CN101486640B - Preparation of sec-butyl acetate - Google Patents
Preparation of sec-butyl acetate Download PDFInfo
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- CN101486640B CN101486640B CN2009100056792A CN200910005679A CN101486640B CN 101486640 B CN101486640 B CN 101486640B CN 2009100056792 A CN2009100056792 A CN 2009100056792A CN 200910005679 A CN200910005679 A CN 200910005679A CN 101486640 B CN101486640 B CN 101486640B
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- acetate
- sec
- alkene
- rectification column
- azeotropy rectification
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- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 title claims abstract description 127
- 238000002360 preparation method Methods 0.000 title claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 120
- 239000000047 product Substances 0.000 claims abstract description 106
- 150000001336 alkenes Chemical class 0.000 claims abstract description 98
- 238000000034 method Methods 0.000 claims abstract description 88
- 238000000926 separation method Methods 0.000 claims abstract description 34
- 238000007259 addition reaction Methods 0.000 claims abstract description 28
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 26
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 139
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 74
- 238000006243 chemical reaction Methods 0.000 claims description 66
- 238000000605 extraction Methods 0.000 claims description 61
- 241000282326 Felis catus Species 0.000 claims description 49
- 238000009835 boiling Methods 0.000 claims description 46
- 239000000463 material Substances 0.000 claims description 42
- 238000010533 azeotropic distillation Methods 0.000 claims description 37
- 239000000203 mixture Substances 0.000 claims description 30
- 239000000470 constituent Substances 0.000 claims description 26
- 150000002500 ions Chemical class 0.000 claims description 10
- 238000009833 condensation Methods 0.000 claims description 5
- 230000005494 condensation Effects 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 abstract description 65
- 239000012071 phase Substances 0.000 abstract description 30
- 239000003054 catalyst Substances 0.000 abstract description 19
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 7
- 239000008346 aqueous phase Substances 0.000 abstract 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 31
- 239000000945 filler Substances 0.000 description 29
- 239000004215 Carbon black (E152) Substances 0.000 description 25
- 229930195733 hydrocarbon Natural products 0.000 description 24
- 150000002430 hydrocarbons Chemical class 0.000 description 24
- 238000010992 reflux Methods 0.000 description 20
- 229960000583 acetic acid Drugs 0.000 description 19
- 239000002253 acid Substances 0.000 description 16
- 230000008569 process Effects 0.000 description 13
- 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 description 12
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 12
- 239000002994 raw material Substances 0.000 description 12
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 11
- 239000011964 heteropoly acid Substances 0.000 description 11
- 238000012856 packing Methods 0.000 description 11
- 238000004458 analytical method Methods 0.000 description 10
- 238000005070 sampling Methods 0.000 description 9
- 235000014113 dietary fatty acids Nutrition 0.000 description 7
- 239000000194 fatty acid Substances 0.000 description 7
- 229930195729 fatty acid Natural products 0.000 description 7
- -1 fatty acid ester Chemical class 0.000 description 7
- 239000003456 ion exchange resin Substances 0.000 description 7
- 229920003303 ion-exchange polymer Polymers 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 230000004044 response Effects 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 239000003729 cation exchange resin Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000009849 deactivation Effects 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 230000032050 esterification Effects 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 238000007701 flash-distillation Methods 0.000 description 4
- 230000002779 inactivation Effects 0.000 description 4
- 239000002808 molecular sieve Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- RGCLLPNLLBQHPF-HJWRWDBZSA-N phosphamidon Chemical group CCN(CC)C(=O)C(\Cl)=C(/C)OP(=O)(OC)OC RGCLLPNLLBQHPF-HJWRWDBZSA-N 0.000 description 4
- 238000007670 refining Methods 0.000 description 4
- GQKZRWSUJHVIPE-UHFFFAOYSA-N sec-amyl acetate Natural products CCCC(C)OC(C)=O GQKZRWSUJHVIPE-UHFFFAOYSA-N 0.000 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 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 3
- 235000019687 Lamb Nutrition 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical class [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 3
- 238000007036 catalytic synthesis reaction Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000284 extract Substances 0.000 description 3
- 239000012451 post-reaction mixture Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- OAIYNRAQCIOEBD-UHFFFAOYSA-N butyl acetate;hydrate Chemical compound O.CCCCOC(C)=O OAIYNRAQCIOEBD-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000003915 liquefied petroleum gas Substances 0.000 description 2
- 238000006384 oligomerization reaction Methods 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229960001866 silicon dioxide Drugs 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910021654 trace metal Inorganic materials 0.000 description 2
- 238000005829 trimerization reaction Methods 0.000 description 2
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 description 1
- XTVRLCUJHGUXCP-UHFFFAOYSA-N 3-methyleneheptane Chemical compound CCCCC(=C)CC XTVRLCUJHGUXCP-UHFFFAOYSA-N 0.000 description 1
