotrope, send into after supercharging mixing tank 311 then further dereaction device 312 react; Outputting material at the bottom of the tower of described raw materials recovery tower 331 is mainly the mixing solutions of ethanol, methyl alcohol, ritalin, a small amount of water, enters refining methanol tower 332.
The tower top outputting material of described refining methanol tower 332 is mainly methanol solution; Outputting material at the bottom of the tower of described refining methanol tower 332 is the ethanol liquid containing a small amount of water, and it enters film water trap 333 and obtain dehydrated alcohol product after dehydration after cooling.
Described technique can pass through thermal coupling, utilizes remaining used heat rationally and effectively, reduces production cost further.Such as, the outputting material of reactor 312 needs cooling, and polyvinyl alcohol technique is transported to the ritalin of mixing tank 311 and the mixture of methyl alcohol, the tower top of raw materials recovery tower 331 is transported to the hydrogen that the methyl acetate and methanol azeotrope of mixing tank 311 and knockout drum 321 top turn back to mixing tank 311 and all needs preheating, can give the mixed material preheating of described mixing tank 311 with the outputting material of reactor 312, its insufficient section is supplemented by live steam and provides heat.In addition, the reaction that ritalin and hydrogen generate ethanol and methyl alcohol is a thermopositive reaction, is necessary temperature of reaction to be controlled, prescribed value (this prescribed value is different with the performance of catalyzer), therefore to need reaction heat to shift out.Reclaim described reaction heat and can solve heat problem in technique needed for self for the production of steam, such as, available described reaction heat is supplied raw materials steam needed for recovery tower 331 reboiler, methanol rectifying tower 332 reboiler, the object reaching save energy, reduce environmental pollution, reduce production cost.
The methyl alcohol that described refining methanol tower 332 tower top obtains not only can be used as methanol product, also can deliver to the alcoholysis workshop section of polyvinyl alcohol, generates polyvinyl alcohol as raw material and polyvinyl acetate (PVA).
Claims (20)
1. the technique of the crude methyl acetate hydrogenation of net product ethanol of by-product in polyvinyl alcohol production process, it comprises:
A the ritalin of by-product in polyvinyl alcohol production process and the mixture of methyl alcohol and hydrogen are added to reaction unit as raw material by (), make ritalin and hydrogen carry out reaction and generate ethanol and methyl alcohol;
B () isolates the gas material of hydrogen and the liquid material containing ethanol, methyl alcohol and ritalin from the outputting material of described reaction unit;
C described liquid material is sent into methanol distillation column by (), tower top isolates methyl acetate and methanol azeotropic material, isolates the mixture containing methyl alcohol and ethanol at the bottom of tower; And
D described mixture is sent into methanol rectifying tower and is isolated methyl alcohol and ethanol by ().
2. technique as claimed in claim 1, it comprises further: the gas material of at least part of described hydrogen is looped back described reaction unit.
3. technique as claimed in claim 1, it comprises further: at least part of described methyl acetate and methanol azeotropic material is looped back described reaction unit.
4. technique as claimed in claim 1, it is characterized in that: described step (b) comprising: the outputting material of described reaction unit is sent into knockout drum, isolate the gas material of hydrogen and the liquid material containing ethanol, methyl alcohol and ritalin.
5. technique as claimed in claim 1, it is characterized in that: also containing water in described mixture, described step (d) comprising: from described mixture, isolate methyl alcohol and moisture ethanol, and separation obtains dehydrated alcohol product from described moisture ethanol.
6. technique as claimed in claim 5, it is characterized in that: the described step isolating methyl alcohol and moisture ethanol from mixture comprises: the mixture of described methyl alcohol, ethanol, water is sent into methanol rectifying tower, tower top isolates methyl alcohol, isolates moisture ethanol at the bottom of tower.
7. technique as claimed in claim 5, is characterized in that: the described step obtaining dehydrated alcohol product that is separated from moisture ethanol comprises: described moisture ethanol is sent into membrane separation apparatus separation and obtain dehydrated alcohol product.
8. the system of the crude methyl acetate hydrogenation of net product ethanol of by-product in polyvinyl alcohol production process, it is characterized in that, it comprises:
Reaction unit, can to receive in hydrogen and polyvinyl alcohol production process the ritalin of by-product and the mixture of methyl alcohol as raw material, and makes ritalin wherein and hydrogen carry out reaction to generate ethanol and methyl alcohol;
Gas-liquid separation device, can isolate the gas material of hydrogen and the liquid material containing ethanol, methyl alcohol and ritalin from the outputting material of described reaction unit; And
Product separation device, it comprises:
Raw materials recovery tower, can obtain methyl acetate and methanol azeotropic material and contain the mixture of methyl alcohol and ethanol from described liquid material; And
Refining methanol tower, can isolate methyl alcohol and ethanol material from described mixture.
9. system as claimed in claim 8, it comprises the circulation device isolated gas material of at least part of described gas-liquid separation device being looped back described reaction unit further.
10. system as claimed in claim 9, is characterized in that: described circulation device comprises compressor, is used for compressing it before described gas material is looped back described reaction unit.
11. systems as claimed in claim 8, it comprises the circulation device at least part of methyl acetate and methanol azeotropic material obtained from described raw materials recovery tower being looped back described reaction unit further.
12. systems as claimed in claim 8, it is characterized in that: described ethanol material is moisture ethanol, described product separation device also comprises film water trap, can be separated and obtain dehydrated alcohol product from described moisture ethanol.
13. systems as claimed in claim 8, is characterized in that: described reaction unit comprises:
Mixing tank, is used for receiving, the ritalin of by-product and the mixture of methyl alcohol in mixing pre-hot hydrogen and polyvinyl alcohol production process;
Reactor, is used for receiving from the material of described mixing tank, and makes ritalin wherein and hydrogen carry out reaction to generate ethanol and methyl alcohol; And
Discharging water cooler, the material cooling being used for described reactor to export is rear sends into described gas-liquid separation device.
14. systems as claimed in claim 8, is characterized in that: described reaction unit comprises fixed-bed reactor.
15. systems as claimed in claim 14, is characterized in that: described fixed-bed reactor are two-part insulation fix bed reactor, the intersegmental interchangeable heat drop temperature of described two section reactor.
16. systems as claimed in claim 14, is characterized in that: described fixed-bed reactor comprise the insulation fix bed reactor of two or more series connection, described two or more insulation fix bed reactor inter-stage is provided with heat exchange heat sink.
17. systems as claimed in claim 14, is characterized in that: described fixed-bed reactor are isothermal fixed-bed reactor.
18. systems as claimed in claim 17, is characterized in that: described isothermal fixed-bed reactor are shell-and-tube reactor or built-in coil reactor.
19. systems as claimed in claim 14, is characterized in that: be mounted with the bielement nano O composite metallic oxide catalyst comprising copper and aluminium in described fixed-bed reactor.
20. systems as claimed in claim 14, is characterized in that: be mounted with in described fixed-bed reactor and comprise copper, the ternary of aluminium and one or more transition metal or alkaline earth metal oxide or the above nano composite metal oxide of ternary.
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| CN105237349A (en) * | 2015-10-30 | 2016-01-13 | 西南化工研究设计院有限公司 | Method for efficiently using byproduct coarse methyl acetate solution in PVA production process |
| CN113816830A (en) * | 2021-10-12 | 2021-12-21 | 北京石油化工工程有限公司 | Method and system for reducing methanol content in methyl acetate hydrogenation reactor through membrane separation |
| CN114349603A (en) * | 2022-03-04 | 2022-04-15 | 福州大学 | Method for preparing cyclopentanol from cyclopentyl acetate |
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