WO2001027062A2 - Process and device for hydrolytically obtaining a carboxylic acid and alcohol from the corresponding carboxylate - Google Patents
Process and device for hydrolytically obtaining a carboxylic acid and alcohol from the corresponding carboxylate Download PDFInfo
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- WO2001027062A2 WO2001027062A2 PCT/CH2000/000551 CH0000551W WO0127062A2 WO 2001027062 A2 WO2001027062 A2 WO 2001027062A2 CH 0000551 W CH0000551 W CH 0000551W WO 0127062 A2 WO0127062 A2 WO 0127062A2
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- WIPO (PCT)
- Prior art keywords
- distillation column
- reactor
- catalyst
- reactive distillation
- flow
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- 150000007942 carboxylates Chemical class 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 39
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 150000001735 carboxylic acids Chemical class 0.000 title claims 7
- 238000000066 reactive distillation Methods 0.000 claims abstract description 82
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 43
- 239000000203 mixture Substances 0.000 claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- 230000007062 hydrolysis Effects 0.000 claims abstract description 41
- 239000003054 catalyst Substances 0.000 claims description 89
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 54
- 238000004821 distillation Methods 0.000 claims description 37
- 238000000926 separation method Methods 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 21
- 238000012856 packing Methods 0.000 claims description 20
- 239000011541 reaction mixture Substances 0.000 claims description 17
- -1 alcohol Chemical class 0.000 claims description 6
- 239000012530 fluid Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 238000000605 extraction Methods 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 2
- 239000011949 solid catalyst Substances 0.000 claims description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 claims 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- 239000003456 ion exchange resin Substances 0.000 claims 1
- 229920003303 ion-exchange polymer Polymers 0.000 claims 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 abstract description 61
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 abstract description 61
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 abstract description 10
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- HVAMZGADVCBITI-UHFFFAOYSA-M pent-4-enoate Chemical compound [O-]C(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-M 0.000 abstract description 5
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 abstract 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 abstract 2
- GJRQTCIYDGXPES-UHFFFAOYSA-N isobutyl acetate Chemical compound CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 abstract 2
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropyl acetate Chemical compound CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 abstract 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N propyl acetate Chemical compound CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 abstract 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 75
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 71
- 239000000047 product Substances 0.000 description 14
- 239000000306 component Substances 0.000 description 9
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 235000019253 formic acid Nutrition 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 description 1
- 101100441252 Caenorhabditis elegans csp-2 gene Proteins 0.000 description 1
- 229920000114 Corrugated plastic Polymers 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000011491 glass wool Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 238000003260 vortexing Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/083—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid anhydrides
- C07C51/087—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid anhydrides by hydrolysis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/009—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping in combination with chemical reactions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
- B01J8/0446—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical
- B01J8/0476—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical in two or more otherwise shaped beds
- B01J8/0488—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical in two or more otherwise shaped beds the beds being placed in separate reactors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/18—Details relating to the spatial orientation of the reactor
- B01J2219/185—Details relating to the spatial orientation of the reactor vertical
-
- 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
- Y02P20/10—Process efficiency
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S203/00—Distillation: processes, separatory
- Y10S203/06—Reactor-distillation
Definitions
- the present invention relates to a process and to a device for the simultaneous hydrolytic cleavage of a carboxylate into the corresponding carboxylic and alcohol .
- Carboxylates especially low molecular weight carboxylates, occur in the chemical industry during various reactions as by-products or main products.
- methyl acetate is a typical by-product in the production of purified polyvinyl alcohol.
- methyl acetate is not an economically interesting product, since it cannot be profitably sold on the market.
- a better price can be obtained if methyl acetate is hy- drolysed into acetic acid and methanol.
- the hydrolysis can be carried out either as a batch process or continuously, by using either a reactor in conjunction with conventional .distillation or a single reactive distillation column.
- BESTATIGUNGSKOPIE tages (a) since the reaction is an equilibrium reaction with a small equilibrium constant, the yield of reaction product is small, (b) because of the azeo- tropic mixture which is set up in the reaction mixture between methyl acetate/water, on the one hand, and methyl acetate/methanol, on the other, several distillation stages are needed after the reaction. This leads to high investment and running costs, (c) corrosion problems occur because homogeneous catalysts such as sulphuric and hydrochloric acid are used in the known conventional processes.
