CN103420831B - A kind of production method of acetic ester - Google Patents
A kind of production method of acetic ester Download PDFInfo
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- CN103420831B CN103420831B CN201210163002.3A CN201210163002A CN103420831B CN 103420831 B CN103420831 B CN 103420831B CN 201210163002 A CN201210163002 A CN 201210163002A CN 103420831 B CN103420831 B CN 103420831B
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- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 235000019439 ethyl acetate Nutrition 0.000 title claims abstract description 32
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 31
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 99
- 239000000203 mixture Substances 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 29
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 18
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 18
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 18
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 14
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 14
- 150000002168 ethanoic acid esters Chemical class 0.000 claims abstract description 11
- 150000001336 alkenes Chemical class 0.000 claims abstract description 10
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 8
- 238000007259 addition reaction Methods 0.000 claims abstract description 7
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 22
- 239000011964 heteropoly acid Substances 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 13
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 10
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 9
- 239000003729 cation exchange resin Substances 0.000 claims description 8
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 7
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 7
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 7
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 5
- 238000011068 loading method Methods 0.000 claims description 5
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 5
- 239000002808 molecular sieve Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 4
- 239000001294 propane Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000000047 product Substances 0.000 description 12
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 9
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 230000032050 esterification Effects 0.000 description 6
- 238000005886 esterification reaction Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- 229940043232 butyl acetate Drugs 0.000 description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000017525 heat dissipation Effects 0.000 description 3
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 3
- 229940011051 isopropyl acetate Drugs 0.000 description 3
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229940090181 propyl acetate Drugs 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 235000013599 spices Nutrition 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 2
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 2
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 description 1
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- GQKZRWSUJHVIPE-UHFFFAOYSA-N sec-amyl acetate Natural products CCCC(C)OC(C)=O GQKZRWSUJHVIPE-UHFFFAOYSA-N 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- WMOVHXAZOJBABW-UHFFFAOYSA-N tert-butyl acetate Chemical compound CC(=O)OC(C)(C)C WMOVHXAZOJBABW-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a kind of production method of acetic ester, the method comprises: under addition reaction condition, first mixture is sent into heat-insulating many beds fixed-bed reactor from the bottom feed mouth of heat-insulating many beds fixed-bed reactor and contacts with the catalyzer of catalysis acetic acid synthesis of acetic acid ester, obtain the second mixture from the top of reactor; Second mixture is divided into three parts, the hydrocarbon mixture of first part and C3 and/or C4 and acetic acid are mixed to get described first mixture; Second section is cooled, and sends in described fixed-bed reactor and make the temperature in fixed-bed reactor maintain 60-120 DEG C; Part III is discharged aftercut and obtains acetic ester; Wherein, in the hydrocarbon mixture of described C3 and/or C4, olefin(e) centent is 20-100 % by weight.Method device structure of the present invention is simple, and acetic ester selectivity is high, energy consumption is low, is suitable for suitability for industrialized production.
Description
Technical field
The present invention relates to a kind of production method of acetic ester.
Background technology
Butylacetate (comprising n-butyl acetate, sec-butyl acetate, isobutyl acetate and tert.-butyl acetate) is the important organic chemicals of a class, be a kind ofly be widely used as grease, resin, coating, the preparation of paint and the excellent organic solvent of organic reaction process, extraction separation process etc., preparing metal clean-out system and spices etc. can also be used for.Particularly in recent years, due to environmental requirement increasingly stringent, the use containing the solvent of the toxic substances such as benzene, toluene, hydrochloric ether is restricted just gradually, and the consumption of ester class environmentally friendly solvent sharply increases, and acetate product has become market hot-sale products.At present, on market, butylacetate series products is based on n-butyl acetate, but needs to be reacted by the higher propyl carbinol of price and acid esterification to prepare due to n-butyl acetate, and production cost is higher, therefore, domestic and international many companies are developing the sec-butyl acetate as n-butyl acetate substitute one after another.Character and the n-butyl acetate of sec-butyl acetate are close, and the method for a large amount of by-products of refinery, low-cost butylene and acetic acid direct addition can be adopted to prepare, and therefore can greatly reduce costs.
The technology of sec-butyl acetate is prepared, open in many sections of patent applications and document, report about acetic acid and butylene direct addition.
