CN102557870A - Method for preparing fuel ethanol by using acetic acid and methanol - Google Patents
Method for preparing fuel ethanol by using acetic acid and methanol Download PDFInfo
- Publication number
- CN102557870A CN102557870A CN2011104215314A CN201110421531A CN102557870A CN 102557870 A CN102557870 A CN 102557870A CN 2011104215314 A CN2011104215314 A CN 2011104215314A CN 201110421531 A CN201110421531 A CN 201110421531A CN 102557870 A CN102557870 A CN 102557870A
- Authority
- CN
- China
- Prior art keywords
- acetic acid
- ritalin
- rare earth
- reaction
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- C—CHEMISTRY; METALLURGY
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing fuel ethanol by using acetic acid and methanol. The method comprises the following steps of: performing supercritical esterification reaction on acetic acid and methanol to prepare methyl acetate; and performing hydrogenation reaction on methyl acetate and hydrogen to prepare fuel ethanol. According to the method, supercritical esterification reaction is adopted, reaction time is short, catalyst is eliminated, and the conversion rate of acetic acid in esterification is high; and compared with a method in which the conventional copper-zinc-aluminum catalyst is used for hydrogenation reaction, the method in which a copper-zinc-aluminum-rare earth catalyst is used for hydrogenation reaction has the advantages that: the conversion rate of the methyl acetate and the yield of ethanol can be improved obviously, and hydrogenation reaction efficiency is high.
Description
Technical field
The present invention relates to a kind of preparation alcoholic acid method, the biological acetic acid that particularly utilizes the abandoned biomass fermentation to make prepares the method for alcohol fuel.
Background technology
Ethanol is claimed alcohol again, is by C, H, three kinds of elementary composition organic cpds of O, is water white liquid at normal temperatures and pressures, can with water with any mixed and produce heat, volatile, easy firing.Alcohol fuel is meant that generally volumetric concentration reaches the absolute ethyl alcohol more than 99.5%, is the superoctane fuel of combustion cleaning, is a kind of renewable energy source, the CO that its burning is discharged
2With the CO that grows and consumed as the biogenic of raw material
2, quantitatively remain basically stable, significant to reducing topsoil and suppressing Greenhouse effect.Alcohol fuel can be used as new fuel substitute, directly mixes as liquid fuel or with gasoline and uses, and can reduce Nonrenewable energy resources---the dependence of oil.In addition, alcohol fuel is to improving oil quality, and development chemical industry and chemical fibre aspects such as (like trevira and benzene series chemical industry) all have great importance.
Ethanol makes through two kinds of methods in industry, and the one, chemical synthesis promptly uses oil, the resulting ethene of coal cracking to generate ethanol through acid catalysis generation hydration; The 2nd, by glucide (being biomass material) through production of ethanol from microbial fermentation.Producing the alcoholic acid biomass material has three types, and the saccharide biomass raw material comprises sugarcane, sweet sorghum, beet etc.; Starch based comprises corn, wheat, sweet potato, cassava etc.; Cellulose family comprises stalk, crudefiber crop, farm crop shell skin, branch, fallen leaves, forestry limit pin clout etc.At present, the ethanol of China nearly 90% is by biological fermentation process production.
Publication number is that the Chinese invention patent application of CN1283701 discloses a kind of process for preparing alcohol from stress or stalk of agricultural crops; This process method is get liquid glucose by agricultural crop straw is pulverized through vitriolization and milk of lime neutralizing hydrolysis, the gained liquid glucose by conventional ethanol fermentation technology add yeast fermentation, distillation makes ethanol.Publication number is that the Chinese invention patent application of CN101168749 discloses the method with sweet sorghum straw ethanol production: the sweet sorghum straw is got in (1), removes the fringe and the root of sweet sorghum straw, obtains clean sweet sorghum straw; (2) squeeze the juice clean sweet sorghum straw with cane crusher, obtain sweet sorghum straw juice; (3) put into fermentor tank to sweet sorghum straw juice, in sweet sorghum straw juice, add distillery yeast, the weight of distillery yeast is 0.8 ‰～1.2 ‰ of sweet sorghum straw juice weight, and regulating the pH value is 4.5～4.7, obtains inoculating the liquid material; (4) inoculation liquid material 30 ℃～38 ℃ bottom fermentations of temperature 50～56 hours, obtain beer; (5) in distillation tower, distill beer, obtain ethanol.The present invention is a raw material with the sweet sorghum straw, with advanced liquid-state fermentation technology system ethanol, sweet sorghum stalk is extracted juice through squeezing, and after the juice liquid state fermentation, but beer goes out ethanol through the distillation direct production.
Though it is various to utilize biomass material to prepare the alcoholic acid method, adopt traditional yeast fermentation method and zymin method to produce ethanol at present mostly, ethanol conversion is low in the production process, CO
2Quantity discharged is big, and energy consumption is high, and production cost is high.In addition, also there are technical bottlenecks such as the series exploitation of cellulolytic enzyme, the bacterial strain exploitation that is used for five-carbon sugar fermentation technique engineering, lignocellulose preconditioning technique, the ripe raw spirit degree of cellulosic ethanol.
At present, existing research discloses acetic acid esterification, hydrogenation has been generated the alcoholic acid novel method.Like publication number is that the Chinese invention patent of CN101965324A discloses that a kind of to be used for methanol conversion be the alcoholic acid method; It is included under the existence of catalyzer methyl alcohol and reaction of carbon monoxide with preparation methyl acetate and acetic acid product; Then this acetate and at least a alcohol are reacted at least a acetic ester that is selected from methyl acetate, ETHYLE ACETATE and butylacetate with preparation, again should at least a acetic ester hydrogenation preparing ethanol.And for example; Publication number is the method that the Chinese invention patent of CN101941887A discloses a kind of carbon monoxide and the indirect synthesizing alcohol of hydrogen; Promptly adopt CO and methyl alcohol earlier acetic acid synthesized through carbonylation method; Acetic acid generates corresponding acetic ester with different low-carbon alcohol esterifications again, and last acetic ester shortening generates ethanol and ester alcohol corresponding thereof indirectly.
Although above-mentioned reaction can utilize biomass synthetic CO and H
2Prepare ethanol, but prepare CO and H in the gasification of biomass
2Process in can produce problems such as carbon deposit obstruction, corrosion pipeline, gasification efficiency is low.In addition; The normal catalyzer that uses in biomass gasification process; Yet all there are various shortcomings in all kinds of catalyzer, like natural crystal such as rhombspar etc. the polycyclic aromatic hydrocarbons type organic are increased, and cause the tar behind the catalytic pyrolysis to be difficult to more remove; Basic metal is difficult to satisfy to generate rich H to the reformation poor-performing of methane
2With the CO synthetic gas be the biogas metallization processes of purpose, the nickel catalyzator working conditions is harsh, costs an arm and a leg etc.