- US 5,113,015 discloses a process for obtaining acetic acid from methyl acetate, in which methyl acetate and water are brought into contact in the presence of catalyst packing in a distillation column. In this case, the methyl acetate is hydrolysed into acetic acid and methanol. The resulting reaction mixture is in this case partially separated at the same time in the separation column.
- US 5,770,770 likewise discloses a process for the hydrolysis of a methyl acetate mixture in a reactive distillation column. The hydrolysis of a methyl acetate flow, which contains more than 50% methyl acetate, takes place in a reaction zone in which ion ex- change packing is present.
- the methyl acetate mixture is supplied from below to the ion exchange packing, and water from above onto the ion exchange packing.
- the un- reacted methyl acetate and water vapour are collected and condensed in the upper part of the reaction zone, and are then recycled back to the reaction zone.
- the base is collected and separated into the hydrolysis products and impurities.
- the impurities are then returned to the reaction zone.
- US 5,770,770 it is proposed to put the ion exchange material in the form of Raschig rings, by adding a plastic as binder to the ion exchanger and pressing the mixture into appropriate shapes.
- the catalyst material is conserved in glass wool, and the mat formed therefrom is rolled up with a wire mesh between the layers, in order to promote circulation of the fluids.
- the catalyst packing material may be a compliant open-mesh substance, e.g. a metal cloth.
- Another usable material is a more rigid cellular monolith, which can be produced from steel, polymers or ceramic material.
- the catalyst packing material may, however, also be produced from corrugated metal sheets or corrugated plastic or ceramic plates .
- the object of the present invention is therefore to provide an improved process for the hydrolysis of a carboxylate, especially methyl acetate, methyl formate and allyl acetate, by using a reactive distillation column.
- a carboxylate especially methyl acetate, methyl formate and allyl acetate
- a further object is to prevent poisoning of the catalyst used in the distillation column.
- Another object is to optimise the energy budget of the process. It is also intended to offer a process and a hydrolysis device, which allow great flexibility in terms of composition and quantity of the feed.
- the com- position of the product flows is also intended to be controllable in a large range by the process.
- a further object is to improve the conversion ratio of methyl acetate into acetic acid and methanol.
- a further advantage is that, by the use of a pre-reactor, the working life of the reactive distillation column can be substantially lengthened, since catalyst poisons, e.g. metal ions, are predominantly trapped in the pre-reactor.
- catalyst poisons e.g. metal ions
- differences or fluctuations in the feed quantity or in the mixture composition can be compensated.
- the par- ticle size of the catalyst material used in the pre- reactor plays a less important role than in the case of the catalyst packings advantageously used in the reactive distillation column. Batches with a specific particle size are normally used for catalyst packings, since the catalyst material could not otherwise be fully retained by the partially permeable packing walls .
- At least the head flow of the reactive distillation column or the base flow is deliv- ered to at least one further separation stage, and is at least partially separated into the components.
- One or more downstream separation stages are preferably used if the resulting reaction mixture is to be separated as fully as possible into the individual compo- nents.
- the carboxylate flow is mixed with at least an equimolar amount of water, and the carboxylate/water mixture is fed into the pre-reactor.
- the molar ratio between carboxylate and water is expe- trans between approximately 1:1 and 1:15, preferably between 1:2 and 1:10, and more particularly preferably between 1:4 and 1:7.
- the hydrolysis proceeds particularly well if the carboxylate/water ratio in the feed flow is between 1:3 and 1:5.
- the carboxylate/water mixture is preferably heated to a temperature of between 30 and 100 °C, preferably from 40 to 90°C, and more particularly preferably between 50 and 80°C, since the reaction proceeds well and quickly at these temperatures.
- the reaction mixture from the pre-reactor is expediently fed into the reactive distillation column in the region either where the catalyst is arranged, or slightly above or below this region.