Utilize acetic acid and mixed C at present
4the method that (or butylene) prepares sec-butyl acetate is normally carried out esterification and is obtained in calandria type fixed bed reactor.US Patent No. 457228 discloses a kind of method preparing sec-butyl acetate, and it is by by reaction mass and acetic acid and mixed C
4(or butylene) passes into from calandria type fixed bed reactor top, and product mixtures comprises unreacted mixed C
4(or butylene), unreacted acetic acid and the secondary butyl ester of acetic acid product flow out from reactor bottom simultaneously.Product mixtures is successively after recycle pump and interchanger, and a part of product mixtures sends to separation circuit below, and another part mixture sends into reactor as recycle feed together with fresh feed.The deficiency of this method is: due to acetic acid and mixed C
4the reaction that (or butylene) prepares sec-butyl acetate is thermopositive reaction, adopt calandria type fixed bed when making reactor, because the reaction mass in tubulation is by carrying out indirect contact heat exchanger with the water coolant outside tubulation, therefore there is temperature inequality in device structure complexity, tubulation and cause coking, the defects such as energy consumption is large.
CN101948358A discloses a kind of synthetic method of 2-butyl acetate, and this inventive method is as follows: by pressurized operation, raw material acetic acid and C
4alkene continues through three fixed-bed reactor all in liquid form in the same way, wherein the C of 20-50w%
41# and 2# reactor is entered, remaining C after alkene and acetic acid merge
4the resultant of alkene and 1# and 2# reactor merges and enters 3# reactor; After 3# reactor, small portion output object is as the charging of preliminary rectifying tower 4, and rest part is circulated to the import of 3# reactor; The catalyzer adopted is macropore strong acid cation exchange resin.Although the method overcomes the shortcoming of calandria type fixed bed reactor, but the method complex procedures and the equipment needed are too much (3 fixed-bed reactor), therefore there is the problems such as device fabrication difficulty is large, cost of equipment input is higher, this is unfavorable for suitability for industrialized production.
Propyl acetate comprises n-propyl acetate, isopropyl acetate.Isopropyl acetate, has another name called " Iso Butyl Acetate ", is colourless transparent liquid, has special fruit aroma under normal temperature, inflammable, is slightly soluble in water, dissolves each other with ethanol, ether; Be industrially important organic solvent, the synthetic resins such as nitrocellulose, polystyrene, synthetic glass, polyvinyl acetate, chlorinated rubber can be dissolved, also for medicine industry and manufacture spices.N-propyl acetate is also industrial important organic solvent, is widely used in medicine industry and manufactures spices.The production technique of propyl acetate is substantially identical with the production technique of butylacetate, and therefore its production technique also exists the defect of the existence in aforementioned butylacetate production technique.
Therefore how to provide one that calandria type fixed bed reactor can not be adopted to carry out esterification synthesis of acetic acid ester (as: propyl acetate and butylacetate) on the basis of existing technology, and acetate yields is high, heat dissipation is few, and the technique of the simple synthesis of acetic acid ester of device structure is the important research direction in the future producing acetic ester.
Summary of the invention
The object of the invention is to provide on the basis of existing technology that a kind of acetic ester selectivity is high, heat dissipation is few, and the production method of the simple acetic ester of device structure.
Because acetic acid and alkene are strong exothermal reactions by esterification synthesis of acetic acid ester, therefore, in order to make the temperature of reaction system homogeneous thus the generation of side reaction can be reduced, at present, the major part research of the synthetic method of acetic ester is all carry out based on the esterification in calandria type fixed bed reactor, and there is the aforementioned drawback introduced in background technology due to calandria type fixed bed reactor, investigator is had to transfer research direction, as the CN101948358A introduced in background technology, the method uses three fixed-bed reactor effectively to achieve the synthesis of acetic ester, but so many conversion unit is extremely unfavorable to suitability for industrialized production, therefore the synthesis technique how improving acetic ester has further become Research Challenges and focus, the present inventor finds through long-term test, adopt conventional non-calandria type fixed bed reactor to carry out esterification and can walk always to reduce the number of the fixed-bed reactor of use by reasonably arranging the material in fixed-bed reactor.The present invention is completed based on this discovery.