- GJONDLRNIMOQNU-UHFFFAOYSA-N CC(O)=O.CCC(C)OC(C)=O Chemical compound CC(O)=O.CCC(C)OC(C)=O GJONDLRNIMOQNU-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- PCWZHTGDXLRULT-UHFFFAOYSA-N buta-1,3-dienylbenzene styrene Chemical compound C(=C)C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 PCWZHTGDXLRULT-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229940043232 butyl acetate Drugs 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229920001429 chelating resin Polymers 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
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000019439 ethyl acetate Nutrition 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 1
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 239000007788 liquid 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
- 150000001457 metallic cations Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 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
- 239000003208 petroleum Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 230000011218 segmentation Effects 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
- 239000007787 solid Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 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
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for preparing sec-butyl acetate, which includes steps as follows: (1) with the existence of a catalyst and under the condition of addition reaction, C4 olefin contacts and reacts with acetic acid for a plurality of times; (2) the reaction products obtained in Step (1) are rectified and separated, C4 light components are obtained from the top of a tower and tower bottoms are obtained from the bottom of the tower; (3) the tower bottoms obtained in Step (2) and water are boiled and rectified, sec-butyl acetate and C8 olefin are obtained from the top of the towerin the form of azeotrope and acetic acid is obtained from the bottom of the tower; (4) the azeotrope obtained in Step (3) is condensed, oil and water separation is carried out and aqueous phase products and oil phase products containing C8 olefin and sec-butyl acetate are obtained; and (5) the oil phase products obtained in Step (4) and water are boiled and rectified, C8 olefin is obtained from the top of the tower in the form of azeotrope and sec-butyl acetate is obtained from the bottom of the tower. The method provided by the invention can obtain relatively high yield of sec-butyl acetate and can obtain sec-butyl acetate and recycle acetic acid at a relatively high purity.
Description
Technical field
The present invention relates to a kind of preparation method of sec-butyl acetate.
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 the good organic solvent of a kind of preparation that is widely used as grease, resin, coating, paint and organic reaction process, extraction separation process etc., can also be used for preparing metal clean-out system and spices etc.Particularly in recent years, because the environmental requirement increasingly stringent, the use that contains the solvent of 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 the market hot-sale products.At present, the butylacetate series products is based on n-butyl acetate on the market, but because n-butyl acetate need be by price higher propyl carbinol and acid esterification prepared in reaction, production cost is higher, therefore, domestic and international many companies are developing the sec-butyl acetate as the n-butyl acetate substitute one after another.The character and the n-butyl acetate of sec-butyl acetate are close, and can adopt the method preparation of a large amount of by-products of refinery, low-cost butylene and acetate direct addition, therefore can reduce cost greatly.
Prepare the technology of sec-butyl acetate, open in many pieces of patent applications and document, report about acetate and butylene direct addition.
For example, EP483826, US5457288 have proposed the employing acidic cation-exchange resin as catalyzer, carry out acetate/butylene addition reaction.Acetate and alkene are crossed with the liquid form Continuous Flow and are equipped with the catalytic tubular fixed-bed reactor of acidic cation-exchange resin.Reaction conditions is: the mol ratio of acetate and alkene is 1-2, and temperature of reaction is 80-120 ℃, and pressure is 2MPa, and air speed (LHSV) is 0.1-10h
-1Wherein, also mention the method separating acetic acid that can adopt rectifying and the adduct of butylene, but do not specify separation method.
CN1099381A and CN1358112A have proposed a kind of preparation method of low-grade fatty acid ester, and this method adopts carried heteropoly acid (salt) as catalyzer, generate low-grade fatty acid ester by low-carbon (LC) carboxylic acid and olefine reaction.
CN1184807A has proposed a kind of preparation method of organic acid acetic, adopt homogeneous phase or heterogeneous catalyst such as sulfuric acid, phosphoric acid, heteropolyacid, strong-acid ion exchange resin, zeolite, by liquefied petroleum gas (LPG) that contains mixed olefins and acetic acidreaction, obtain the blended organic acid acetic.
CN1428327A has proposed a kind of Catalyst And Method that is used to prepare low-grade fatty acid ester, adopts carried heteropoly acid or heteropolyacid salt as catalyzer, generates low-grade fatty acid ester by carboxylic acid and olefine reaction.
CN101007759A and CN101081812A have proposed a kind of method and a kind of method for preparing the used acidic ion exchange resin catalyst of lower fatty acid fat of protecting for preparing low-grade fatty acid ester respectively; the addition reaction of its alkene and lipid acid also is to adopt ion exchange resin as catalyzer; but the water washing device and the protection bed that in the MTBE production process, extensively adopt before main reactor, have been increased; removing in the raw material the deleterious material of resin catalyst, and to propose with the titanium be that material is made reactor.
CN101121656A has proposed a kind of method by acetate and linear butylene catalytic Synthesis of sec-Butyl Acetate, and this method adopts fixed-bed reactor, uses solid catalyst, and acetate and butylene are reacted catalytic Synthesis of sec-Butyl Acetate under the condition of gas-liquid-solid phase reaction.