- the head flow containing alcohol, water, carboxylate and volatile components may be delivered to a further separation stage, preferably a distillation column, in which the mixture is further separated.
- the reactive distillation column is operated in such a way that the carboxylic acid and at least one part of the water remain in the base of the reactive distillation column.
- the reaction mixture from the pre-reactor is preferably introduced into the reactive distillation column at a point above the catalyst zone centre.
- the base flow produced which essentially contains alcohol, water and carboxylic acid, may be delivered to a further separation stage, preferably a distillation col- umn, in which the mixture is further separated. It is also conceivable for both the head flow and the base flow of the reactive distillation column to be delivered to further separation stages, e.g. distillation columns, and separated. As a variant, the head product may be delivered partially to the pre-reactor or to the feed flow of the reaction column, in order to further convert carboxylate contained in the head flow. Such recycling of the head flow of the reactive distillation column allows the capacity of the plant to be increased substantially.
- the reactive distillation column is operated in such a way that the added water and the volatile components are essentially contained in the head flow.
- This has the advantage that the carboxylic acid is produced in the base with a proportion by weight > 95%, preferably > 99%.
- the highest conversion ratio can in this case be achieved if the reaction ix- ture from the pre-reactor is introduced into the reactive distillation column at a point below the catalyst zone centre.
- the process according to the invention is advantageously operated continuously, i.e. carboxylate and water or a mixture thereof, respectively, are continuously fed into the pre-reactor, and the resulting reaction mixture is drawn off continuously from the pre- reactor and fed into the reactive distillation column, where unreacted carboxylate is for the most part con- verted into its hydrolysis products, the hydrolysis products being drawn off continuously as a head flow or as a bottom fraction (base flow) , and optionally delivered to a further separation stage.
- the volume flow delivered per unit volume of catalyst is advantageously between 0-15 h "1 , preferably 0.5-8 h "1 and particularly preferably between 1-4 h "1 .
- the present invention also relates to a reaction and separation device according to the precharacteris- ing clause of Claim 16, characterised by at least one pre-reactor having at least one inlet and one outlet for respectively supplying and discharging a fluid flow comprising the carboxylate or the carboxylate mixture into the pre-reactor and therefrom, respectively, a first catalyst, which is arranged or deposited in the pre-reactor, a connecting line, which connects the outlet of the pre-reactor to the inlet of the reactive distillation column, and first heating means for heating the fluid flow or the pre-reactor.
- a reaction and separation device according to the precharacteris- ing clause of Claim 16, characterised by at least one pre-reactor having at least one inlet and one outlet for respectively supplying and discharging a fluid flow comprising the carboxylate or the carboxylate mixture into the pre-reactor and therefrom, respectively, a first catalyst, which is arranged or deposited in the pre-reactor, a connecting line, which connects the outlet of the pre-
- the catalyst material in the pre-reactor experiences vor- texing, since the flow direction of the reaction flow and gravity keep the catalyst material at the bottom of the pre-reactor. It is thereby possible to prevent un- desired attrition of the catalyst material . It is also conceivable for the inlet and outlet to be provided laterally on opposite sides above or below the catalyst zone, respectively. It is in principle also conceivable for the inlet to be arranged at the bottom and the outlet at the top.
- two pre- reactors or one pre-reactor having two reaction chambers are used, and means are provided for making it possible to send the feed flow respectively through one of the pre-reactors or one of the reaction chambers, so that the other pre-reactor or the other reaction chamber, respectively, can be provided with fresh catalyst.
- This has the advantage that the device can be operated continuously for a long period of time. It is also conceivable to arrange the two pre-reactors one behind the other. Such an arrangement has the advantage that different temperatures can be maintained in the two reactors, in order to positively exploit the dependency of the equilibrium reaction on temperature (e.g. 1st reactor is operated at a higher temperature than 2nd reactor) .
- the flow leaving the pre-reactor may be partially re- turned to the pre-reactor.
- the pre-reactor can be dimensioned smaller than if no recycling line is provided around the pre-reactor, and the capacity of the plant is variable in a larger range.
- phase separation in the feed to the pre-reactor can be avoided by a recycled flow.
