CN101293817A - Method for preparing methyl-ethyl ketone - Google Patents
Method for preparing methyl-ethyl ketone Download PDFInfo
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- CN101293817A CN101293817A CNA2008101224894A CN200810122489A CN101293817A CN 101293817 A CN101293817 A CN 101293817A CN A2008101224894 A CNA2008101224894 A CN A2008101224894A CN 200810122489 A CN200810122489 A CN 200810122489A CN 101293817 A CN101293817 A CN 101293817A
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- butyleneglycol
- molecular sieve
- methylethylketone
- reaction
- reaction solution
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- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 title claims abstract description 117
- 238000000034 method Methods 0.000 title claims abstract description 35
- 229940032007 methylethyl ketone Drugs 0.000 title 1
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 239000003054 catalyst Substances 0.000 claims abstract description 26
- 239000002808 molecular sieve Substances 0.000 claims abstract description 22
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 22
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims description 50
- 238000000855 fermentation Methods 0.000 claims description 28
- 230000004151 fermentation Effects 0.000 claims description 28
- 230000003197 catalytic effect Effects 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 18
- 238000002309 gasification Methods 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 12
- 238000006297 dehydration reaction Methods 0.000 claims description 11
- FRXSZNDVFUDTIR-UHFFFAOYSA-N 6-methoxy-1,2,3,4-tetrahydroquinoline Chemical compound N1CCCC2=CC(OC)=CC=C21 FRXSZNDVFUDTIR-UHFFFAOYSA-N 0.000 claims description 10
- 238000006555 catalytic reaction Methods 0.000 claims description 10
- 239000007795 chemical reaction product Substances 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 10
- 230000018044 dehydration Effects 0.000 claims description 8
- 241000193830 Bacillus <bacterium> Species 0.000 claims description 6
- 241000894006 Bacteria Species 0.000 claims description 6
- 238000005189 flocculation Methods 0.000 claims description 6
- 230000016615 flocculation Effects 0.000 claims description 6
- 241000588748 Klebsiella Species 0.000 claims description 5
- 239000002028 Biomass Substances 0.000 claims description 4
- 241000588914 Enterobacter Species 0.000 claims description 4
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- 238000001914 filtration Methods 0.000 claims description 4
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 230000000813 microbial effect Effects 0.000 description 5
- 230000001105 regulatory effect Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000008103 glucose Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 241000588747 Klebsiella pneumoniae Species 0.000 description 3
- 230000001580 bacterial effect Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 241000588697 Enterobacter cloacae Species 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 201000008225 Klebsiella pneumonia Diseases 0.000 description 2
- 241000194105 Paenibacillus polymyxa Species 0.000 description 2
- 206010035717 Pneumonia klebsiella Diseases 0.000 description 2
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- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 235000005822 corn Nutrition 0.000 description 2
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
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- 229910001220 stainless steel Inorganic materials 0.000 description 2
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- 239000002699 waste material Substances 0.000 description 2
- HNSDLXPSAYFUHK-UHFFFAOYSA-N 1,4-bis(2-ethylhexyl) sulfosuccinate Chemical compound CCCCC(CC)COC(=O)CC(S(O)(=O)=O)C(=O)OCC(CC)CCCC HNSDLXPSAYFUHK-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- PKAUICCNAWQPAU-UHFFFAOYSA-N 2-(4-chloro-2-methylphenoxy)acetic acid;n-methylmethanamine Chemical compound CNC.CC1=CC(Cl)=CC=C1OCC(O)=O PKAUICCNAWQPAU-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
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- 244000063299 Bacillus subtilis Species 0.000 description 1
- 235000014469 Bacillus subtilis Nutrition 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 241000370738 Chlorion Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241000588749 Klebsiella oxytoca Species 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 240000003183 Manihot esculenta Species 0.000 description 1
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- 244000138286 Sorghum saccharatum Species 0.000 description 1
- 235000011684 Sorghum saccharatum Nutrition 0.000 description 1
- -1 Synolac Polymers 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229920006387 Vinylite Polymers 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229940041514 candida albicans extract Drugs 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
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- 238000010812 external standard method Methods 0.000 description 1
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- 239000008187 granular material Substances 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229940045505 klebsiella pneumoniae Drugs 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
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- 238000012544 monitoring process Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000000050 nutritive effect Effects 0.000 description 1
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- 229920003987 resole Polymers 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
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- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
The invention belongs to the chemical technology field, and discloses a method for preparing methyl ethyl ketone. The methyl ethyl ketone is prepared from 2,3-butanediol by dehydrating in the presence of ZSM-5 or NaY molecular sieve catalyst. Under process conditions, the catalyst is not easily deactivated and has good stability. The method has the advantages of high substrate conversion and product yield, simple process, low production cost and less environmental pollution, and can satisfy industrial requirement. With the method, the conversion rate of 2,3-butanediol is 90.5%-100%, and the selectivity of methyl ethyl ketone is 83.7%-91.3%.