Publication number is that the Chinese invention patent of CN101532038A discloses a kind of method of utilizing straw to prepare alcohol fuel; The hydrolyzed solution that the straw acid hydrolysis is processed carries out anaerobically fermenting and makes the acetic acid mixed solution; Then acetic acid mixed solution and methyl alcohol are carried out esterification under catalyst action; Process mixed ester, again mixed ester is carried out hydrogenation under second catalyst action and process alcohol fuel.This inventive method combining with fermentation method and chemical method prepare ethanol; Waste straw kind biomass with agricultural, forestry are raw material, not only save production cost but also reduced environmental pollution, and the alcohol fuel yield of preparation is high; Octane value is high, have good burning performance; The burning and exhausting pollutent is few, yet the ritalin transformation efficiency of this invention preparation method is low, and the alcoholic acid yield is low.
Summary of the invention
Primary and foremost purpose of the present invention is to the problem that above-mentioned prior art exists a kind of method of utilizing acetic acid and methyl alcohol to prepare alcohol fuel to be provided; The inventive method adopts the supercritical esterification reaction; The acetic acid transformation efficiency is high, and the ritalin selectivity is high, and the present invention adopts copper zinc-aluminium-rare earth composite catalyst to carry out hydrogenation in addition; The ritalin transformation efficiency is high, and the ethanol yield is high.
In order to achieve the above object, one aspect of the present invention provides a kind of method of utilizing acetic acid and methyl alcohol to prepare alcohol fuel, comprises as follows step in sequence:
1) acetic acid and methyl alcohol are carried out the supercritical esterification reaction, make ritalin;
2) ritalin and hydrogen are carried out hydrogenation, make alcohol fuel.
Wherein, the mol ratio of acetic acid described in the step 1) and methyl alcohol is 1: 2-20, and the temperature of said supercritical esterification reaction is 220-350 ℃, and the reaction absolute pressure is 10-20MPa, and the reaction times is 1-3h; Under these conditions, the methanol treatment supercritical state, the reaction mass transfer resistance is little, and reactant is uniformly dispersed, the esterification mild condition, thus reduce corrosion to conversion unit.
Particularly, acetic acid described in the step 1) can adopt common commercially available acetic acid, wherein quality percentage composition >=99% of acetic acid; Also can adopt the acetic acid that utilizes the acetic acid bacteria fermentative prepn in addition.
Especially, the preparation method of acetic acid described in the step 1) comprises as follows step in sequence:
A) abandoned biomass is carried out acid hydrolytic reaction, make hydrolyzed solution;
B) utilize acetic acid bacteria that hydrolyzed solution is carried out anaerobically fermenting, make the acetic acid mixed solution.
Wherein, steps A) utilize dilute sulphuric acid that abandoned biomass is carried out described acid hydrolytic reaction in, wherein, the mass percent concentration of dilute sulphuric acid is 0.5-1%, and the weight proportion of abandoned biomass and dilute sulphuric acid is 1: 2-4; The acid hydrolytic reaction temperature is 120-150 ℃, and the absolute pressure of reaction is 0.2-0.6MPa, and the reaction times is 1-3 hour.
Particularly, the mass percentage content of the sugar that contains in the said hydrolyzed solution is 10-15%, and the abandoned biomass of employing can comprise corn cob, sunflower shell, soybean straw, corn stalk etc.
Wherein, step B) temperature of anaerobically fermenting is 50 ± 2 ℃ described in, and fermentation time is 48-60 hour; Particularly, comprise that also the Dichlorodiphenyl Acetate mixed solution carries out underpressure distillation, makes acetic acid.
Wherein, step 2) under the effect of copper zinc-aluminium-rare earth composite catalyst, carry out described hydrogenation in, wherein the weight proportion of copper zinc-aluminium-rare earth composite catalyst and ritalin is 1.0-1.5: 100.
Particularly, said copper zinc-aluminium-rare earth composite catalyst comprises CuZnAl catalyst and rare earth composite catalyst, and the weight proportion of CuZnAl catalyst and rare earth composite catalyst is 8-10: 1.
Wherein, said CuZnAl catalyst comprises cupric oxide, zinc oxide and aluminum oxide, and wherein the mass percentage content of cupric oxide is 50-70%, and the mass percentage content of zinc oxide is 20-30%, and aluminum oxide quality degree is 10-20%; Said rare earth composite catalyst comprises lanthanum trioxide and cerium oxide, and wherein the mol ratio of lanthanum element and Ce elements is 1-2: 1.
Particularly, copper zinc-aluminium-rare earth composite catalyst reduces processing with hydrogen before use, and the treatment temperature of wherein reducing is 180-250 ℃, and the recovery time is 10-20 hour.
Wherein, step 2) hydrogen described in and the mol ratio of ritalin are 20-60: 1, and the temperature of said hydrogenation is 200-300 ℃, and absolute pressure is 2-5Mpa, and the reaction times is 0.5-2h.
The present invention provides a kind of alcohol fuel of preparation according to the method described above on the other hand.
The present invention has the following advantages:
1, the present invention adopts super critical condition to carry out esterification; Need not Dichlorodiphenyl Acetate before the reaction and methyl alcohol removes water treatment, the reaction mass transfer resistance is little, and RM is uniformly dispersed; Reaction times is short; Need not to use catalyzer, acetic acid conversion reaches 100% in the esterification, and the selectivity of ritalin reaches 93-96%;
2, the present invention adopts copper zinc-aluminium-rare earth composite catalyst to carry out hydrogenation; Compare with traditional CuZnAl catalyst; Can obviously improve the transformation efficiency and the alcoholic acid yield of ritalin, wherein the transformation efficiency of ritalin reaches 94-96%, and the alcoholic acid yield reaches 93-94%; And adopt traditional CuZnAl catalyst to carry out hydrogenation under the same conditions, and the transformation efficiency of ritalin is merely 86%, and the alcoholic acid yield is merely 80%.
3, preparation technology of the present invention is simple, and is easy to operate, can also utilize abandoned biomass fermentative prepn acetic acid, saves production cost, and the alcohol fuel purity of preparation is high, alcoholic acid volume percent content >=99.5%, constant product quality.
Description of drawings
Fig. 1 prepares the process flow sheet of alcohol fuel for the present invention utilizes acetic acid and methyl alcohol.