CN101100425A has proposed a kind of method of synthesizing acetic ester; propylene that this method employing mol ratio is 0.3-3.0 or butylene and acetic acid are raw material; be the main body catalyzer again with the solid acid after pre-protective material by catalyzer; in upflow fixed bed reactor, carry out building-up reactions; above-mentioned reaction conditions comprises that temperature of reaction is 50-170 ℃; reaction pressure is 0.2-4.0MPa, and the acetic acid air speed is 0.1-4.0h
-1
(petrochemical complex, 1988,17 (9): 565-567) studied with the 12-phospho-wolframic acid is catalyzer to Cai Tianxi etc., intermittent kettle reactor, the solution-air addition esterification of butene-1 and acetate.
(Fushun petroleum journal such as Song Xuchun, 2001,21 (1): 8-11) having studied with activated carbon supported 12-phospho-wolframic acid is catalyzer, intermittent kettle reactor, the addition esterification of butene-1 and acetate, at 1.5MPa, 120 ℃, reacted 7 hours, acetate transformation efficiency 85.8%, the esterification selectivity is near 98%, but the easy inactivation of catalyzer, use 5 times after activity just become very poor.
SnCl such as Zhu Minliang
4Modified ion-exchange resin is acetic acid and the acetic acid synthesized secondary butyl ester of butene reaction in tank reactor, and the discovery modified catalyst is compared the acetic acid transformation efficiency with unmodified catalyzer and is doubled, and brings up to 70% by 35%.
Above-mentioned patent application and open source literature mainly are catalyzer and the reaction process about acetate and butylene addition reaction, seldom mention the separation problem of reaction product.For the addition reaction of acetate and butylene, except that sec-butyl acetate, also contain unreacted acetate, C in the reaction product
4Hydrocarbon and butylene are built up
C8 alkene particularly adopt aforesaid method can produce a large amount of superimposed by products; When raw material contains or adopts sec-butyl alcohol to make reaction control agent, also contain a certain amount of sec-butyl alcohol in the product.Because butylene and other component boiling point differ greatly, and are easy to adopt the method for conventional distillation that it is separated, and acetate (118 ℃ of boiling points), sec-butyl acetate (113 ℃ of boiling points), C
8The boiling point of alkene (boiling point 101-120 ℃) and sec-butyl alcohol (99.5 ℃) is approaching, is difficult to adopt the method for conventional rectification that it is separated.Therefore, for the route that adopts acetate and butylene additive process catalytic Synthesis of sec-Butyl Acetate, how separating secondary butyl ester of purifying acetic acid and acetate from reaction mixture, is one of key of this technology.But in the prior art, it is few in number to relate to the isolating report of this system.
For example, CN101130495A has proposed a kind of from acetate and butylene or mixed C
4The method of the secondary butyl ester of separating acetic acid at first adopts flashing tower A separation of C in the post reaction mixture
4And light constituent; Again by rectifying tower B separating acetic acid and sec-butyl acetate; By treating tower C sec-butyl acetate is made with extra care at last.Because the boiling point of acetate and sec-butyl acetate is very approaching, therefore in fact adopt the method for conventional distillation to be difficult to realize both effective separation.
CN101007761A has proposed a kind of from acetate and mixed C
4The method of the secondary butyl ester of separating acetic acid in the post reaction mixture, earlier with product by flashing tower from removed overhead C
4Again with the flashing tower bottom product by being that the azeotropic distillation of entrainer separates with A (water); Azeotropy rectification column cat head material is entered the refining sec-butyl acetate that obtains for the treatment of tower; Azeotropy rectification column bottoms material directly recycled or by being to recycle after the azeotropic distillation process of entrainer concentrates with B (water).This application has proposed a kind of from acetate and mixed C
4The method of the secondary butyl ester of separating acetic acid in the post reaction mixture, but have the following disadvantages: (1) adopts the method for flash distillation to be difficult to complete separation of C
4And light constituent, so flashing tower substrate material contains the C of a great deal of
4And light constituent, and have a certain amount of acetate and sec-butyl acetate in the cat head effluent; (2) can generate C in the addition reaction process of not mentioned acetate and butylene
8And C
8Above heavy alkene is not mentioned sec-butyl alcohol yet, does not therefore just mention how they being separated from reaction product yet.
CN101168504A has proposed the method for the secondary butyl ester of a kind of separating acetic acid, acetate and heavy hydrocarbon, at first adding entrainer (water) in mixture to be separated enters azeotropy rectification column and separates, the azeotrope that sec-butyl acetate and entrainer form steams from cat head, acetate and heavy hydrocarbon then fall into the tower still, and the acetate that falls into the tower still removes heavy hydrocarbon by the method for washing again.This application is mentioned in the addition reaction process of acetate and butylene can generate C
8And C
8Above heavy hydrocarbon, heavy hydrocarbon falls into the tower still in the azeotropy rectification column azeotropy rectification column, and the method for proposition employing washing removes the heavy hydrocarbon in the acetate.