Description
Technical field
The invention belongs to chemical technology field, be specifically related to a kind of preparation method of methylethylketone.
Background technology
Methylethylketone is the fine solvent of macromolecular compound such as soluble cotton, urethane, Vinylite, acrylic resin, Synolac, resol, pharmaceuticals production and lubricating oil dewaxing, is the best substitute of " triphen " solvent.In addition, methylethylketone also is a kind of important fine chemical material, is widely used in industrial circles such as oil refining, coating, tackiness agent, printing ink, tape, medicine and electronic component.The major industry route of methylethylketone has at present: and n-butene method, normal butane liquid phase oxidation and Isobuytel Benzene method etc. (Cui Xiaoming. fine chemical material and intermediate, 2006,4 (4): 20-26).But these method three wastes discharge amounts are big, pollution to environment is comparatively serious, and their employed raw materials all come from non-renewable fossil resource, present worsening shortages along with fossil resource, constantly riseing of oil price, the production cost that utilizes aforesaid method to produce methylethylketone will certainly raise gradually.Therefore, seeking a kind of suitable novel method, to replace the petroleum base route production method of methylethylketone extremely urgent.
Utilize 2 of microbe fermentation method preparation, 3-butyleneglycol catalytic dehydration prepares methylethylketone and is expected to realize this goal.As far back as nineteen eighty-two, Emerson etc. just once utilized 2.5～10% (v/v) the various concentration of sulfuric acid homogeneous catalysis 2,3-butyleneglycol (pure 2, the 3-butyleneglycol is formulated) dehydration preparation methylethylketone (Emerson R R, Flicklnger M C, Tsao G T.Industrial﹠amp; Engineering Chemistry Product Research and Development, 1982,21 (3): 473-477); Wang Di etc. also once with the sulphuric acid soln catalysis of 5～45% (v/v) with the acid-producing Klebsiella bacterium glucose fermentation make 2,3-butyleneglycol fermentation liquid prepares methylethylketone (Wang Di, Wang Fanqiang, Wang Jianhua. meticulous and specialty chemicals, 2000,8 (9): 19-20), but these two kinds of methods are because of adopting sulfuric acid serious and how big for environment pollution acid waste liquid is to equipment corrosion as catalyzer, product is difficult to separate, and possesses industrial production foreground hardly.Tran etc. are catalyzer for the solid acid (aluminum oxide) that overcomes above-mentioned shortcoming and use instead to be made up of sulfonic acid covalency group and inorganic carrier; catalysis makes 2 by the Klebsiella pneumonia fermentation; 3-butyleneglycol fermentation fluid dewatering generates methylethylketone (Tran A V; Chambers R P.Biotechnology and Bioengineering; 1987; 29 (3): 343-351); but the catalyzer of its use (aluminum oxide) is subjected to the influence of impurity in the fermented liquid comparatively obvious in reaction process; than easy inactivation, be unfavorable for the continuous production of mass-producing.
Therefore, develop and a kind ofly be suitable for 2 efficiently, the catalyzer of 3-butyleneglycol dehydration preparation methylethylketone, and with this effective catalyst be used for that direct catalytic pretreatment crosses 2, it is necessary that 3-butyleneglycol fermentation liquid prepares methylethylketone.
Summary of the invention
The purpose of this invention is to provide a kind of employing molecular sieve catalyst catalysis 2, the dehydration of 3-butyleneglycol prepares the method for methylethylketone.
The objective of the invention is to realize by following technical measures:
A kind of preparation method of methylethylketone, this method is a catalyzer with ZSM-5 molecular sieve or NaY molecular sieve, catalysis 2,3-butyleneglycol reaction solution dehydration preparation methylethylketone.