The specific embodiment mode
Embodiment 1
1, raw materials pretreatment
With water ratio is 25% corn straw, and pulverizing is subsequent use behind broken section of the stalk of 3～5cm;
2, acid hydrolytic reaction makes hydrolyzed solution
Behind broken section hydrolysis kettle of packing into of corn straw, the adding mass percent concentration is 0.5% dilution heat of sulfuric acid, wherein, hydrolysis kettle inner-wall spraying enamel anticorrosion material, hydrolysis kettle is withstand voltage >=1Mpa, the hydrolysis kettle bottom adopts steam heater to heat; Broken section weight part proportioning with dilution heat of sulfuric acid of soybean stalk is 1: 4, and corn straw is a hydrolysis kettle volumetrical 70% with the mixed volume of dilution heat of sulfuric acid for broken section in the hydrolysis kettle;
Close reinforced flap, open hydrolysis kettle top vent valve, the steam heater of opening the hydrolysis kettle bottom heats; Temperature in the kettle is raise, and the material boiling was closed the top vent valve after 10 minutes in the still; Temperature in the kettle, pressure raise, and absolute pressure in the still is reached and remain 0.6MPa, and temperature is 120 ℃; Reach 120 ℃, absolute pressure with temperature in the kettle and begin to calculate hydrolysis time when being 0.6MPa; Behind the hydrolysis reaction 1 hour, stop to heat and opening simultaneously the tapping valve of hydrolysis kettle bottom, utilize the still internal pressure that hydrolyzed solution is pressed into evaporating pot;
In the hydrolyzed solution that is pressed into evaporating pot, add Na
2CO
3Solution, the pH that regulates hydrolyzed solution most 7, the acid in the neutralizing hydrolysis liquid is that 7 hydrolyzed solution carries out evaporation concentration with neutralization back pH value, obtains concentrating hydrolysate, wherein Na
2CO
3The mass percent concentration of solution is 10%; The quality percentage composition of the sugar that contains in the concentrating hydrolysate is 10%;
3, anaerobically fermenting prepares the acetic acid mixed solution
1) bacterial classification collection and screening
According to application number is screening and the enlarged culturing that 200910082901.9 Chinese invention patent disclosed method is carried out bacterial classification, makes the enlarged culturing bacterial classification;
2) strain activation and culture
Adding concentrating hydrolysate, Semen Maydis powder, KH2PO4 through in the anaerobism activation pot of 100-120 ℃ of high-temperature sterilization; Behind urea and the Na3PO4, stir, adding mass percent concentration again and be 10% acetum, to regulate pH be 4-4.5; Sterilized 10-12 minute down at 90-100 ℃, cooling makes the strain activation and culture base, wherein; The content of Semen Maydis powder is 30-50g/L in the strain activation and culture base, KH
2PO
4Content be 2g/L, content of urea is that the content of 0.1g/LNa3PO4 is 1g/L, the volume of concentrating hydrolysate is an anaerobism activation pot volumetrical 60%;
Be inoculated into after the enlarged culturing bacterial classification of step 1) preparation stirred in the above-mentioned anaerobism activation pot that the strain activation and culture base is housed and carry out the anaerobism activation culture, keeping the temperature of activation culture is 50 ± 2 ℃, every 4-6 hour; Stirred 2-3 minute; Stir speed (S.S.) is 30 rev/mins, and the pH value of sample detecting strain activation and culture liquid, and using mass percent concentration is the pH value that 10% NaOH solution is regulated strain activation and culture liquid; Make and remain 4-4.5; Activation culture 24 hours obtains activated spawn, wherein inoculates enlarged culturing bacterial classification 200-300ml in every liter of strain activation and culture base;
3) anaerobically fermenting
After hydrolyzed solution after concentrating is cooled to 50 ℃, send in the anaerobic fermentation tank inoculation step 2) activated spawn of preparation carries out anaerobically fermenting; Obtain fermented liquid, wherein, the temperature of anaerobically fermenting is 50 ± 2 ℃; Fermentation time is 48 hours, and every separated 6-8 hour vacuum pump taken out the H of tank deck
2And CO
2Mixed gas; Circulation is stirred fermented liquid 3-5 minute; The activated spawn of inoculation and the volume proportion of concentrating hydrolysate are 20: 100, and the TV of activated spawn and concentrating hydrolysate is a fermentor tank volumetrical 80%, and the mass percent concentration of acetic acid is 8% in the fermented liquid;
4) fermented liquid is purified
With sending into vacuum still behind the filtering fermentation liquor, concentrate purification, the relative pressure of control vacuum still is-0.07MPa; Tower top temperature is 95 ℃; The tower middle part is 110-120 ℃, and tower bottom is 140-150 ℃, collects 110-120 ℃ of fraction; Be cooled to≤harvest and store after 60 ℃, obtain the quality percentage composition and be 95% acetic acid;
4, supercritical esterification reaction
Acetic acid and methyl alcohol that anaerobically fermenting is made feed in the supercritical esterification reactor drum, carry out the supercritical esterification reaction, make esterification reaction mixture; Wherein, the mol ratio of acetic acid and methyl alcohol is 1: 5,300 ℃ of the temperature of control reaction; Absolute pressure is 10MPa, and the reaction times is 2h;
Contain ritalin and a small amount of unreacted acetic acid and methyl alcohol in the esterification reaction mixture, wherein the acetic acid transformation efficiency is 100%, and the selectivity of ritalin is 93.4%;
Esterification reaction mixture is cooled to≤40 ℃ after, send distillation tower to separate, adopt thermal oil to heat; Control tower still temperature is 95-100 ℃, and the temperature of tower middle and upper part is 65-70 ℃, and tower top temperature is 52-56 ℃; Relative pressure in the distillation tower is-0.01Mpa; Collect 65-70 ℃ cut, through condenser condenses and be cooled to≤35 ℃ after, enter the methyl alcohol basin; Collect 52-56 ℃ cut, through condenser condenses and be cooled to≤enter the ritalin basin after 30 ℃, obtain mass percentage content and be 98% ritalin;
The reaction formula that reacts in the supercritical esterification process is following:
5, hydrogenation
1) preparation copper zinc-aluminium-rare earth composite catalyst
With cupric nitrate (Cu (NO
3)
23H
2O), zinc nitrate (Zn (NO
3)
26H
2O) and aluminum nitrate (Al (NO
3)
39H