- the reactive distillation column has a catalyst zone and one lower and one upper rectification zone, the upper rectification zone being pro- vided above the catalyst zone and the lower rectification zone being provided below the catalyst zone .
- the rectification zone may have separating stages, Raschig rings, structured material exchange packings etc.
- the pre-reactor is advantageously designed as a tube, in which the first catalyst is deposited.
- the first and second catalysts are acid solid- state catalysts, the first catalyst having a particle size of between approximately 0.35 and 3 mm and the second catalyst having one between approximately 0.5 and 1.5 mm, preferably 0.63 and 1 mm, and more particularly preferably between 0.7 and 1 mm.
- the second catalyst is advantageously introduced into the reactive distillation column as so-called structured catalyst packing.
- structured catalyst packings are described, for example, in US 5,417,939 (Shelden) , US 5,470,542 (Stringaro) and US 5,536,699 (Ghelfi) , the content of which is hereby included by reference.
- the term structured catalyst packing should be understood to mean a structure having retaining devices (e.g. bags) for solid catalyst material and having flow channels, which are present in the structure. It is also conceivable to use such structured catalyst packings both in the pre-reactor and in the reactive distillation column.
- Figure 1 diagrammatically shows a first embodiment of a device for the catalytic hydrolysis of carboxylates, with a pre-reactor and a reactive distillation column
- Figure 2 diagrammatically shows a second embodiment of a device for the catalytic hydrolysis of carboxylates, with a pre-reactor, a reactive distillation column and a distillation column for further separation of the bottom fraction of the reactive distillation column
- Figure 3 diagrammatically shows a third embodiment of a device for the catalytic hydrolysis of carboxylates, with a pre-reactor, a reactive distillation column and a distillation column for further separation of the head flow of the reactive distillation column
- Figure 4 diagrammatically shows a fourth embodiment of a device for the catalytic hydrolysis of carboxylates, with two pre-reactors
- Figure 5 diagrammatically shows a fifth embodiment of a device for the catalytic hydrolysis of carboxylates, with two pre-reactors, the feed from the pre-reactors being fed into the, reactive distillation column at dif- ferent points.
- the device 11 for the simultaneous catalytic hydrolysis of a carboxylate, especially methyl acetate, methyl formate or allyl acetate, into the hydrolysis products and at least partial separation of the reac- tion mixture comprises essentially a pre-reactor 13 and a reactive distillation column 15, which are connected to one another by a connecting line 17.
- the pre-reactor 13 has an inlet 19 for feeding a fluid flow into the reactor space and an outlet 21 for drawing off the reaction mixture.
- the connecting line 17 connects the outlet 21 of the reactor to an inlet 23 on the reactive distillation column 15.
- the pre-reactor 13 is preferably tubular, the inlet 19 and the inlet [sic] 21 being arranged on opposite end sides of the tube.
- the pre-reactor 13 has a catalyst bed 25 of a solid first catalyst material.
- the reactive distillation column 15 has a catalyst zone 27 and an upper and lower rectification zone 29, 31, which are provided respectively below and above the catalyst zone 27.
- a second solid-state catalyst 33 preferably contained in so-called catalyst packing, is provided in the catalyst zone 27.
- the rectification zones are formed in a known way e.g. by Raschig rings, column stages, structured (material exchange) packings etc.
- a line 35 for drawing off the base flow is provided at the column foot, and a line 37 for drawing off the head flow of the reactive distillation column 15 is provided at the column head.
- the line 35 is in connec- tion by means of a line 39 with a heat exchanger 41, which is connected via a line 43 in turn to the column foot.
- the heat exchanger 41 is used to heat the column base.
- a branch line 44 part of the base can be removed as , a base or base [sic] flow from the hydrolysis and separation device.
- the line 37 for the head flow leads to a condenser 45, by which the gaseous head flow can be liquefied.
- a recycling line 47 connected to the condenser part of the distillate can be returned as recycle to the reactive distillation column 15.
- Part or all of the distillate from the reactive distillation column 15 can be removed via the line 49.