Described method, wherein the Si of ZSM-5 molecular sieve is 25～60 with the ratio of Al; The Si of NaY molecular sieve is 2～5 with the ratio of Al.
Described method, wherein 2,3-butyleneglycol reaction solution is by 2, the aqueous solution that the 3-butyleneglycol is formulated or be the fermented liquid that raw material obtains by fermentation using bacteria with the sugar in biomass source.Bacterium is that Klebsiella (Klebisella), enterobacter (Enterobacter), series bacillus belong to a kind of in the bacterium of (Paenibacillus), bacillus (Bacillus), serratia (Serratia).In the fermented liquid 2, the concentration of 3-butyleneglycol is 30～200g/L.Biomass are selected from one or more in corn, cassava, sweet sorghum, sugarcane, Herba Eichhorniae, the grain crop material etc.
Fermented liquid need carry out pre-treatment before carrying out catalyzed reaction; The fermentation liquor pretreatment mode is to remove thalline earlier, and re-adjustment fermented liquid pH to 6.0～8.0 are adsorbed 30～60min after-filtration with gac at last under 65～85 ℃ of conditions, collect filtrate for later use.The mode of wherein removing thalline is filtration, flocculation, micro-filtration or centrifugal.Flocculation agent can adopt chitosan, polyvinyl alcohol or polyacrylamide.
Described method, wherein the step of catalytic and dehydration reaction is: with pack into the constant temperature zone of fixed-bed reactor of molecular sieve catalyst, at N
2Protection is warmed up to 200～350 ℃ with catalytic bed down, and with 2,3-butyleneglycol reaction solution joins in the reactor, and react by catalytic bed the gasification back, and reaction product obtains methylethylketone through after the refrigerated separation.
Described method, wherein N
2Volume space velocity be 1～10h
-1, preferred 3～6h
-1The mass space velocity of reaction solution is 0.5～3h
-1, preferred 1～2h
-1
Beneficial effect of the present invention:
The catalyzer that uses among the present invention is to 2, the catalytic efficiency height of 3-butyleneglycol, and target product methylethylketone transformation efficiency is higher, is a kind ofly can satisfy the very strong methylethylketone new process for producing of industrialization demand, practicality.
The present invention adopts the sugar-fermenting preparation 2 in biomass material source, and 3-butyleneglycol and then catalytic dehydration prepare methylethylketone, can avoid using the fossil resource that generally uses in the present methylethylketone industrialized preparing process, meet the trend of Sustainable development; In addition, 2,3-butyleneglycol fermentation liquid need not separate purification, promptly can be used as the substrate catalytic dehydration that sets out through pre-treatment and prepare methylethylketone, and after pre-treatment, directly adopt ZSM-5 or this reaction system of NaY molecular sieve catalytic, under this invented technology condition, catalyzer is difficult for inactivation, good stability, and substrate conversion efficiency and target product yield are higher, the entire reaction operating process is simple, production cost is low, and environmental pollution is little, and 2,3-butyleneglycol transformation efficiency can reach 90.5%～100%, and the methylethylketone selectivity can reach 83.7%～91.3%.
Embodiment
The following examples elaborate to the present invention, but to the present invention without limits.
General explanation:
In the embodiment of the invention, described fermented liquid is to adopt microorganism strains batch fermentation or batch formula stream to add glucose fermentation to obtain, possesses the required nutritive ingredient of microorganism growth in the fermention medium, as carbon sources such as glucose, nitrogenous sources such as yeast extract paste, corn steep liquor or urea, negatively charged ion such as positively charged ions such as sodium, potassium, ammonia, magnesium, calcium and phosphate radical, sulfate radical, chlorion, and trace elements such as zinc, iron, manganese, copper, cobalt, boron and molybdenum.Described fermentation produces 2, and the bacterial classification of 3-butyleneglycol all is prior art bacterial classifications commonly used, and fermentation process also is to well known to a person skilled in the art technology.When fermentation stops, 2, the concentration of 3-butyleneglycol is 30～200g/L.Residual substrate glucose and product 2 in the fermented liquid, 3-butyleneglycol adopt DIONEX summit P680 high performance liquid chromatograph to measure.Chromatographic column is an Aminex HPX-87H post (Bio-Rad), and column temperature is 60 ℃, and detector is a SHODEXRI-101 refractive power differential detector, and moving phase is 0.005mol/L H
2SO
4, flow velocity is 0.2mL/min, sample size is 20 μ L (external standard method is quantitative).