The invention provides a kind of production method of acetic ester, the method comprises:
Under addition reaction condition, first mixture is sent into heat-insulating many beds fixed-bed reactor from the bottom feed mouth of heat-insulating many beds fixed-bed reactor and contacts with the catalyzer of catalysis acetic acid synthesis of acetic acid ester, obtain the second mixture from the top of reactor;
Second mixture is divided into three parts, the hydrocarbon mixture of first part and C3 and/or C4 and acetic acid are mixed to get described first mixture; Second section is cooled, and sends in described fixed-bed reactor and make the temperature in described fixed-bed reactor maintain 60-120 DEG C; Part III is discharged aftercut and obtains acetic ester; Wherein, in the hydrocarbon mixture of described C3 and/or C4, olefin(e) centent is 20-100 % by weight.
Method required equipment of the present invention is few, and acetic ester selectivity is high, heat dissipation is few, is highly susceptible to suitability for industrialized production.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and forms a part for specification sheets, is used from explanation the present invention, but is not construed as limiting the invention with embodiment one below.In the accompanying drawings:
Fig. 1 is the schematic flow sheet of the production method of acetic ester of the present invention.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
As shown in Figure 1, the invention provides a kind of production method of acetic ester, the method comprises:
Under addition reaction condition, first mixture is sent into heat-insulating many beds fixed-bed reactor from the bottom feed mouth of heat-insulating many beds fixed-bed reactor and contacts with the catalyzer of catalysis acetic acid synthesis of acetic acid ester, obtain the second mixture from the top of reactor;
Second mixture is divided into three parts, the hydrocarbon mixture of first part and C3 and/or C4 and acetic acid are mixed to get described first mixture; Second section is cooled, and sends in described fixed-bed reactor and make the temperature in described fixed-bed reactor maintain 60-120 DEG C, be preferably 60-100 DEG C, be more preferably 70-80 DEG C; Part III is discharged aftercut and obtains acetic ester; Wherein, in the hydrocarbon mixture of described C3 and/or C4, olefin(e) centent is 20-100 % by weight.
According to the present invention, object of the present invention can be realized according to preceding solution of the present invention, what realize to make goal of the invention of the present invention is more abundant, and cooled second section is sent into described fixed-bed reactor by the position being preferably the 1/4-4/5 of fixed-bed reactor total height from the distance bottom distance fixed-bed reactor.
According to one of the present invention preferred embodiment, under preferable case, described cooled second section is divided into multiply (not shown), sends into described fixed-bed reactor respectively from the different positions of described fixed-bed reactor.
According to the present invention, cooled second section is divided into more multiply, it is better that temperature of reaction in fixed-bed reactor controls, reaction effect is better, but the manufacturing expense of fixed-bed reactor is also higher and operation is more complicated, in order to cost-saving while guarantee reaction efficiency, the preferred embodiment of one according to the present invention, under preferable case, described cooled second section is divided into 2 strands (as shown in Figure 1), the volume ratio of first strand and second strand is 1-3:1, send into described fixed-bed reactor from the position being the 1/4-2/3 of fixed-bed reactor total height apart from the distance bottom fixed-bed reactor for first strand, send into described fixed-bed reactor from the position being the 2/3-4/5 of fixed-bed reactor total height apart from the distance bottom fixed-bed reactor for second strand.
According to the present invention, the range of choices of the volume ratio of described first part, second section, Part III is wider, can regulate according to the change of all the other processing parameters in specific operation process.Under preferable case, the volume ratio of described first part, second section and Part III is 1-12:1-6:1, is preferably 2-10:1-5:1, is more preferably 6-8:1-2:1.
According to the present invention, in order to make the temperature in described fixed-bed reactor maintain 60-120 DEG C, being preferably 60-100 DEG C, being more preferably 70-80 DEG C; Under preferable case, the cooled temperature of described second section is 20-60 DEG C, is preferably 30-50 DEG C, is more preferably 40-45 DEG C.
In the present invention, described addition reaction condition can be carried out with reference to prior art, and its range of choices is wider, and for the present invention, under preferable case, it is 60-120 DEG C that described addition reaction condition comprises temperature, is preferably 60-100 DEG C; Pressure is 1-5MPa, is preferably 1-4MPa; Liquid hourly space velocity is 0.1-10h
-1, be preferably 1-9h
-1, be more preferably 4-8h
-1; In the hydrocarbon mixture of acetic acid and C3 and/or C4, the mol ratio of alkene is 1-10:1, is preferably 2-6:1.In the present invention, described pressure refers to absolute pressure.