- the carboxylate compound to be hydrolysed can be delivered into the pre-reactor 13 via a line 51, which is connected to the inlet 19. Water can be added to the line 51 via a line 53.
- the carboxylate/water mixture can be heated by a heat exchanger 55, which is in connection with the line 51.
- distillation column 57 differs from the first in that a distillation column 57 is connected to the line 44, which is in connection with the column foot.
- the same reference numbers as in the de- scription of the first illustrative embodiment are therefore used for identical parts, and the description is limited to the additional features of the second illustrative embodiment.
- the distillation column 57 also has a heat exchanger 61, integrated in a circulation line 59, in order to heat the base of the distillation column 57. Part of the distillation base can be removed from the hydrolysis device by a branch line 63.
- a condenser 65 is connected by means of a line 67 to the column.
- the condensate can be returned via the line 69 into the distillation column, or can be removed via the line 71 from the hydrolysis and separation device.
- the illustrative embodiment in Figure 3 differs from that in Figure 2 in that the distillation column 57 is connected to the line 49, which is in connection with the condenser 45 of the reactive distillation column.
- the head flow which may be a compound mixture, can be separated at least partially into the components.
- a further difference is that a recycling or recirculation line 73 is provided around the pre-reactor 13, in order to make it possible for part of the flow leaving the pre-reactor 13 to be delivered newly thereto.
- an extraction column may also be used instead of the distillation column.
- the illustrative embodiment in Figure 4 has the distinguishing feature of two pre-reactors 13a and 13b, which can be used simultaneously or alternately. The reaction flow can in this case be fed through valves
- the illustrative embodiment in Figure 5 differs from that in Figure 4 in that the pre-reactors 13a and 13b are connected by means of separate lines 17a and 17b to the reactive distillation column 15.
- the line 17a is connected to an inlet 23a, and the line 17b to an inlet 23b.
- the inlet 23a is arranged in the region of the reaction zone or below the latter, and the inlet 23b in the region of the reaction zone or above the latter.
- the composition of the feed can be adjusted individually for each pre-reactor.
- the reaction conver- sion and the productivity can thereby be improved.
- the use of a second pre-reactor may also be omitted.
- the hydrolysis of a carboxylate will be described below with reference to the hydrolysis of methyl acetate as an example of other carboxylates .
- Methyl acetate flow having a proportion by weight of at least 50% methyl acetate is mixed with an amount of water at least equimolar with respect to methyl acetate, preferably a 4 to 7 times molar excess of water.
- the mixture is then heated by the heat exchanger 55, preferably to a temperature between 30 and 100°C, prefera- bly 50 and 80°C, and fed into the preferably vertically arranged pre-reactor 13.
- the pre-reactor 13 is packed with an acid solid- state catalyst, e.g. a cationic ion exchanger.
- the catalyst preferably has a particle size between ap- proximately 0.35 to 3 mm.
- a catalyst material is available, for example, under the name Amberlyst 15 from the company Rohm and Haas.
- Alternative catalysts are, for example, zeolites, aluminium oxide, silicon oxide etc.
- the methyl acetate/water mixture flows through the pre-reactor 13 in cocurrent from top to bottom, and comes into contact with the catalyst material during this. In this case, partial hydrolysis of the methyl acetate takes place.
- the conversion of the methyl ace- tate in the pre-reactor is between 20 and 100%, preferably between 50 and 80%, of the equilibrium conversion.
- the resulting reaction mixture is introduced via the line 17 into the catalyst zone 27 of the reactive distillation column 15, although the introduction may also take place above or below the catalyst zone. As a variant, part of the reaction mixture may be recycled back to the pre-reactor 15 (Fig. 3) .
- the reactive distillation column 15 is preferably operated in such a way that the more volatile methyl acetate rises in the catalyst zone, and the less volatile water flows down over the catalyst as reflux. In this case, intense contact between catalyst material, water and methyl acetate takes place, in the course of which methyl acetate is cleaved into acetic acid and methanol .
- the reactive distillation column may be operated in such a way that unreacted water collects together with the acetic acid in the base of the column (case 1) or is essentially contained in the head flow of the reactive distillation column (case 2) .