The product methylethylketone adopts Agilent 6890N gas chromatograph (FID flame ionization ditector, HP ChemStation chem workstation) detects, chromatographic column is: FFAP modified poly (ethylene glycol) capillary column (L=30m, ID=0.32mm, DF=1 μ m), column temperature: 80 ℃ keep 1min, rise to 200 ℃ with 40 ℃/min then, keep 3min; Temperature of vaporization chamber is 240 ℃, and the fid detector temperature is 220 ℃; Carrier gas: high purity nitrogen; Column flow rate: 0.5ml/min (constant current); Splitting ratio 40: 1; Sample size 1 μ L (with propyl carbinol is interior mark, inner mark method ration).The methylethylketone separation method adopts the technology that well known to a person skilled in the art.
The catalytic and dehydration reaction process is carried out on fixed-bed reactor among the embodiment.Pipe is the silica tube of internal diameter 8mm, long 300mm, wall thickness 1mm in the fixed-bed reactor.Catalyst layer is positioned at the position placed in the middle of silica tube.Crystal reaction tube places the aluminum heating jacket, and heating jacket heats by electrically heated rod, and thermopair is positioned at the heating jacket layer near inner wall section.The working order of heating rod is carried out real-time monitoring according to the feedback information of thermopair.The reactor feed mouth is introduced gas and liquid respectively by Y-junction.What the injection port of gas connected is gas bomb, middle gas flow with mass flow controller control nitrogen.What the liquid injection port connected is 2,3-butyleneglycol reaction solution, and its flow is controlled with constant flow pump in the centre.Reactor exit is drawn reaction product by the stainless steel pipeline, and the stainless steel pipeline feeds receiving flask through condensate trap.Fixed-bed reactor of the prior art all can be used for the present invention.
ZSM-5 (Si/Al=25～60) molecular sieve or NaY (Si/Al=2～5) molecular sieve catalyst are made suitable particle (according to the size of reactor used size decision granules of catalyst, according to the size of used reactor, select 30～50 orders for use in the example of the present invention).
Revivification of catalyst (i.e. regeneration) method: can adopt the method for in-situ regeneration, promptly when catalyst activity reduced, changing carrier gas was oxygen, and volume space velocity is 3h
-1, and be warming up to 500 ℃, and kept 2 hours, cause the carbon distribution that catalyst activity reduces with elimination.
Embodiment 1
Step 1:
The preparation of reaction solution: with 40g 2, it is standby that 3-butyleneglycol (chemical pure) is mixed with the aqueous solution 200mL of 200g/L.
Step 2:
With pack into the constant temperature zone of tubular fixed-bed reactor of 30～50 purpose ZSM-5 (Si/Al=25) molecular sieve catalyst 1.2g, rest part is filled with quartz sand.After the systems inspection sealing, be 3h at volume space velocity
-1N
2With catalytic bed temperature programming to 300 ℃, the reaction solution that step 1 is obtained is 2h by mass space velocity then under the gas velocity
-1Inject gasification system, react by catalytic bed the gasification back, product is after ice-water bath cooling and gas-liquid separation, the gas emptying is analyzed the liquid sampling that reaction was collected after 1.5 hours, according to the content of reaction product component, calculate 2 with the carbon atom mole number, the transformation efficiency of 3-butyleneglycol and the selectivity of methylethylketone are respectively 97% and 88.2%, move one month continuously, and catalyst activity does not have obvious decline.
Embodiment 2:
Step 1:
The preparation of reaction solution: collect 200mL by acid-producing Klebsiella bacterium (Klebsiella oxytoca) CCTCC M 207023 (from application number be 200710021641.5, publication number is the bacterial classification that CN101063095A, name are called preservation in the patent application document of " a kind of acid-producing Klebsiella bacterium and application thereof ") fermentation make 2,3-butyleneglycol fermentation liquid (wherein 2, the concentration of 3-butyleneglycol is 125g/L), fermented liquid is obtained clear liquid through flocculate with chitosan after removing thalline, regulate pH with NaOH, making its pH is 7.0.