In the present invention, according to needs, when reacting and starting, the hydrocarbon mixture of described C3 and/or C4 and/or described acetic acid can be preheated to 30-100 DEG C.
In the present invention, the catalyzer of described catalysis acetic acid synthesis of acetic acid ester can be carried heteropoly acid, carried heteropoly acid salt, non-loading type heteropolyacid, non-loading type heteropolyacid salt, storng-acid cation exchange resin, molecular sieve and SO
4 2-/ ZrO
2one or more in type solid super-strong acid.Storng-acid cation exchange resin as catalyzer mainly obtains polystyrene resin by styrene-divinylbenzene in the low suspension copolymerization that exists of pore-creating agent, and then with the vitriol oil, oleum or SO
3carry out that sulfonation obtains.This resinoid can according to well known to a person skilled in the art that method synthesis obtains, also can buy from market easily, if the trade mark is the resins such as D72, D005, D006, D008, D007, S54, Amberlyst15, Amberlyst35, Dowex50, K2611, K2431, Puolite175, Puolite275, KC117, KC118.Selectable molecular sieve has the serial equimolecular sieve of Y-series, ZSM series, serial, the β of MCM.Selectable heteropolyacid comprises the heteropolyacid of structure with Keggin, Dawson structure, Anderson structure, Silverton structure, and this area uses the catalyzer heteropolyacid of more catalysis acetic acid synthesis of acetic acid ester to be generally the heteropolyacid of structure with Keggin as 12 phospho-wolframic acid (H
3pW
12o
40xH
2o), 12 silicotungstic acid (H
4siW
12o
40xH
2o), 12 phosphomolybdate (H
3pMo
12o
40xH
2o), 12 molybdovanaphosphoric acid (H
3pMo
12-yv
yo
40xH
2o etc.For heteropolyacid, because its specific surface area is less and be difficult to shaping separately, therefore usually preferred by its load on suitable carrier, form carried heteropoly acid catalyst, available carrier comprises one or more in the metal oxide carrier such as silicon-dioxide, aluminum oxide, large pore molecular sieve carrier, absorbent charcoal carrier, treated ion exchange resin carrier.The catalyzer of the catalysis acetic acid synthesis of acetic acid ester used in a particular embodiment of the present invention is commercially available storng-acid cation exchange resin, and the such as trade mark is the storng-acid cation exchange resin of D007, KC117, KC118.
According to one of the present invention preferred embodiment, in order to realize effective utilization of various raw material in course of industrialization, the hydrocarbon mixture of described C3 and/or C4 is C4 after mixed C 3, hybrid C 4 or ether, after described ether, C4 refers to hydrocarbon feed containing iso-butylene and methyl alcohol generates after methyl tertiary butyl ether through MTBE device, transform the hydrocarbon feed after the overwhelming majority (more than 80 % by weight) iso-butylene, described mixed C 3, hybrid C 4 are technical terms conventional in this area, are no longer described at this.
Under preferable case, containing the propylene of 20-99.99 % by weight and the propane of 0.01-80 % by weight in described mixed C 3; N-butene containing 20-99.97 % by weight in described hybrid C 4, the normal butane of 0.01-30 % by weight, the Trimethylmethane of 0.01-50 % by weight and the iso-butylene of 0.01-10 % by weight; N-butene, the normal butane of 10-30 % by weight, the Trimethylmethane of 20-50 % by weight, the iso-butylene of 0.1-10 % by weight and the propylene of 0.1-10 % by weight containing 30-60 % by weight in C4 after described ether.
According to one of the present invention preferred embodiment, under preferable case, described heat-insulating many beds fixed-bed reactor are axial heat-insulating many beds fixed-bed reactor.
According to the present invention, described acetic acid supply source can be variously acetic acid is housed thus can provides the container of acetic acid for the reaction preparing sec-butyl acetate, can be the form of conventional can, may not be this form.
According to the present invention, the hydrocarbon mixture supply source of described C3 and/or C4 can be the hydrocarbon mixture of the various C3 of being equipped with and/or C4 thus can provide the container of the hydrocarbon mixture of C3 and/or C4 for the reaction preparing acetic ester, can be the form of conventional can, may not be this form.
Below by specific embodiment, the present invention is described in detail, but the present invention is not limited to this.