- an acetic acid/water/methanol mixture is produced, which can be further separated e.g. by a downstream separation stage (Fig. 2) .
- aqueous or essentially anhydrous acetic acid with a purity > 99% can be obtained.
- the temperature of the pre-reactor, or of the reactive distillation column, respectively, may be es- tablished as a function of pressure, a certain overpressure making it possible to operate at a higher temperature.
- the head flow of the reactive distillation column con- tains methyl acetate, methanol, water and low-boiling components.
- the base which contains methanol, water, acetic acid and traces of methyl acetate, is removed as a so-called base flow.
- the volume ratio between the head flow 37 and Jhe base flow 35 varies between 1:1 and 1:1000, preferably 1:30 to 1:200.
- the reflux ratio of the reactive distillation column is between 1 and 300, and preferably between 80 and 200.
- the base flow 35 of the reactive distillation column can be further separated in the distillation column 57.
- the head flow of the reactive distillation column 15 contains methyl acetate, methanol, water and low- boiling components.
- the base flow contains either pure acetic acid, i.e. acetic acid at more than 99% propor- tion by weight, or aqueous acetic acid.
- the volume ratio between the base flow 35 and the head flow 37 preferably varies between 1:1 and 1:10, and more particularly preferably between 1:1 to 1:4.
- the reflux ratio of the reactive distillation column is between 1 and 100, and preferably between 5 and 50.
- the head flow of the reactive distillation column can be further separated in the distillation column 57.
- the head flow of the distillation column 57, exiting through the line 67, contains methanol, methyl acetate, water and low- boiling components.
- the base flow (line 59) contains essentially water.
- the base flow contained a mixture of methyl acetate, methanol, acetic acid and water, which was separated in an additional purification column into a methyl ace- tate/methanol mixture and an acetic acid/water mixture.
- the methyl acetate flow to be hydrolysed had the following composition (in per cent by weight) : acetaldehyde: 0.4% methyl acetate: 98.3% methanol: 1.3%
- a combination of pre-reactor with reactive distillation column was used.
- the base flow of the reactive distillation column contains methanol, acetic acid, water and traces of methyl acetate. This mixture was separated in a distillation column into a methanol flow containing traces of methyl acetate and an acetic acid/water mixture.
- methyl acetate flow to be hydrolysed had the following composition (in per cent by weight) : acetaldehyde: 0.001% methyl acetate: 96.53% methanol: 3.46% Reactive Distillation Column: inner diameter: 220 mm rectification zone: 7 theoretical stages (TS) reaction zone: 6 TS stripping zone: 8 TS Feed Flows: methyl acetate: 38.61 kg/h water: 58.20 kg/h
- Example 3 simulation of the hydrolysis and separation reaction by means of the simulation program PRO/II of the company SIMSCI (Simulation Sciences Inc.) with the aim of obtaining pure acetic acid from a methyl acetate flow utilising a pre-reactor/reactive distillation column combination according to the invention:
- Feed Flows (in kg/h) feed flow: 6500 kg/h (of acetaldehyde,
- Allyl alcohol can inter alia be produced by the hydrolysis of allyl acetate.
- the hydrolysis is in this case carried out according to known conventional methods in the presence of mineral acids or ion exchangers as catalyst.
- the production of formic acid likewise takes place by a hydrolysis reaction. In this case, methyl formate is reacted with excess water to give formic acid and methanol.
- the reaction can in this case be carried out autocatalysed by formic acid (DE-A-44 449 79) or in the presence of acid catalyst, e.g. ion exchanger (DE-A-42 373 39) .
- the processing of the hydrolysis products conventionally takes place with separation methods such as distillation, extraction, etc.