Step 2:
With pack into the constant temperature zone of tubular fixed-bed reactor of 30～50 purpose ZSM-5 (Si/Al=30) molecular sieve catalyst 1.2g, rest part is filled with quartz sand.After the systems inspection sealing, be 3h at volume space velocity
-1N
2With catalytic bed temperature programming to 200 ℃, the reaction solution that step 1 is obtained is 2h by mass space velocity then under the gas velocity
-1Inject gasification system, react by catalytic bed the gasification back, product is after ice-water bath cooling and gas-liquid separation, the gas emptying is analyzed the liquid sampling that reaction was collected after 1.5 hours, according to the content of reaction product component, calculate 2 with the carbon atom mole number, the transformation efficiency of 3-butyleneglycol and the selectivity of methylethylketone are respectively 98.5% and 90.5%, move one month continuously, and catalyst activity does not have obvious decline.
Embodiment 3
Step 1:
Collect 200mL by Klebsiella pneumonia (Klebsiellapneumoniae) CICC 10011 (administrative center provides by the preservation of Chinese industrial microbial strains) fermentation make 2,3-butyleneglycol fermentation liquid (wherein 2, the concentration of 3-butyleneglycol is 92.4g/L), fermented liquid is obtained clear liquid through centrifugal after removing thalline, and regulating pH with NaOH is 7.0.
Step 2:
With pack into the constant temperature zone of tubular fixed-bed reactor of 30～50 purpose ZSM-5 (Si/Al=38) molecular sieve catalyst 1.2g, rest part is filled with quartz sand.After the systems inspection sealing, be 3h at volume space velocity
-1N
2With catalytic bed temperature programming to 250 ℃, the reaction solution that step 1 is obtained is 2h by mass space velocity then under the gas velocity
-1Inject gasification system, react by catalytic bed the gasification back, product is after ice-water bath cooling and gas-liquid separation, the gas emptying is analyzed the liquid sampling that reaction was collected after 1.5 hours, according to the content of reaction product component, calculate 2 with the carbon atom mole number, the transformation efficiency of 3-butyleneglycol and the selectivity of methylethylketone are respectively 100% and 83.7%, move one month continuously, and catalyst activity does not have obvious decline.
Embodiment 4
Step 1:
Collect 200mL by enterobacter cloacae (Enterobacter cloacae) CICC 10014 (administrative center provides by the preservation of Chinese industrial microbial strains) fermentation make 2,3-butyleneglycol fermentation liquid (wherein 2, the concentration of 3-butyleneglycol is 100.8g/L), obtain clear liquid after fermented liquid removed by filter thalline, regulating pH with KOH is 7.0.
Step 2:
With pack into the constant temperature zone of tubular fixed-bed reactor of 30～50 purpose ZSM-5 (Si/Al=60) molecular sieve catalyst 1.2g, rest part is filled with quartz sand.After the systems inspection sealing, be 3h at volume space velocity
-1N
2With catalytic bed temperature programming to 200 ℃, the reaction solution that step 1 is obtained is 2h by mass space velocity then under the gas velocity
-1Inject gasification system, react by catalytic bed the gasification back, product is after ice-water bath cooling and gas-liquid separation, the gas emptying is analyzed the liquid sampling that reaction was collected after 1.5 hours, according to the content of reaction product component, calculate 2 with the carbon atom mole number, the transformation efficiency of 3-butyleneglycol and the selectivity of methylethylketone are respectively 99.2% and 87%, move one month continuously, and catalyst activity does not have obvious decline.
Embodiment 5
Step 1:
Collect 300mL by Paenibacillus polymyxa (Paenibacillus polymyxa) CICC 10010 (administrative center provides by the preservation of Chinese industrial microbial strains) fermentation make 2,3-butyleneglycol fermentation liquid (wherein 2, the concentration of 3-butyleneglycol is 87.2g/L), fermented liquid is obtained clear liquid through micro-filtration after removing thalline, and regulating pH with KOH is 7.0.