Comprehensive existing sec-butyl acetate synthetic public information finds that prior art has the following disadvantages: butylene is converted into the selectivity variation of sec-butyl acetate in (1) sour alkene addition reaction, and the easy inactivation of catalyzer; (2) behind catalyst deactivation, need close down the replacing that reactive system carries out catalyzer; (3) for preventing catalyst deactivation, need set up protection bed and remove detrimental impurity in the raw material, because the protection bed catalyst is different with reactor with operational condition, increased the complicacy of process; (4) the separation system separation efficiency of prior art is not high, causes the waste of raw material and product purity not high.
Summary of the invention
The objective of the invention is to overcome have in the preparation of prior art sec-butyl acetate that butylene in the sour alkene addition reaction is converted into that the selectivity of sec-butyl acetate is lower, the easy inactivation of catalyzer, defective that product purity is not high, can effectively improve selectivity that butylene in the sour alkene addition reaction is converted into sec-butyl acetate and improve the preparation method that the yield of target product sec-butyl acetate and catalyzer are not easy inactivation, sec-butyl acetate product that product purity is high thereby provide a kind of.
The invention provides a kind of preparation method of sec-butyl acetate, this method comprises:
(1) in the presence of catalyzer and under the addition reaction condition, with C
4Alkene contacts, reacts with acetate several times;
(2) under the rectifying condition, step (1) gained reaction product is carried out rectifying separation in first rectifying tower, from cat head extraction C
4Light constituent, extraction bottom product at the bottom of the tower, this bottom product contains sec-butyl acetate, C
8Alkene and unreacted acetate;
(3) under the azeotropic distillation condition, contain sec-butyl acetate, C with what step (2) obtained
8The bottom product of alkene and unreacted acetate and water enter and carry out azeotropic distillation in first azeotropy rectification column, and the amount that enters the described water in first azeotropy rectification column can make sec-butyl acetate and C
8Alkene with the form of azeotrope from the cat head extraction, acetate extraction at the bottom of the tower;
(4) azeotrope that step (3) is obtained carries out oily water separation after condensation, obtains water-phase product and contains C
8The oil-phase product of alkene and sec-butyl acetate;
(5) under the azeotropic distillation condition, oil-phase product that step (4) is obtained and water enter and carry out azeotropic distillation in second azeotropy rectification column, and the amount that enters the described water in second azeotropy rectification column can make C
8Alkene with the form of azeotrope from the cat head extraction, sec-butyl acetate extraction at the bottom of the tower.
The preparation method of sec-butyl acetate provided by the present invention has following advantage: in addition reaction with C
4Alkene contacts, reacts with acetate several times, can effectively disperse concentration of olefin, at acetate consumption and described C
4Under the constant situation of the mol ratio of total consumption of alkene, improve the sour alkene ratio of each contact, help the rising of control reaction temperature, prevent that focus from producing, thereby reduce the superimposed product of alkene, improve reaction preference, prolong life of catalyst significantly; By the addition reaction products therefrom is carried out rectifying separation, can thoroughly remove C
4Light constituent, the purity of raising target product sec-butyl acetate.According to method provided by the invention, can prepare wherein acetate, C
8The sec-butyl acetate product of the higher degree that the content of alkene and sec-butyl alcohol is all very low; And operating process is simple, energy consumption is low and the investment of whole device is lower.And, in the preferred case, by control to the water consumption that makes in the whole process, need not to resulting acetate and water in the sec-butyl acetate separate once more can make acetate and sec-butyl acetate purity up to more than 99%, thereby can simplify the operation, water saving, and separation efficiency is very high.And product is separated method of the present invention and feed purification concentrates in together, and flow process is simple, and energy consumption is low.
Description of drawings
Fig. 1 is expressed as of the present invention by acetate and C
4The alkene addition reaction prepares the schema of sec-butyl acetate.
Embodiment
Below in conjunction with Fig. 1 to of the present invention by acetate and C
4The method that the alkene addition reaction prepares sec-butyl acetate is elaborated.
In the step (1), described with C
4The method that alkene contacts, reacts with acetate several times comprises acetate elder generation and portion C
4Alkene contact, then with the product after the gained contact again with rest part C
4The alkene contact, the C of rest part
4Alkene once or several times contacts with acetate and carries out addition reaction.
The preparation method of sec-butyl acetate provided by the invention can continous way carry out, and also can carry out by intermittent type.When the preparation method of described sec-butyl acetate carries out with intermittent type, under the preferable case, described C
4The method that alkene contacts with acetate several times comprises whole described acetate once joined in the reaction vessel, and then with C
4Alkene joins in this reaction vessel in batches.When the preparation method of described sec-butyl acetate carries out with continous way, under the preferable case, as shown in Figure 1, described C
4The method that alkene contacts with acetate several times comprises the flow direction of material according to acetate, and whole acetate is directly fed in first reactor, with described C
4Alkene be divided into several strands be passed into this first reactor and with the placed in-line successively a plurality of reactors of this first reactor in, make C
4Alkene divides multistage to contact, react with acetate.