In the present invention, adopting gas-chromatography to carry out each organic analysis in system, being undertaken quantitatively, all can refer to prior art and carrying out, calculate the evaluation indexes such as the transformation efficiency of reactant, selectivity of product on this basis by correcting normalization method.
In the present invention, transformation efficiency and selectivity are the implication of this area routine, and the present invention is not described in detail its definition, particularly:
Conversion of olefines rate calculation formula is as follows:
Acetic ester optionally calculation formula is as follows:
Wherein, X is transformation efficiency; S is selectivity; M is the quality (referring to the quality of component in Part III in the present invention) of discharge port component; N is the amount of substance (referring to the amount of substance of component in Part III in the present invention) of discharge port component; Wherein m
0and n
0represent the quality that reactant feeds intake and amount of substance respectively.
Embodiment 1
The present embodiment is for illustration of the production method of acetic ester provided by the invention.
Acetic ester is produced according to flow process shown in Fig. 1, at axial heat-insulating many beds fixed-bed reactor (2 beds, the height of each bed is identical, following examples are roughly the same) middle loading strong acid cation exchange resin catalyst (the triumphant auspicious chemical industry in Hebei, KC117), the quality group of C4 after C4(ether after acetic acid and ether is become: the n-butene of 48 % by weight, the normal butane of 15 % by weight, the Trimethylmethane of 35 % by weight, the iso-butylene of 1 % by weight, the propylene of 1 % by weight, after ether, the temperature of C4 is 75 DEG C) mixing after pass into continuously fixed-bed reactor from the bottom feed mouth of fixed-bed reactor, wherein, after acetic acid and ether, in C4, total mol ratio of alkene is 4, liquid hourly space velocity in fixed-bed reactor is 8h
-1, temperature is 80 DEG C, pressure is 2MPa, obtains the product after contacting from the top of fixed-bed reactor,
Product after contact is divided into three parts, first part is mixed with C4 after ether and acetic acid; From being that 1/2 of fixed bed total height is sent in described fixed-bed reactor apart from the distance bottom fixed-bed reactor after being cooled by second section, the temperature in described fixed-bed reactor is made to maintain 80 DEG C; Part III is discharged aftercut and obtains acetic ester, wherein the volume ratio of first part, second section and Part III is 8:2:1, and the cooled temperature of second section is 45 DEG C.After steady running 4h, get Part III analysis, the selectivity of conversion of olefines rate and acetic ester is all more than 90%.
Embodiment 2
The present embodiment is for illustration of the production method of acetic ester provided by the invention.
Acetic ester is produced according to flow process shown in Fig. 1, strong acid cation exchange resin catalyst (the triumphant auspicious chemical industry in Hebei is loaded in axial heat-insulating many beds fixed-bed reactor, KC117), by propylene 99.5 % by weight in acetic acid and mixed C 3(mixed C 3, all the other are propane, and the temperature of mixed C 3 is 70 DEG C) mixing after pass into continuously described fixed-bed reactor from the bottom feed mouth of described fixed-bed reactor.In acetic acid and mixed C 3, total mol ratio of propylene is 4, and the liquid hourly space velocity in fixed-bed reactor is 4h
-1, temperature is 75 DEG C, pressure is 3MPa, obtains the product after contacting from the top of described fixed-bed reactor;
Product after contact is divided into three parts, first part is mixed with raw material mixed C 3 and acetic acid; From being that 1/2 of fixed bed total height is sent in described fixed-bed reactor apart from the distance bottom fixed-bed reactor after being cooled by second section, the temperature in described fixed-bed reactor is made to maintain 75 DEG C; Part III is discharged aftercut and obtains isopropyl acetate, wherein the volume ratio of first part, second section and Part III is 6:1:1, and second section is cooled to 40 DEG C.After steady running 4h, get Part III analysis, conversion of olefines rate is more than 80%, and the selectivity of acetic ester is about 95%.