Step 2:
With pack into the constant temperature zone of tubular fixed-bed reactor of 30～50 purpose NaY (Si/Al=2.7) molecular sieve catalyst 1.2g, rest part is filled with quartz sand.After the systems inspection sealing, be 3h at volume space velocity
-1N
2With catalytic bed temperature programming to 200 ℃, the reaction solution that step 1 is obtained is 3h by mass space velocity then under the gas velocity
-1Inject gasification system, react by catalytic bed the gasification back, product is after ice-water bath cooling and gas-liquid separation, the gas emptying is reacted the liquid sampling of collecting after 1.5 hours and is analyzed, according to the content of reaction product component, calculate 2 with the carbon atom mole number, the transformation efficiency of 3-butyleneglycol and the selectivity of methylethylketone are respectively 95% and 86.4%, move one month continuously, and catalyst activity does not have obvious decline.
Embodiment 6
Step 1:
Collect 200mL by subtilis (Bacillus subtilis) CICC 10026 (administrative center provides by the preservation of Chinese industrial microbial strains) fermentation make 2,3-butyleneglycol fermentation liquid (wherein 2, the concentration of 3-butyleneglycol is 84.6g/L), obtain clear liquid after thalline is removed in flocculation through polyvinyl alcohol with fermented liquid, regulating pH with NaOH is 7.0.
Step 2:
With pack into the constant temperature zone of tubular fixed-bed reactor of 30～50 purpose NaY (Si/Al=3.6) molecular sieve catalyst 1.2g, rest part is filled with quartz sand.After the systems inspection sealing, be 3h at volume space velocity
-1N
2With catalytic bed temperature programming to 200 ℃, the reaction solution that step 1 is obtained is 2h by mass space velocity then under the gas velocity
-1Inject gasification system, react by catalytic bed the gasification back, product is after ice-water bath cooling and gas-liquid separation, the gas emptying is analyzed the liquid sampling that reaction was collected after 1.5 hours, according to the content of reaction product component, calculate 2 with the carbon atom mole number, the transformation efficiency of 3-butyleneglycol and the selectivity of methylethylketone are respectively 92.6% and 89%, move one month continuously, and catalyst activity does not have obvious decline.
Embodiment 7
Step 1: collect 300mL by serratia marcescens (Serratia marcescens) CICC 10187 (administrative center provides by the preservation of Chinese industrial microbial strains) fermentation make 2,3-butyleneglycol fermentation liquid (wherein 2, the concentration of 3-butyleneglycol is 97.5g/L), obtain clear liquid after thalline is removed in flocculation through polyacrylamide with fermented liquid, regulating pH with KOH is 7.0.
Step 2:
With pack into the constant temperature zone of tubular fixed-bed reactor of 30～50 purpose NaY (Si/Al=5) molecular sieve catalyst 1.2g, rest part is filled with quartz sand.After the systems inspection sealing, be 3h at volume space velocity
-1N
2With catalytic bed temperature programming to 200 ℃, the reaction solution that step 1 is obtained is 2h by mass space velocity then under the gas velocity
-1Inject gasification system, react by catalytic bed the gasification back, product is after ice-water bath cooling and gas-liquid separation, the gas emptying is analyzed the liquid sampling that reaction was collected after 1.5 hours, according to the content of reaction product component, calculate 2 with the carbon atom mole number, the transformation efficiency of 3-butyleneglycol and the selectivity of methylethylketone are respectively 90.5% and 91.3%, move one month continuously, and catalyst activity does not have obvious decline.
Claims (10)
1, a kind of preparation method of methylethylketone is characterized in that with ZSM-5 molecular sieve or NaY molecular sieve be catalyzer, catalysis 2,3-butyleneglycol reaction solution dehydration preparation methylethylketone.
2, method according to claim 1, the Si that it is characterized in that the ZSM-5 molecular sieve is 25～60 with the ratio of Al; The Si of NaY molecular sieve is 2～5 with the ratio of Al.
3, method according to claim 1 is characterized in that 2, and 3-butyleneglycol reaction solution is by 2, the aqueous solution that the 3-butyleneglycol is formulated or be the fermented liquid that raw material obtains by fermentation using bacteria with the sugar in biomass sources.
4, method according to claim 3 is characterized in that in the fermented liquid 2, and the concentration of 3-butyleneglycol is 30～200g/L.