By making described C
4Alkene contacts with acetate several times, can reduce the concentration of alkene in each reactor, thereby suppress the generation of addition reaction between alkene, improve the selectivity of reaction to the direction that generates sec-butyl acetate, improve the yield of sec-butyl acetate, reduced the product separation amount.
To described C
4The adjacent time that contacts for twice with acetate of alkene is not particularly limited, as long as can make described C
4Alkene fully contacts with acetate, generates after the sec-butyl acetate C with next batch again
4The alkene contact gets final product C
4Alkene and acetate adjacent twice duration of contact is 5-200 minute, is preferably 10-30 minute.
Though described C
4The number of times that alkene contacts with acetate is many more, at every turn the C that contacts with acetate
4The amount of alkene is few more, because of C
4Alkene and acetate generation addition reaction and liberated heat are just few more, temperature rise is also just low more in the reaction system like this, the transformation efficiency of alkene and carboxylic acid is high more, and conversion of olefines is that the selectivity of fatty acid ester is high more, thereby but increasing frequency of exposure need increase equipment and increased production cost.Therefore, take all factors into consideration production cost and reaction effect, described C
4The number of times that alkene contacts with acetate is preferably 2-10 time, more preferably 2-6 time, more preferably 3-5 time, most preferably is 4 times.Among the present invention, described temperature rise refers to the lift-off value of temperature.
In the present invention, the consumption of described acetate and described C
4The mol ratio of total consumption of alkene can be 0.5-10, is preferably 0.8-5, more preferably 1-5, more preferably 1-2.In order further to reduce C
4Conversion of olefines is C
8The transformation efficiency of hydrocarbon, in each contact, described acetate and C
4The mol ratio of alkene is not less than 1, is preferably 1-2.
In each contact, described C
4Alkene and described C
4The part by weight of total consumption of alkene is 0.05-0.9.And, at described C
4The number of times that alkene contacts with acetate is under the situation more than four times or four times, along the flow direction of material, and C described in the contact for the first time and the second time contact
4Alkene with contact for the third time and C described in the 4th time contacts
4The weight ratio of alkene is preferably 1.2-1.8.
Described C as the addition reaction raw material
4Alkene can be 1-butylene, suitable 2-butylene, anti-2-butylene or their mixture, also can be the mixed C that contains above-mentioned alkene
4Adopt mixed C
4During for raw material, C
4In also may contain normal butane and Trimethylmethane, they do not participate in the reaction.
The catalyzer of Cai Yonging can comprise carried heteropoly acid or salt, unsupported property heteropolyacid or salt, storng-acid cation exchange resin, molecular sieve, SO in the present invention
4 2-/ ZrO
2Type solid super-strong acid, or their mixture.As the storng-acid cation exchange resin of catalyzer mainly is to obtain polystyrene resin by vinylbenzene-Vinylstyrene 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 obtain according to the method that well known to a person skilled in the art is synthetic, also can buy from market easily, be D72 as the trade mark, D005, D006, D008, S54, Amberlyst 15, Amberlyst 35, Dowex 50, K2611, K2431, Puolite 175, Puolite 275 resins such as grade. selectable molecular sieve has Y series, ZSM series, MCM series, β series equimolecular sieve. selectable heteropolyacid comprises the Keggin structure, the Dawson structure, the Anderson structure, the heteropolyacid of Silverton structure. the heteropolyacid that uses the Keggin structure usually is as 12 phospho-wolframic acid (H
3PW
12O
40), 12 silicotungstic acid (H
4SiW
12O
40), 12 phosphomolybdate (H
3PMo
12O
40), 12 molybdovanaphosphoric acids and their hydrate be as catalyzer.For heteropolyacid, because its specific surface area is less and be difficult to independent moulding, therefore preferably it is loaded on the suitable carriers usually, form carried heteropoly acid catalyst.Available carrier comprises metal oxide carriers such as silicon-dioxide, aluminum oxide, large pore molecular sieve, gac, in the ion exchange resin of special processing (as charing) one or more.
In the preparation method of sec-butyl acetate provided by the invention, described acetate and C
4It is 30-300 ℃ that the condition that alkene carries out addition reaction can adopt temperature of reaction, is preferably 50-200 ℃, most preferably is 70-150 ℃; The charging air speed is 0.2-20h
-1, be preferably 0.5-10h
-1, most preferably be 0.8-5h
-1Reaction pressure is 0.1-10MPa, is preferably 0.6-2MPa.Described reaction pressure refers to absolute pressure.