This shows, method of the present invention simplifies flow process, decreases equipment (only needing fixed-bed reactor), and gets final product the production acetic ester of highly selective without the need to additionally supplying heat, and namely method of the present invention has very high industrial application value.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each the concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (8)
1. a production method for acetic ester, the method comprises:
Under addition reaction condition, first mixture is sent into heat-insulating many beds fixed-bed reactor from the bottom feed mouth of heat-insulating many beds fixed-bed reactor and contacts with the catalyzer of catalysis acetic acid synthesis of acetic acid ester, obtain the second mixture from the top of reactor;
Second mixture is divided into three parts, the hydrocarbon mixture of first part and C3 and/or C4 and acetic acid are mixed to get described first mixture; Second section is cooled, and sends in described fixed-bed reactor and make the temperature in described fixed-bed reactor maintain 60-120 DEG C; Part III is discharged aftercut and obtains acetic ester; Wherein, in the hydrocarbon mixture of described C3 and/or C4, olefin(e) centent is 20-100 % by weight,
Described cooled second section is divided into 2 strands, the volume ratio of first strand and second strand is 1-3:1, send into described fixed-bed reactor from the position being the 1/4-2/3 of fixed-bed reactor total height apart from the distance bottom fixed-bed reactor for first strand, send into described fixed-bed reactor from the position being the 2/3-4/5 of fixed-bed reactor total height apart from the distance bottom fixed-bed reactor for second strand
The volume ratio of described first part, second section and Part III is 1-12:1-6:1.
2. production method according to claim 1, wherein, the volume ratio of described first part, second section and Part III is 2-10:1-5:1.
3. according to the production method in claim 1-2 described in any one, wherein, the cooled temperature of described second section is 20-60 DEG C.
4. production method according to claim 3, wherein, the cooled temperature of described second section is 30-50 DEG C.
5. according to the production method in claim 1-2 described in any one, wherein, described addition reaction condition comprises that temperature is 60-120 DEG C, pressure is 1-5MPa, and liquid hourly space velocity is 0.1-10h
-1, in the hydrocarbon mixture of acetic acid and C3 and/or C4, the mol ratio of alkene is 1-10:1.
6. according to the production method in claim 1-2 described in any one, wherein, the catalyzer of described catalysis acetic acid synthesis of acetic acid ester is carried heteropoly acid, carried heteropoly acid salt, non-loading type heteropolyacid, non-loading type heteropolyacid salt, storng-acid cation exchange resin, molecular sieve and SO
4 2-/ ZrO
2one or more in type solid super-strong acid.
7. according to the production method in claim 1-2 described in any one, wherein, the hydrocarbon mixture of described C3 and/or C4 is C4 after mixed C 3, hybrid C 4 or ether; Containing the propylene of 20-99.99 % by weight and the propane of 0.01-80 % by weight in described mixed C 3; N-butene containing 20-99.97 % by weight in described hybrid C 4, the normal butane of 0.01-30 % by weight, the Trimethylmethane of 0.01-50 % by weight and the iso-butylene of 0.01-10 % by weight; N-butene, the normal butane of 10-30 % by weight, the Trimethylmethane of 20-50 % by weight, the iso-butylene of 0.1-10 % by weight and the propylene of 0.1-10 % by weight containing 30-60 % by weight in C4 after described ether.
8. according to the production method in claim 1-2 described in any one, wherein, described heat-insulating many beds fixed-bed reactor are axial heat-insulating many beds fixed-bed reactor.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5457228A (en) * | 1990-10-31 | 1995-10-10 | Daicel Chemical Industries, Ltd. | Method for producing lower alkyl acetate |
| CN101481306A (en) * | 2009-01-13 | 2009-07-15 | 湖南瑞源石化股份有限公司 | Preparation of lower fatty acid ester and apparatus for preparing lower fatty acid ester |
| CN101486640A (en) * | 2009-01-13 | 2009-07-22 | 湖南瑞源石化股份有限公司 | Preparation of sec-butyl acetate |
| CN101948385A (en) * | 2010-07-12 | 2011-01-19 | 江门谦信化工发展有限公司 | Method for composing butyl acetate |
-
2012
- 2012-05-23 CN CN201210163002.3A patent/CN103420831B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5457228A (en) * | 1990-10-31 | 1995-10-10 | Daicel Chemical Industries, Ltd. | Method for producing lower alkyl acetate |
| CN101481306A (en) * | 2009-01-13 | 2009-07-15 | 湖南瑞源石化股份有限公司 | Preparation of lower fatty acid ester and apparatus for preparing lower fatty acid ester |
| CN101486640A (en) * | 2009-01-13 | 2009-07-22 | 湖南瑞源石化股份有限公司 | Preparation of sec-butyl acetate |
| CN101948385A (en) * | 2010-07-12 | 2011-01-19 | 江门谦信化工发展有限公司 | Method for composing butyl acetate |
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