2O) and urea be dissolved in the zero(ppm) water, make copper zinc-aluminium mixing solutions; Copper zinc-aluminium mixing solutions is joined in the autoclave, be warming up to 120 ℃, treat that deposition fully, is cooled to 50 ℃; Behind the aging 2h of deposition, wash, suction filtration, in 120 ℃ carry out drying after; Be 500 ℃ of roastings 3 hours, make CuZnAl catalyst, wherein the mol ratio between cupric nitrate, zinc nitrate and the aluminum nitrate is 7.5: 3.7: 1; The mass percentage content of cupric oxide is 60% in the CuZnAl catalyst, and the mass percentage content of zinc oxide is 30%, and aluminum oxide quality degree is 10%;
With Lanthanum trinitrate (La (NO
3)
36H
2O) and cerous nitrate (Ce (NO
3)
36H
2O) be dissolved in the zero(ppm) water, make mixed solution of rare earth; To under 60 ℃, sodium carbonate solution and the drip of mixed solution of rare earth and 1mol/L be gone into to be equipped with in the container of zero(ppm) water, form vs; The rate of addition of regulating mixed rare earth solution and sodium carbonate solution is 7-8 with the pH value that keeps vs; After titration finishes,, wash then the aging 2h of vs deposition, suction filtration, after carrying out drying under 120 ℃, be 500 ℃ of roastings 3 hours, make the Rare Earth Lanthanum cerium catalyst, wherein the mol ratio of Lanthanum trinitrate and cerous nitrate is 1.5: 1;
The CuZnAl catalyst and the Rare Earth Lanthanum cerium catalyst mechanically mixing of above-mentioned preparation is even, make copper zinc-aluminium-rare earth composite catalyst, wherein the weight proportion of CuZnAl catalyst and Rare Earth Lanthanum cerium catalyst is 8: 1; Copper zinc-aluminium-rare earth composite catalyst reduces processing with hydrogen before use, and the treatment temperature of wherein reducing is 180 ℃, and the recovery time is 20 hours;
2) hydrogenation
Ritalin, copper zinc-aluminium-rare earth composite catalyst are mixed the back send into from the top the hydrogenation reactor to mix with hydrogen and carry out hydrogenation, obtain hydrogenation mixture, wherein, the mass ratio of catalyzer and ritalin is 1.0: 100, H
2With the mol ratio of ritalin be 40: 1, the temperature of hydrogenation is 260 ℃, absolute pressure is 2.8MPa, the reaction times is 30min;
Contain ethanol, methyl alcohol and unreacted ritalin and hydrogen in the hydrogenation mixture, wherein the transformation efficiency of ritalin is 95%, and the alcoholic acid yield is 93%;
With hydrogenation mixture through heat exchanger cooling after≤45 ℃; Get into cold high score gas-liquid separator, leave standstill extracting with hydrogen recovery through high pressure, liquid is removed composite catalyst through filtering; Make the ritalin bullion; Wherein, absolute pressure is 3Mpa in the cold high score gas-liquid separator, separation temperature≤45 ℃;
The ritalin bullion is sent into rectifying tower separate, heat with thermal oil, the temperature of control tower still is 80-85 ℃; The temperature at middle part is 74-78 ℃, and relative pressure is-0.02Mpa that the top fraction is methyl alcohol and a small amount of unreacted ritalin; The fraction that the middle part is 74-78 ℃ is an ethanol; Ethanol makes alcohol fuel after condenser condenses, the alcoholic acid volumn concentration is 99.5% in the alcohol fuel;
The reaction formula that reacts in the hydrogenation process is following:
The performance index of the alcohol fuel that makes are as shown in table 1.
Embodiment 2
1, raw materials pretreatment
With water ratio is 20% soybean stalk, and pulverizing is subsequent use behind broken section of the stalk of 3～5cm;
2, acid hydrolytic reaction makes hydrolyzed solution
Behind broken section hydrolysis kettle of packing into of corn straw, the adding mass percent concentration is 1% dilution heat of sulfuric acid, wherein, hydrolysis kettle inner-wall spraying enamel anticorrosion material, hydrolysis kettle is withstand voltage >=1Mpa, the hydrolysis kettle bottom adopts steam heater to heat; Broken section weight part proportioning with dilution heat of sulfuric acid of soybean stalk is 1: 2, and corn straw is a hydrolysis kettle volumetrical 70% with the mixed volume of dilution heat of sulfuric acid for broken section in the hydrolysis kettle;
Close reinforced flap, open hydrolysis kettle top vent valve, the steam heater of opening the hydrolysis kettle bottom heats; Temperature in the kettle is raise, and the material boiling was closed the top vent valve after 10 minutes in the still; Temperature in the kettle, pressure raise, and absolute pressure in the still is reached and remain 0.2MPa, and temperature is 150 ℃; Reach 150 ℃, absolute pressure with temperature in the kettle and begin to calculate hydrolysis time when being 0.2MPa; Behind the hydrolysis reaction 3 hours, stop to heat and opening simultaneously the tapping valve of hydrolysis kettle bottom, utilize the still internal pressure that hydrolyzed solution is pressed into evaporating pot;
In the hydrolyzed solution that is pressed into evaporating pot, add Na
2CO
3Solution, the pH that regulates hydrolyzed solution most 6, the acid in the neutralizing hydrolysis liquid is that 7 hydrolyzed solution carries out evaporation concentration with neutralization back pH value, obtains concentrating hydrolysate, wherein Na
2CO
3The mass percent concentration of solution is 10%; The quality percentage composition of the sugar that contains in the concentrating hydrolysate is 15%;
3, anaerobically fermenting prepares the acetic acid mixed solution
1) bacterial classification collection and screening
According to application number is screening and the enlarged culturing that 200910082901.9 Chinese invention patent disclosed method is carried out bacterial classification, makes the enlarged culturing bacterial classification;
2) strain activation and culture
Adding concentrating hydrolysate, Semen Maydis powder, KH2PO4 through in the anaerobism activation pot of 100-120 ℃ of high-temperature sterilization; Behind urea and the Na3PO4, stir, adding mass percent concentration again and be 10% acetum, to regulate pH be 4-4.5; Sterilized 10-12 minute down at 90-100 ℃, cooling makes the strain activation and culture base, wherein; The content of Semen Maydis powder is 30-50g/L in the strain activation and culture base, KH
2PO
4Content be 2g/L, content of urea is that the content of 0.1g/LNa3PO4 is 1g/L, the volume of concentrating hydrolysate is an anaerobism activation pot volumetrical 60%;