Above-mentioned addition reaction can be carried out in various devices, for example can in following apparatus, carry out, this device comprises at least two placed in-line fixed-bed reactor, the flow direction along material, described first fixed-bed reactor directly are communicated with the acetate supply source, comprise all direct and C of each fixed-bed reactor of first fixed-bed reactor
4The alkene supply source is communicated with, like this, and acetate elder generation and the C that feeds in first fixed-bed reactor
4Alkene contact, reaction, unreacted acetate again with the C that feeds in second fixed-bed reactor
4Alkene contact, reaction, the rest may be inferred, until with last fixed-bed reactor in C
4Discharge alkene contact, reaction back, obtains the addition reaction product, and this addition reaction product carries out follow-up lock out operation again.By above-mentioned with C
4Alkene branch multiply feeds a plurality of placed in-line fixed-bed reactor can realize C
4Alkene contacts, reacts with acetate several times.
The reactive system of preparation sec-butyl acetate provided by the invention, acetate enters from first reactor, and the alkene segmentation enters reactor.Alkene sectional benefit is effectively to reduce the concentration of alkene, avoid focus to produce, and can be under the lower situation of total acid alkene, improve sour alkene ratio actual in the reactor, uniformly temperature of reaction and high sour alkene are than helping suppressing the generation that alkene oligomerization reacts, select thereby improve reaction, reduce the product separation difficulty, and prevent catalyst deactivation.
Described fixed-bed reactor can be shell and tube reactor, cartridge reactor or radial reactor separately.Described fixed-bed reactor can be adiabatic reactors, also can be isothermal reactors.As select adiabatic reactor, then between reactor, should establish interchanger, so that the extraction heat of reaction.Under the situation of selecting adiabatic reactor, between reactor, should establish interchanger, so that take out heat of reaction.Number of reactors is also many, and alkene charging segments is many more, and temperature of reaction control is good more, and reaction effect is good more, but the manufacturing expense of reactor is also high more.In order to save cost when guaranteeing reaction efficiency, the number of described fixed-bed reactor is preferably 2-10, more preferably 2-6, more preferably 3-5, most preferably is 4.
Thereby described acetate supply source can be the various containers that acetate can provide acetate for the reaction of preparation sec-butyl acetate that are equipped with, and can be the form of conventional can, also can not be this form.
Described C
4Source olefins can be the various C of being equipped with
4Thereby alkene can provide C for the reaction of preparation sec-butyl acetate
4The container of alkene can be the form of conventional can, also can not be this form.
The adduct of acetate and butylene is formed with the catalyzer, reactor and the reaction conditions that adopt much relations.In general, reaction also contains a certain amount of by C except that generating sec-butyl acetate
4Alkene oligomerization reacts and the C of generation
8Alkene, these C
8Alkene comprises various isomer, and therefore its boiling point is difficult to separate with acetic acid (117 ℃ of boiling points) with sec-butyl acetate (113.2 ℃ of boiling points) between 100-120 ℃.In addition, when in the raw material when moisture, or during as reaction control agent, also contain a certain amount of sec-butyl alcohol (99.5 ℃) in the reaction product with sec-butyl alcohol.In addition, also may contain the high boiling material of trace in the reaction product, as by C
4Alkene trimerization, trimerization be above generate greater than C
8Above heavy hydrocarbon.Because the present invention adopts C
4The mode that alkene contacts, reacts with acetate several times, therefore, compared with prior art, the content of high boiling material obviously reduces in the reaction product, even be low to moderate 0 content, thereby the high boiling material content that need not especially to remove in the acetate that the high boiling material step can make the sec-butyl acetate that obtains and recovery is lower. so may contain sec-butyl acetate, C in the reaction product
8Alkene, sec-butyl alcohol, acetate and high boiling material, its quality is formed may be sec-butyl acetate 5-90%, acetate 10-80%, C
8Alkene 0.2-40%, sec-butyl alcohol 0-10%, high boiling material are 0-5%.
Under the preferable case, as shown in Figure 1, be respectively arranged with bypass between the outlet of each described fixed-bed reactor and the inlet, described bypass is controlled with adjacent fixed-bed reactor and/or bypass by valve and is communicated with.Described bypass can be with for example various forms setting of other pipe.Between the outlet of each described fixed-bed reactor and inlet, be respectively arranged with under the situation of other pipe, when the valve closes of other pipe and during the valve open of the outlet of reactor and inlet, material directly passes through from reactor; When the valve open of other pipe and during the valve closes of the outlet of reactor and inlet, material can directly flow to the other pipe of another reactor or another reactor by other pipe.Like this, in case in operation process the catalyst deactivation in the reactor, can open the valve of other pipe, make material pass through other pipe, therefore can be under the situation of not influence process running catalyst changeout or carry out catalyst regeneration more.