5, method according to claim 3 is characterized in that described bacterium is that Klebsiella (Klebisella), enterobacter (Enterobacter), series bacillus belong to a kind of in the bacterium of (Paenibacillus), bacillus (Bacillus), serratia (Serratia).
6, method according to claim 3 is characterized in that fermented liquid need carry out pre-treatment before carrying out catalyzed reaction; The fermentation liquor pretreatment mode is to remove thalline earlier, and re-adjustment fermented liquid pH to 6.0～8.0 are adsorbed 30～60min after-filtration with gac at last under 65～85 ℃ of conditions, collect filtrate for later use.
7, method according to claim 6, the mode that it is characterized in that removing thalline is filtration, flocculation, micro-filtration or centrifugal.
8, method according to claim 7 is characterized in that flocculation agent is chitosan, polyvinyl alcohol or polyacrylamide.
9, method according to claim 1 is characterized in that the step of catalytic and dehydration reaction is: with pack into the constant temperature zone of fixed-bed reactor of molecular sieve catalyst, at N
2Protection is warmed up to 200～350 ℃ with catalytic bed down, and with 2,3-butyleneglycol reaction solution joins in the reactor, and react by catalytic bed the gasification back, and reaction product obtains methylethylketone through after the refrigerated separation.
10, method according to claim 7 is characterized in that N
2Volume space velocity be 1～10h
-1, the mass space velocity of reaction solution is 0.5～3h
-1
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| CNA2008101224894A CN101293817A (en) | 2008-06-20 | 2008-06-20 | Method for preparing methyl-ethyl ketone |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101580462B (en) * | 2009-05-08 | 2012-05-23 | 清华大学 | Method for preparing ethyl methyl ketone by dehydrating 2,3-butanediol efficiently |
| CN102826980A (en) * | 2012-09-04 | 2012-12-19 | 华东理工大学 | Method for preparing methyl ethyl ketone by performing gas phase dehydration on 2,3-butanediol |
| CN102962092A (en) * | 2012-12-14 | 2013-03-13 | 南京工业大学 | High-performance catalyst for preparing methyl ethyl ketone by dehydrating 2,3-butanediol |
| CN103691479A (en) * | 2013-12-12 | 2014-04-02 | 大连理工大学 | Preparation method and application of composite catalyst |
| RU2574060C1 (en) * | 2014-12-08 | 2016-02-10 | Ирина Игоревна Иванова | Method of producing methyl ethyl ketone and butadiene-1,3 |
| KR20180076069A (en) * | 2016-12-27 | 2018-07-05 | 서강대학교산학협력단 | Method for manufacturing methylethylketone and 2,3-butanediol |
-
2008
- 2008-06-20 CN CNA2008101224894A patent/CN101293817A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101580462B (en) * | 2009-05-08 | 2012-05-23 | 清华大学 | Method for preparing ethyl methyl ketone by dehydrating 2,3-butanediol efficiently |
| CN102826980A (en) * | 2012-09-04 | 2012-12-19 | 华东理工大学 | Method for preparing methyl ethyl ketone by performing gas phase dehydration on 2,3-butanediol |
| CN102826980B (en) * | 2012-09-04 | 2014-10-15 | 华东理工大学 | Method for preparing methyl ethyl ketone by performing gas phase dehydration on 2,3-butanediol |
| CN102962092A (en) * | 2012-12-14 | 2013-03-13 | 南京工业大学 | High-performance catalyst for preparing methyl ethyl ketone by dehydrating 2,3-butanediol |
| CN103691479A (en) * | 2013-12-12 | 2014-04-02 | 大连理工大学 | Preparation method and application of composite catalyst |
| CN103691479B (en) * | 2013-12-12 | 2016-04-06 | 大连理工大学 | A kind of preparation method of composite catalyst and application |
| RU2574060C1 (en) * | 2014-12-08 | 2016-02-10 | Ирина Игоревна Иванова | Method of producing methyl ethyl ketone and butadiene-1,3 |
| KR20180076069A (en) * | 2016-12-27 | 2018-07-05 | 서강대학교산학협력단 | Method for manufacturing methylethylketone and 2,3-butanediol |
| KR101882588B1 (en) * | 2016-12-27 | 2018-07-27 | 서강대학교산학협력단 | Method for manufacturing methylethylketone and 2,3-butanediol |
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