Be inoculated into after the enlarged culturing bacterial classification of step 1) preparation stirred in the above-mentioned anaerobism activation pot that the strain activation and culture base is housed and carry out the anaerobism activation culture, keeping the temperature of activation culture is 50 ± 2 ℃, every 4-6 hour; Stirred 2-3 minute; Stir speed (S.S.) is 30 rev/mins, and the pH value of sample detecting strain activation and culture liquid, and using mass percent concentration is the pH value that 10% NaOH solution is regulated strain activation and culture liquid; Make and remain 4-4.5; Activation culture 24 hours obtains activated spawn, wherein inoculates enlarged culturing bacterial classification 200-300ml in every liter of strain activation and culture base;
3) anaerobically fermenting
After hydrolyzed solution after concentrating is cooled to 50 ℃, send in the anaerobic fermentation tank inoculation step 2) activated spawn of preparation carries out anaerobically fermenting; Obtain fermented liquid, wherein, the temperature of anaerobically fermenting is 50 ± 2 ℃; Fermentation time is 60 hours, and every separated 6-8 hour vacuum pump taken out the H of tank deck
2And CO
2Mixed gas; Circulation is stirred fermented liquid 3-5 minute; The activated spawn of inoculation and the volume proportion of concentrating hydrolysate are 20: 100, and the TV of activated spawn and concentrating hydrolysate is a fermentor tank volumetrical 80%, and the mass percent concentration of acetic acid is 10% in the fermented liquid;
4) fermented liquid is purified
With sending into vacuum still behind the filtering fermentation liquor, concentrate purification, the relative pressure of control vacuum still is-0.07MPa; Tower top temperature is 95 ℃; The tower middle part is 110-120 ℃, and tower bottom is 140-150 ℃, collects 110-120 ℃ of fraction; Be cooled to≤harvest and store after 60 ℃, obtain the quality percentage composition and be 97% acetic acid;
4, supercritical esterification reaction
Acetic acid that anaerobically fermenting is made and methyl alcohol are packed in the supercritical esterification reactor drum, carry out the supercritical esterification reaction, make esterification reaction mixture; Wherein, the mol ratio of acetic acid and methyl alcohol is 1: 2,350 ℃ of the temperature of control reaction; Absolute pressure is 20MPa, and the reaction times is 3h;
Contain ritalin and a small amount of unreacted acetic acid and methyl alcohol in the esterification reaction mixture, wherein the acetic acid transformation efficiency is 100%, and the selectivity of ritalin is 95.2%;
Esterification reaction mixture is cooled to≤40 ℃ after, send distillation tower to separate, adopt thermal oil to heat; Control tower still temperature is 95-100 ℃, and the temperature of tower middle and upper part is 65-70 ℃, and tower top temperature is 52-56 ℃; Relative pressure in the distillation tower is-0.01Mpa; Collect 65-70 ℃ cut, through condenser condenses and be cooled to≤35 ℃ after, enter the methyl alcohol basin; Collect 52-56 ℃ cut, through condenser condenses and be cooled to≤enter the ritalin basin after 30 ℃, obtain mass percentage content and be 98% ritalin;
5, hydrogenation
1) preparation copper zinc-aluminium-rare earth composite catalyst
With cupric nitrate (Cu (NO
3)
23H
2O), zinc nitrate (Zn (NO
3)
26H
2O) and aluminum nitrate (Al (NO
3)
39H
2O) and urea be dissolved in the zero(ppm) water, make copper zinc-aluminium mixing solutions; Copper zinc-aluminium mixing solutions is joined in the autoclave, be warming up to 120 ℃, treat that deposition fully; Be cooled to 50 ℃, behind the aging 2h of deposition, wash, suction filtration; In 120 ℃ carry out drying after, be 500 ℃ of roastings 4 hours, make CuZnAl catalyst; Wherein the mol ratio between cupric nitrate, zinc nitrate and the aluminum nitrate is 8.2: 2.5: 1.5; The mass percentage content of cupric oxide is 65% in the CuZnAl catalyst, and the mass percentage content of zinc oxide is 20%, and aluminum oxide quality degree is 15%;
With Lanthanum trinitrate (La (NO
3)
36H
2O) and cerous nitrate (Ce (NO
3)
36H
2O) be dissolved in the zero(ppm) water, make mixed solution of rare earth; To under 60 ℃, sodium carbonate solution and the drip of mixed solution of rare earth and 1mol/L be gone into to be equipped with in the container of zero(ppm) water, form vs; The rate of addition of regulating mixed rare earth solution and sodium carbonate solution is 7-8 with the pH value that keeps vs; After titration finishes,, wash then the aging 2h of vs deposition, suction filtration, after carrying out drying under 120 ℃, be 500 ℃ of roastings 4 hours, make the Rare Earth Lanthanum cerium catalyst, wherein the mol ratio of Lanthanum trinitrate and cerous nitrate is 2: 1;
The CuZnAl catalyst and the Rare Earth Lanthanum cerium catalyst mechanically mixing of above-mentioned preparation is even, make copper zinc-aluminium-rare earth composite catalyst, wherein the weight proportion of CuZnAl catalyst and Rare Earth Lanthanum cerium catalyst is 10: 1; Copper zinc-aluminium-rare earth composite catalyst reduces processing with hydrogen before use, and the treatment temperature of wherein reducing is 250 ℃, and the recovery time is 15 hours;
2) hydrogenation
Ritalin, copper zinc-aluminium-rare earth composite catalyst are mixed the back send into from the top the hydrogenation reactor to mix with hydrogen and carry out hydrogenation, obtain hydrogenation mixture, wherein, the mass ratio of catalyzer and ritalin is 1.5: 100, H
2With the mol ratio of ritalin be 20: 1, the temperature of hydrogenation is 300 ℃, absolute pressure is 4MPa, the reaction times is 1h;
Contain ethanol, methyl alcohol and unreacted ritalin and hydrogen in the hydrogenation mixture, wherein the transformation efficiency of ritalin is 94%, and the alcoholic acid yield is 93%;
With hydrogenation mixture through heat exchanger cooling after≤45 ℃; Get into cold high score gas-liquid separator, leave standstill extracting with hydrogen recovery through high pressure, liquid is removed composite catalyst through filtering; Make the ritalin bullion; Wherein, absolute pressure is 3Mpa in the cold high score gas-liquid separator, separation temperature≤45 ℃;
The ritalin bullion is sent into rectifying tower separate, heat with thermal oil, the temperature of control tower still is 80-85 ℃; The temperature at middle part is 74-78 ℃, and relative pressure is-0.02Mpa that the top fraction is methyl alcohol and a small amount of unreacted ritalin; The fraction that the middle part is 74-78 ℃ is an ethanol; Ethanol makes alcohol fuel after condenser condenses, the alcoholic acid volumn concentration is 99.7% in the alcohol fuel;
The performance index of the alcohol fuel that makes are as shown in table 1.