In described step (2), under the rectifying condition, with step (1) gained reaction product with (take off C as the water of entrainer at the first rectifying tower T1
4Rectifying tower) carries out rectifying separation in, from cat head extraction C
4Light constituent takes out bottom product at the bottom of tower, this bottom product contains sec-butyl acetate, C
8Alkene and unreacted acetate.Sec-butyl acetate, C in the bottom product
8The content of alkene and unreacted acetate changes with the addition reaction condition of the sour alkene mol ratio that comprises addition reaction.Because method provided by the invention adopts C when addition reaction
4The mode that alkene contacts with acetate several times can effectively suppress C in the bottom product
8Alkene and greater than C
8The content of heavy hydrocarbon, therefore C in the described bottom product
8Alkene and greater than C
8The content of heavy hydrocarbon generally is no more than 2 weight % of bottom product total amount.
According to the present invention, under the rectifying condition, with C
4Alkene contacts, reacts the gained reaction product several times and carry out rectifying separation in first rectifying tower with acetate, comprise unreacted C from the cat head extraction
4Alkene is at interior C
4Light constituent, extraction bottom product at the bottom of the tower, this bottom product contains sec-butyl acetate, C
8Alkene and unreacted acetate.In CN101130495A, mention the adduct of acetate and butylene fed flashing tower, by flash distillation with C
4Separate from cat head.Though adopt the method for flash distillation can save the construction cost and the separating energy consumption of tower, the present inventor confirms by repetition test, adopts the method for flash distillation can not realize C
4Light constituent separates fully with other component, can be entrained with a certain amount of acetate and sec-butyl acetate in overhead product, and also can be entrained with a certain amount of C in bottom product
4Light constituent.Because the small amount of acetic acid that has in the cat head light constituent is corroded the rear portion system easily, and bottom product contains C
4Light constituent also can have a strong impact on separating effect, and causes C
4Therefore the loss of light constituent is necessary to make the C4 light constituent fully to separate with bottom product.
And the present invention adopts rectifying tower to carry out the method for rectifying separation, can remove fully to comprise unreacted C
4Alkene is at interior C
4Light constituent, C in the bottom product
4Light constituent can reach 0 content.According to method provided by the invention, described C
4Light constituent is meant that carbonatoms is 4 various hydrocarbon, is one or more the general designation in butane, n-butene, iso-butylene, maleic and the anti-butylene.
According to method provided by the invention, described rectifying condition comprises: the stage number of described first rectifying tower or theoretical plate number can be the 5-100 piece, are preferably the 10-60 piece, more preferably the 20-40 piece; Reflux ratio can be 0.2-10: 1, be preferably 0.5-2: 1.Tower top temperature can be 30-60 ℃, and column bottom temperature can be 100-200 ℃; Pressure (absolute pressure) can be 0.05-1MPa.
Described first rectifying tower promptly takes off C
4Rectifying tower can be packing tower and/or tray column, and described packing tower is filled with one or more in Raschig ring, Pall ring, cascade ring, saddle type ring, arc saddle type, square saddle type, Dixon ring, Cannon ring, Lamb wave line and the net corrugated regular filler; Tray column is equipped with one or more in bubble-cap, sieve plate, inclined hole and the float valve.
Because sec-butyl acetate (113.2 ℃ of boiling points), acetic acid (117 ℃ of boiling points), C
8The boiling point of alkene (boiling point 100-120 ℃) and sec-butyl alcohol (99.5 ℃ of boiling points) is very approaching, therefore, be difficult to adopt the method for conventional distillation that it is separated. according to chemical industry general knowledge as can be known, acid esters compound can both form the azeotropic azeotrope with water mostly, from the chemical industry handbook, can find the azeotropic of sec-butyl acetate and water and form (water 19.5%, sec-butyl acetate 80.5%), azeotropic temperature (87.3 ℃). therefore, the method that those skilled in the art will readily appreciate that the employing azeotropic distillation is come secondary butyl ester of separating acetic acid and acetate, as described in CN101007761A and the CN101168504A, aforesaid method discloses the method that the separation of adopting azeotropic distillation contains acetate and sec-butyl acetate, but the former only relates to the azeotropic separation of acetate-sec-butyl acetate, though the latter relates to acetate-sec-butyl acetate-heavy hydrocarbon system, does not find heavy hydrocarbon (C
8Alkene and heavier hydrocarbon) also can form azeotrope with water under certain condition, therefore, this method just utilizes water and sec-butyl acetate formation azeotrope to separate from cat head, and acetate and heavy hydrocarbon then fall into the tower still, and propose to adopt the method for washing to separate heavy hydrocarbon.In addition, do not mention the separation problem of sec-butyl alcohol yet.
Owing to contain the approaching sec-butyl acetate of boiling point (113.2 ℃ of boiling points), acetic acid (117 ℃ of boiling points), C simultaneously in the product that adopts method of the present invention to obtain
8The sec-butyl alcohol (99.5 ℃ of boiling points) that alkene (boiling point 100-120 ℃) and selectivity contain, form different with the product that adopts the prior art for preparing sec-butyl acetate, therefore, the present inventor has proposed a kind of azeotropic distillation separation scheme that is different from prior art.The inventor has carried out a large amount of research, finally finds these C
8Alkene all can form the lower boiling azeotrope with water, and its azeotropic temperature is lower than the temperature of the azeotrope that water and sec-butyl acetate form, and notices that sec-butyl alcohol can form ternary azeotrope with water, 2-butyl acetate.