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
Abstract
Description
Claims
Priority Applications (10)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU75028/00A AU7502800A (en) | 1999-10-13 | 2000-10-11 | Process and device for hydrolytically obtaining a carboxylic acid and alcohol from the corresponding carboxylate |
JP2001530084A JP2003511432A (en) | 1999-10-13 | 2000-10-11 | Method and apparatus for obtaining carboxylic acids and alcohols from the corresponding carboxylic esters by hydrolysis |
SK466-2002A SK287406B6 (en) | 1999-10-13 | 2000-10-11 | Process for hydrolytically obtaining a carboxylic acid and alcohol and the use of hydrolytic and dividing device for conversion corresponding carboxylic acid and alcohol |
EP00963849A EP1220825B1 (en) | 1999-10-13 | 2000-10-11 | Process for hydrolytically obtaining a carboxylic acid and alcohol from the corresponding carboxylate |
AT00963849T ATE239689T1 (en) | 1999-10-13 | 2000-10-11 | METHOD FOR THE HYDROLYTICAL PRODUCTION OF A CARBOXYLIC ACID AND AN ALCOHOL FROM THE CORRESPONDING CARBOXYLATE |
DE60002597T DE60002597T2 (en) | 1999-10-13 | 2000-10-11 | METHOD FOR THE HYDROLYTIC PRODUCTION OF A CARBOXYLIC ACID AND ALCOHOL FROM THE CORRESPONDING CARBOXYLATE |
UA2002053847A UA72938C2 (en) | 1999-10-13 | 2000-10-11 | A method and apparatus for hydrolytic preparation of carboxylic acid and alcohol from respective carboxylate |
US10/110,474 US7041199B1 (en) | 1999-10-13 | 2000-10-11 | Process and device for hydrolytically obtaining a carboxylic acid alcohol from the corresponding carboxylate |
CA2382831A CA2382831C (en) | 1999-10-13 | 2000-10-11 | Process and device for hydrolytically obtaining a carboxylic acid and alcohol from the corresponding carboxylate |
MXPA02003643A MXPA02003643A (en) | 1999-10-13 | 2000-10-11 | Process and device for hydrolytically obtaining a carboxylic acid and alcohol from the corresponding carboxylate. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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CH186999 | 1999-10-13 | ||
CH1869/99 | 1999-10-13 |
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WO2001027062A2 true WO2001027062A2 (en) | 2001-04-19 |
WO2001027062A3 WO2001027062A3 (en) | 2001-11-29 |
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Family Applications (1)
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PCT/CH2000/000551 WO2001027062A2 (en) | 1999-10-13 | 2000-10-11 | Process and device for hydrolytically obtaining a carboxylic acid and alcohol from the corresponding carboxylate |
Country Status (17)
Country | Link |
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US (1) | US7041199B1 (en) |
EP (1) | EP1220825B1 (en) |
JP (1) | JP2003511432A (en) |
KR (1) | KR100679156B1 (en) |
CN (1) | CN1213014C (en) |
AT (1) | ATE239689T1 (en) |
AU (1) | AU7502800A (en) |
CA (1) | CA2382831C (en) |
DE (1) | DE60002597T2 (en) |
ES (1) | ES2194773T3 (en) |
MX (1) | MXPA02003643A (en) |
MY (1) | MY130282A (en) |
RU (1) | RU2257373C2 (en) |
SK (1) | SK287406B6 (en) |
TW (1) | TW524795B (en) |
UA (1) | UA72938C2 (en) |
WO (1) | WO2001027062A2 (en) |
Cited By (3)
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DE10244632A1 (en) * | 2002-09-25 | 2004-04-15 | Wacker-Chemie Gmbh | Process and device for acid-catalyzed hydrolysis of carboxylic acid esters from azeotropic mixtures |
WO2004048308A2 (en) * | 2002-11-28 | 2004-06-10 | Wacker-Chemie Gmbh | Method and device for hydrolytically obtaining a carboxylic acid and alcohol from the corresponding carboxylic ester |