Embodiment 3
1, supercritical esterification reaction
Common commercially available acetic acid (mass percentage content >=99%) and methyl alcohol are packed in the supercritical esterification reactor drum; Carry out the supercritical esterification reaction, make esterification reaction mixture, wherein; The mol ratio of acetic acid and methyl alcohol is 1: 20; 280 ℃ of the temperature of control reaction, absolute pressure is 15MPa, the reaction times is 2.5h;
Contain ritalin and a small amount of unreacted acetic acid and methyl alcohol in the esterification reaction mixture, wherein the acetic acid transformation efficiency is 100%, and the selectivity of ritalin is 95%;
Esterification reaction mixture is cooled to≤40 ℃ after, send distillation tower to separate, adopt thermal oil to heat; Control tower still temperature is 95-100 ℃, and the temperature of tower middle and upper part is 65-70 ℃, and tower top temperature is 52-56 ℃; Relative pressure in the distillation tower is-0.01Mpa; Collect 65-70 ℃ cut, through condenser condenses and be cooled to≤35 ℃ after, enter the methyl alcohol basin; Collect 52-56 ℃ cut, through condenser condenses and be cooled to≤enter the ritalin basin after 30 ℃, obtain mass percentage content and be 98% ritalin;
2, hydrogenation
1) preparation copper zinc-aluminium-rare earth composite catalyst
With cupric nitrate (Cu (NO
3)
23H
2O), zinc nitrate (Zn (NO
3)
26H
2O) and aluminum nitrate (Al (NO
3)
39H
2O) and urea be dissolved in the zero(ppm) water, make copper zinc-aluminium mixing solutions; Copper zinc-aluminium mixing solutions is joined in the autoclave, be warming up to 120 ℃, treat that deposition fully, is cooled to 50 ℃; Behind the aging 2h of deposition, wash, suction filtration, in 120 ℃ carry out drying after; Be 500 ℃ of roastings 3 hours, make CuZnAl catalyst, wherein the mol ratio between cupric nitrate, zinc nitrate and the aluminum nitrate is 6.3: 3.7: 2; The mass percentage content of cupric oxide is 70% in the CuZnAl catalyst, and the mass percentage content of zinc oxide is 20%, and aluminum oxide quality degree is 10%;
With Lanthanum trinitrate (La (NO
3)
36H
2O) and cerous nitrate (Ce (NO
3)
36H
2O) be dissolved in the zero(ppm) water, make mixed solution of rare earth; To under 60 ℃, sodium carbonate solution and the drip of mixed solution of rare earth and 1mol/L be gone into to be equipped with in the container of zero(ppm) water, form vs; The rate of addition of regulating mixed rare earth solution and sodium carbonate solution is 7-8 with the pH value that keeps vs; After titration finishes,, wash then the aging 2h of vs deposition, suction filtration, after carrying out drying under 120 ℃, be 500 ℃ of roastings 3 hours, make the Rare Earth Lanthanum cerium catalyst, wherein the mol ratio of Lanthanum trinitrate and cerous nitrate is 1.8: 1;
With the CuZnAl catalyst of above-mentioned preparation and Rare Earth Lanthanum cerium catalyst mechanically mixing evenly after, make copper zinc-aluminium-rare earth composite catalyst, wherein the weight proportion of CuZnAl catalyst and Rare Earth Lanthanum cerium catalyst is 8.5: 1; Copper zinc-aluminium-rare earth composite catalyst reduces processing with hydrogen before use, and the treatment temperature of wherein reducing is 200 ℃, and the recovery time is 18 hours;
2) hydrogenation
Ritalin, copper zinc-aluminium-rare earth composite catalyst are mixed the back send into from the top the hydrogenation reactor to mix with hydrogen and carry out hydrogenation, obtain hydrogenation mixture, wherein, the mass ratio of catalyzer and ritalin is 1.5: 100, H
2With the mol ratio of ritalin be 60: 1, the temperature of hydrogenation is 280 ℃, absolute pressure is 2MPa, the reaction times is 2h;
Contain ethanol, methyl alcohol and unreacted ritalin and hydrogen in the hydrogenation mixture, wherein the transformation efficiency of ritalin is 95%, and the alcoholic acid yield is 93%;
With hydrogenation mixture through heat exchanger cooling after≤45 ℃; Get into cold high score gas-liquid separator, leave standstill extracting with hydrogen recovery through high pressure, liquid is removed composite catalyst through filtering; Make the ritalin bullion; Wherein, absolute pressure is 3Mpa in the cold high score gas-liquid separator, separation temperature≤45 ℃;
The ritalin bullion is sent into rectifying tower separate, heat with thermal oil, the temperature of control tower still is 80-85 ℃; The temperature at middle part is 74-78 ℃, and relative pressure is-0.02Mpa that the top fraction is methyl alcohol and a small amount of unreacted ritalin; The fraction that the middle part is 74-78 ℃ is an ethanol; Ethanol makes alcohol fuel after condenser condenses, the alcoholic acid volumn concentration is 99.6% in the alcohol fuel;
The performance index of the alcohol fuel that makes are as shown in table 1.
Embodiment 4
1, supercritical esterification reaction
Common commercially available acetic acid (mass percentage content >=99%) and methyl alcohol are packed in the supercritical esterification reactor drum; Carry out the supercritical esterification reaction, make esterification reaction mixture, wherein; The mol ratio of acetic acid and methyl alcohol is 1: 10; 220 ℃ of the temperature of control reaction, absolute pressure is 15MPa, the reaction times is 1h;
Contain ritalin and a small amount of unreacted acetic acid and methyl alcohol in the esterification reaction mixture, wherein the acetic acid transformation efficiency is 100%, and the selectivity of ritalin is 94.1%;
Esterification reaction mixture is cooled to≤40 ℃ after, send distillation tower to separate, adopt thermal oil to heat; Control tower still temperature is 95-100 ℃, and the temperature of tower middle and upper part is 65-70 ℃, and tower top temperature is 52-56 ℃; Relative pressure in the distillation tower is-0.01Mpa; Collect 65-70 ℃ cut, through condenser condenses and be cooled to≤35 ℃ after, enter the methyl alcohol basin; Collect 52-56 ℃ cut, through condenser condenses and be cooled to≤enter the ritalin basin after 30 ℃, obtain mass percentage content and be 97% ritalin;
2, hydrogenation
1) preparation copper zinc-aluminium-rare earth composite catalyst
With cupric nitrate (Cu (NO
3)
23H
2O), zinc nitrate (Zn (NO
3)
26H
2O) and aluminum nitrate (Al (NO
3)
39H
2O) and urea be dissolved in the zero(ppm) water, make copper zinc-aluminium mixing solutions; Copper zinc-aluminium mixing solutions is joined in the autoclave, be warming up to 120 ℃, treat that deposition fully, is cooled to 50 ℃; Behind the aging 2h of deposition, wash, suction filtration, in 120 ℃ carry out drying after; Be 500 ℃ of roastings 3 hours, make CuZnAl catalyst, wherein the mol ratio between cupric nitrate, zinc nitrate and the aluminum nitrate is 8.8: 2.5: 1; The mass percentage content of cupric oxide is 50% in the CuZnAl catalyst, and the mass percentage content of zinc oxide is 30%, and aluminum oxide quality degree is 20%;
With Lanthanum trinitrate (La (NO
3)
36H
2O) and cerous nitrate (Ce (NO
3)
36H
2O) be dissolved in the zero(ppm) water, make mixed solution of rare earth; To under 60 ℃, sodium carbonate solution and the drip of mixed solution of rare earth and 1mol/L be gone into to be equipped with in the container of zero(ppm) water, form vs; The rate of addition of regulating mixed rare earth solution and sodium carbonate solution is 7-8 with the pH value that keeps vs; After titration finishes,, wash then the aging 2h of vs deposition, suction filtration, after carrying out drying under 120 ℃, be 500 ℃ of roastings 3 hours, make the Rare Earth Lanthanum cerium catalyst, wherein the mol ratio of Lanthanum trinitrate and cerous nitrate is 1: 1;
The CuZnAl catalyst and the Rare Earth Lanthanum cerium catalyst mechanically mixing of above-mentioned preparation is even, make copper zinc-aluminium-rare earth composite catalyst, wherein the weight proportion of CuZnAl catalyst and Rare Earth Lanthanum cerium catalyst is 9: 1; Copper zinc-aluminium-rare earth composite catalyst reduces processing with hydrogen before use, and the treatment temperature of wherein reducing is 220 ℃, and the recovery time is 10 hours;
2) hydrogenation
Ritalin, copper zinc-aluminium-rare earth composite catalyst are mixed the back send into from the top the hydrogenation reactor to mix with hydrogen and carry out hydrogenation, obtain hydrogenation mixture, wherein, the mass ratio of catalyzer and ritalin is 1.2: 100, H
2With the mol ratio of ritalin be 50: 1, the temperature of hydrogenation is 200 ℃, absolute pressure is 5MPa, the reaction times is 1.5h;
Contain ethanol, methyl alcohol and unreacted ritalin and hydrogen in the hydrogenation mixture, wherein the transformation efficiency of ritalin is 96%, and the alcoholic acid yield is 94%;
With hydrogenation mixture through heat exchanger cooling after≤45 ℃; Get into cold high score gas-liquid separator, leave standstill extracting with hydrogen recovery through high pressure, liquid is removed composite catalyst through filtering; Make the ritalin bullion; Wherein, absolute pressure is 3Mpa in the cold high score gas-liquid separator, separation temperature≤45 ℃;
The ritalin bullion is sent into rectifying tower separate, heat with thermal oil, the temperature of control tower still is 80-85 ℃; The temperature at middle part is 74-78 ℃, and relative pressure is-0.02Mpa that the top fraction is methyl alcohol and a small amount of unreacted ritalin; The fraction that the middle part is 74-78 ℃ is an ethanol; Ethanol makes alcohol fuel after condenser condenses, the alcoholic acid volumn concentration is 99.7% in the alcohol fuel;
The performance index of the alcohol fuel that makes are as shown in table 1.
Reference examples
1, preparation copper zinc-aluminium composite catalyst
With cupric nitrate (Cu (NO
3)
23H
2O), zinc nitrate (Zn (NO
3)
26H
2O) and aluminum nitrate (Al (NO
3)
39H
2O) and urea be dissolved in the zero(ppm) water, make copper zinc-aluminium mixing solutions; Copper zinc-aluminium mixing solutions is joined in the autoclave, be warming up to 120 ℃, treat that deposition fully, is cooled to 50 ℃; Behind the aging 2h of deposition, wash, suction filtration, in 120 ℃ carry out drying after; In 500 ℃ of roastings 4 hours, make CuZnAl catalyst again, wherein the mol ratio between cupric nitrate, zinc nitrate and the aluminum nitrate is 6.3: 3.7: 2; The mass percentage content of cupric oxide is 70% in the CuZnAl catalyst, and the mass percentage content of zinc oxide is 20%, and aluminum oxide quality degree is 10%;
2, hydrogenation
The ritalin of embodiment 3 preparation and copper zinc-aluminium composite catalyst mixed afterwards to send into from the top the hydrogenation reactor to mix with hydrogen carry out hydrogenation; Obtain hydrogenation mixture, wherein, the mass ratio of copper zinc-aluminium composite catalyst and ritalin is 1.5: 100; The mol ratio of hydrogen and ritalin is 60: 1; The temperature of hydrogenation is 280 ℃, and absolute pressure is 2MPa, and the reaction times is 2h;
Contain ethanol, methyl alcohol and unreacted ritalin and hydrogen in the hydrogenation mixture, wherein the transformation efficiency of ritalin is 86%, and the alcoholic acid yield is 80%.
The performance index of table 1 alcohol fuel
Table 1 is the result show:
1, the alcohol fuel purity of the present invention's preparation is high, alcoholic acid volume percent content >=99.5%, constant product quality;
2, the present invention adopts the supercritical esterification reaction, and the reaction mass transfer resistance is little, and RM is uniformly dispersed, and the reaction times is short, and need not to use catalyzer, and acetic acid conversion reaches 100% in the esterification, the selectivity of ritalin >=90%;
3, the present invention adopts copper zinc-aluminium-rare earth composite catalyst to carry out hydrogenation, compares with traditional CuZnAl catalyst, can obviously improve the transformation efficiency and the alcoholic acid yield of ritalin, and hydrogenation efficient is high.
Claims (10)
1. method of utilizing acetic acid and methyl alcohol to prepare alcohol fuel comprises as follows step in sequence:
1) acetic acid and methyl alcohol are carried out the supercritical esterification reaction, make ritalin;
2) ritalin and hydrogen are carried out hydrogenation, make alcohol fuel.
2. the method for claim 1 is characterized in that, the mol ratio of acetic acid described in the step 1) and methyl alcohol is 1: 2-20, and the temperature of said supercritical esterification reaction is 220-350 ℃, and the reaction absolute pressure is 10-20MPa, and the reaction times is 1-3h.
3. the method for claim 1 is characterized in that, the preparation method of acetic acid described in the step 1) comprises as follows step in sequence:
A) abandoned biomass is carried out acid hydrolytic reaction, make hydrolyzed solution;
B) utilize acetic acid bacteria that hydrolyzed solution is carried out anaerobically fermenting, make the acetic acid mixed solution.
4. method as claimed in claim 3; It is characterized in that steps A) in utilize dilute sulphuric acid that abandoned biomass is carried out described acid hydrolytic reaction, wherein; The mass percent concentration of dilute sulphuric acid is 0.5-1%, and the weight proportion of abandoned biomass and dilute sulphuric acid is 1: 2-4; The acid hydrolytic reaction temperature is 120-150 ℃, and the absolute pressure of reaction is 0.2-0.6MPa, and the reaction times is 1-3 hour.
5. the method for claim 1 is characterized in that step 2) under the effect of copper zinc-aluminium-rare earth composite catalyst, carry out described hydrogenation, wherein the weight proportion of copper zinc-aluminium-rare earth composite catalyst and ritalin is 1.0-1.5: 100.
6. method as claimed in claim 5 is characterized in that, said copper zinc-aluminium-rare earth composite catalyst comprises CuZnAl catalyst and rare earth composite catalyst, and the weight proportion of CuZnAl catalyst and rare earth composite catalyst is 8-10: 1.
7. method as claimed in claim 5; It is characterized in that said CuZnAl catalyst comprises cupric oxide, zinc oxide and aluminum oxide, wherein the mass percentage content of cupric oxide is 50-70%; The mass percentage content of zinc oxide is 20-30%, and aluminum oxide quality degree is 10-20%.
8. method as claimed in claim 5 is characterized in that said rare earth composite catalyst comprises lanthanum trioxide and cerium oxide, and wherein the mol ratio of lanthanum element and Ce elements is 1-2: 1.
9. the method for claim 1 is characterized in that step 2) described in hydrogen and the mol ratio of ritalin be 20-60: 1, the temperature of said hydrogenation is 200-300 ℃, absolute pressure is 2-5Mpa, the reaction times is 0.5-2h.