CN114229932A (en) * | 2021-11-23 | 2022-03-25 | 安徽金禾实业股份有限公司 | Device and method for treating acidic wastewater in chloroethane production |
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CN101186575B (en) * | 2007-12-04 | 2010-04-14 | 南京工业大学 | Methyl acetate catalytic rectification hydrolysis process |
WO2010017624A1 (en) * | 2008-08-13 | 2010-02-18 | Kuang-Yeu Wu | Process and apparatus for recovery of acetic acid from a feed stream containing the corresponding ester |
CN101481304B (en) * | 2009-02-20 | 2012-07-04 | 南京工业大学 | Process for preparing formic acid by hydrolyzing methyl formate |
EP2502655B1 (en) | 2011-03-25 | 2014-05-14 | Sulzer Chemtech AG | Reactive distillation process and plant for obtaining acetic acid and alcohol from the hydrolysis of methyl acetate |
CN102617322B (en) * | 2012-03-12 | 2014-05-07 | 浙江大学 | Method for producing methanoic acid by adopting reactive rectification technology |
TWI518059B (en) | 2013-06-05 | 2016-01-21 | 大連化學工業股份有限公司 | Method for production of allyl alcohol |
CN103588636A (en) * | 2013-11-14 | 2014-02-19 | 中国科学院过程工程研究所 | Method for preparing acrylic acid through hydrolyzation of methyl acrylate under catalysis of acidic resin |
US10954182B2 (en) * | 2017-09-20 | 2021-03-23 | Inventure Renewables, Inc. | Reactive distillation process/equipment for fatty acid ester hydrolysis to produce carboxylic acid and alcohol |
CN110845321B (en) * | 2019-11-27 | 2022-06-03 | 宿迁南翔化学品制造有限公司 | Tower type method and equipment for preparing malonic acid |
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- 2000-10-11 MX MXPA02003643A patent/MXPA02003643A/en active IP Right Grant
- 2000-10-11 AU AU75028/00A patent/AU7502800A/en not_active Abandoned
- 2000-10-11 WO PCT/CH2000/000551 patent/WO2001027062A2/en active IP Right Grant
- 2000-10-11 CN CNB008168733A patent/CN1213014C/en not_active Expired - Fee Related
- 2000-10-11 UA UA2002053847A patent/UA72938C2/en unknown
- 2000-10-11 US US10/110,474 patent/US7041199B1/en not_active Expired - Fee Related
- 2000-10-11 AT AT00963849T patent/ATE239689T1/en not_active IP Right Cessation
- 2000-10-11 KR KR1020027004676A patent/KR100679156B1/en not_active IP Right Cessation
- 2000-10-11 CA CA2382831A patent/CA2382831C/en not_active Expired - Fee Related
- 2000-10-11 JP JP2001530084A patent/JP2003511432A/en active Pending
- 2000-10-11 ES ES00963849T patent/ES2194773T3/en not_active Expired - Lifetime
- 2000-10-11 EP EP00963849A patent/EP1220825B1/en not_active Expired - Lifetime
- 2000-10-11 RU RU2002111871/15A patent/RU2257373C2/en not_active IP Right Cessation
- 2000-10-11 SK SK466-2002A patent/SK287406B6/en not_active IP Right Cessation
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Also Published As
Publication number | Publication date |
---|---|
WO2001027062A3 (en) | 2001-11-29 |
ATE239689T1 (en) | 2003-05-15 |
SK4662002A3 (en) | 2002-08-06 |
EP1220825A2 (en) | 2002-07-10 |
JP2003511432A (en) | 2003-03-25 |
MY130282A (en) | 2007-06-29 |
DE60002597T2 (en) | 2004-08-05 |
MXPA02003643A (en) | 2005-07-25 |
RU2002111871A (en) | 2004-01-27 |
CN1407960A (en) | 2003-04-02 |
EP1220825B1 (en) | 2003-05-07 |
US7041199B1 (en) | 2006-05-09 |
KR20020040858A (en) | 2002-05-30 |
DE60002597D1 (en) | 2003-06-12 |
CN1213014C (en) | 2005-08-03 |
RU2257373C2 (en) | 2005-07-27 |
AU7502800A (en) | 2001-04-23 |
CA2382831A1 (en) | 2001-04-19 |
UA72938C2 (en) | 2005-05-16 |
KR100679156B1 (en) | 2007-02-07 |
TW524795B (en) | 2003-03-21 |
ES2194773T3 (en) | 2003-12-01 |
MX243923B (en) | 2007-03-01 |
SK287406B6 (en) | 2010-09-07 |
CA2382831C (en) | 2010-10-05 |
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