10. an alcohol fuel is characterized in that being prepared from according to the arbitrary described method of claim 1-9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011104215314A CN102557870A (en) | 2011-12-15 | 2011-12-15 | Method for preparing fuel ethanol by using acetic acid and methanol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011104215314A CN102557870A (en) | 2011-12-15 | 2011-12-15 | Method for preparing fuel ethanol by using acetic acid and methanol |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102557870A true CN102557870A (en) | 2012-07-11 |
Family
ID=46404652
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011104215314A Pending CN102557870A (en) | 2011-12-15 | 2011-12-15 | Method for preparing fuel ethanol by using acetic acid and methanol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102557870A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102796573A (en) * | 2012-07-24 | 2012-11-28 | 北京金骄生物质化工有限公司 | Low-freezing biodiesel combined fuel and preparation method thereof |
| CN104058932A (en) * | 2014-07-07 | 2014-09-24 | 海南天材投资有限公司 | Production system and method for producing ethyl alcohol through adding of hydrogen in methyl acetate |
| CN104822643A (en) * | 2012-12-20 | 2015-08-05 | 阿彻丹尼尔斯米德兰德公司 | Hydrogenation products from biologically-derived carboxylic-acid esters |
| CN104854222A (en) * | 2012-12-20 | 2015-08-19 | 阿彻丹尼尔斯米德兰德公司 | Biofuels production from bio-derived carboxylic-acid esters |
| CN108707060A (en) * | 2018-07-14 | 2018-10-26 | 太原理工大学 | A kind of technique using dissociated methanol in-situ reducing acetic acid ethyl alcohol |
| CN110357779A (en) * | 2018-04-10 | 2019-10-22 | 山东华鲁恒升化工股份有限公司 | Prepare acetic acid esters technique and its equipment |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86105765A (en) * | 1985-07-23 | 1987-01-28 | Bp化学有限公司 | Method by carboxylicesters hydrogenation preparing alcohol |
| CN1762973A (en) * | 1999-03-11 | 2006-04-26 | 齐凯姆公司 | Process for producing ethanol |
| CN101468939A (en) * | 2007-12-28 | 2009-07-01 | 中国石油化工股份有限公司 | Method for preparing high-carbon alcohol by supercritical hydrogenation of fatty acid methyl ester |
-
2011
- 2011-12-15 CN CN2011104215314A patent/CN102557870A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86105765A (en) * | 1985-07-23 | 1987-01-28 | Bp化学有限公司 | Method by carboxylicesters hydrogenation preparing alcohol |
| CN1762973A (en) * | 1999-03-11 | 2006-04-26 | 齐凯姆公司 | Process for producing ethanol |
| CN101468939A (en) * | 2007-12-28 | 2009-07-01 | 中国石油化工股份有限公司 | Method for preparing high-carbon alcohol by supercritical hydrogenation of fatty acid methyl ester |
Non-Patent Citations (2)
| Title |
|---|
| 邢存章等: "《超临界甲醇酯化单酸制备生物柴油的研究》", 《中国油脂》 * |
| 鞠庆华等: "《甘油三乙酸酯超临界酯交换反应及其动力学研究》", 《石油化工》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102796573A (en) * | 2012-07-24 | 2012-11-28 | 北京金骄生物质化工有限公司 | Low-freezing biodiesel combined fuel and preparation method thereof |
| CN102796573B (en) * | 2012-07-24 | 2014-09-17 | 北京金骄生物质化工有限公司 | Low-freezing biodiesel combined fuel and preparation method thereof |
| CN104822643A (en) * | 2012-12-20 | 2015-08-05 | 阿彻丹尼尔斯米德兰德公司 | Hydrogenation products from biologically-derived carboxylic-acid esters |
| CN104854222A (en) * | 2012-12-20 | 2015-08-19 | 阿彻丹尼尔斯米德兰德公司 | Biofuels production from bio-derived carboxylic-acid esters |
| CN104822643B (en) * | 2012-12-20 | 2018-06-15 | 阿彻丹尼尔斯米德兰德公司 | Hydrogenated products from biologically-derived carboxylate |
| CN104058932A (en) * | 2014-07-07 | 2014-09-24 | 海南天材投资有限公司 | Production system and method for producing ethyl alcohol through adding of hydrogen in methyl acetate |
| CN110357779A (en) * | 2018-04-10 | 2019-10-22 | 山东华鲁恒升化工股份有限公司 | Prepare acetic acid esters technique and its equipment |
| CN108707060A (en) * | 2018-07-14 | 2018-10-26 | 太原理工大学 | A kind of technique using dissociated methanol in-situ reducing acetic acid ethyl alcohol |
| CN108707060B (en) * | 2018-07-14 | 2022-03-18 | 太原理工大学 | Process for preparing ethanol by in-situ reduction of acetic acid by cracking methanol |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US8835703B2 (en) | Method for the production of one or more olefins, an olefin, and a polymer | |
| CN101358218B (en) | Method for producing xylose coupled cogeneration of propanone, butanol and ethanol using stalk | |
| US7662617B2 (en) | Systems and processes for cellulosic ethanol production | |
| Yong et al. | Second-generation bioenergy from oilseed crop residues: Recent technologies, techno-economic assessments and policies | |
| Liu et al. | A review on the promising fuel of the future–Biobutanol; the hindrances and future perspectives | |
| CN104774876B (en) | A kind of method of lignocellulose biomass comprehensive utilization | |
| US20080299633A1 (en) | Systems and processes for cellulosic ethanol production | |
| CN102557870A (en) | Method for preparing fuel ethanol by using acetic acid and methanol | |
| CN101805767B (en) | High-purity isomaltose hypgather and alcohol co-production preparation method | |
| CN103113187B (en) | By the method for acetic acid ethanol co-production ethyl acetate | |
| CN101575619B (en) | Method for coproducing multiple products by taking shinyleaf yellowhorn as raw material | |
| CN101235392A (en) | Cellulose fuel ethanol and preparation method thereof | |
| CN101608192A (en) | A kind of method of utilizing corn cob to produce Succinic Acid | |
| CN101532038A (en) | Method for preparing fuel ethanol by plant straws | |
| CN112746088B (en) | Method for co-producing xylitol and fuel ethanol by fermenting lignocellulose serving as raw material | |
| CN113087760A (en) | Method for extracting protein from vinasse | |
| CA3162234A1 (en) | Systems and methods for integrated co2 reuse using vapor compression | |
| CN109402196A (en) | A method of biological liquid fuel is produced using biomass | |
| CN108410912B (en) | Method for directly preparing butanol by using starch-containing waste | |
| CN101863765A (en) | Method for preparing fumaric acid ester by using plant straws | |
| CA1168998A (en) | Alcohol manufacturing process | |
| CN221918056U (en) | Green energy power generation device | |
| Senatore et al. | Ethanol: A Brief Review of the Major Production Methods in the World | |
| CN102796573A (en) | Low-freezing biodiesel combined fuel and preparation method thereof | |
| CN102286549A (en) | Method for producing acetone and butanol by co-fermenting cellobiose, pentaglucose and hexose |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20120711 |