Following table 1 is the related representative C of separation system that the inventor measured
8The azeotropic temperature and the composition (P=0.1013MPaA) of alkene and the azeotrope that forms with water thereof.
Table 1
| The superimposed alkene that generates | Normal boiling point/℃ | With the azeotropic temperature of water/℃ | Azeotropic composition/% with water |
| 2-methyl heptene-1 | 119.2 | 81.4 | 86.9 |
| 2,3-dimethyl hexene-1 | 110.4 | 78.0 | 79.1 |
| 2-ethyl hexene-1 | 119.9 | 80.6 | 83.1 |
| 2,4,4-2,4,4-Trimethyl-1-pentene-1 | 101.5 | 76.0 | 87.1 |
| 2,4,4-2,4,4-Trimethyl-1-pentene-2 | 104.9 | 75.3 | 85.8 |
| Different laurylene | 180 | 92 | 83.5 |
In described step (3), under the azeotropic distillation condition, what make that step (2) obtains contains sec-butyl acetate, C
8The bottom product of alkene and unreacted acetate and water enter and carry out azeotropic distillation in first azeotropy rectification column, and the amount that enters the described water in first azeotropy rectification column can make sec-butyl acetate and C
8Alkene is obtained with the form of azeotrope, and obtains this azeotrope from cat head, obtains acetate at the bottom of tower.
In described step (4), the azeotrope that step (3) is obtained carries out oily water separation after condensation, obtains water-phase product and contains C
8The oil-phase product of alkene and sec-butyl acetate.The composition of gained water-phase product is water substantially, and this water can directly circulate and be used for the azeotropic distillation of first azeotropy rectification column, also can be used for the azeotropic distillation of the second follow-up azeotropy rectification column.
In described step (5), under the azeotropic distillation condition, oil-phase product that step (4) is obtained and water enter and carry out azeotropic distillation in second azeotropy rectification column, and the amount that enters the described water in second azeotropy rectification column can make C
8Alkene with the form of azeotrope from the cat head extraction, sec-butyl acetate extraction at the bottom of the tower.
According to the present invention, when carrying out above-mentioned addition reaction and adopt sec-butyl alcohol to contain water in as reaction control agent or reaction raw materials, also contain a certain amount of sec-butyl alcohol in the reaction products resulting, and the content of sec-butyl alcohol can be 0-10 weight % in the described reaction product, is generally 0.1-10 weight %.In addition, in the presence of water, owing to having small part that hydrolysis reaction can take place, sec-butyl acetate generates sec-butyl alcohol, thus, in the method for the invention, the bottom product that obtains in described step (2), the overhead product (azeotrope) that step (3) obtains, this azeotrope is carried out also contain sec-butyl alcohol in the oil-phase product of gained after the oily water separation after condensation, and all may contain sec-butyl alcohol in the oil-phase product that obtains of step (4), in step (3), enter the amount that enters the water of second azeotropy rectification column in the amount of water of first azeotropy rectification column and the step (5) this moment and can also make sec-butyl alcohol respectively with the cat head extraction of the form of azeotrope from the cat head and second azeotropy rectification column of first azeotropy rectification column.
According to method provided by the invention, in the preferred case, in step (3), the amount that enters water described in described first azeotropy rectification column makes that the water-content in the resulting acetate is not higher than 1 weight % at the bottom of the tower, preferably less than 1 weight %.Thus, can make acetate not need directly to get back to through dehydration once more to recycle in the reaction unit, therefore can simplify the operation, and reduce energy consumption, can economize on water simultaneously.
The inventor notices, although sec-butyl acetate and C
8Alkene all can form azeotrope with water, but the latter's azeotropic temperature is lower than the former, therefore, and the preferential and C of water
8Alkene forms azeotrope.The present inventor is also noted that 2-butyl acetate, water and sec-butyl alcohol can form ternary azeotrope.And this ternary azeotropic point (86 ℃) is lower than the temperature of the binary azeotrope of sec-butyl acetate and water, therefore by the control water yield, can make C
8Alkene and sec-butyl alcohol reach the purpose of dehydration simultaneously from the form extraction of cat head with azeotrope.According to method provided by the invention, in the preferred case, the amount that enters water described in described first azeotropy rectification column in the step (3) can adopt following formula 1 and 2 to calculate:
W1＝W1’×(1±A)(1)
Wherein, W1 is amount or the flow that enters water described in described first azeotropy rectification column in the step (3), comprises the total amount of the water that may have in water, round-robin water of adding and the reaction product that enters tower, represents that with weight or weight rate dimension is identical with W1 ';
A is 0-10%, is preferably 0-5%, more preferably 0-2%;
W1’＝F1×[X2×15/85+X3×32/45+(X1-X3×23/45)×19.5/80.5](2)
F1 is amount or the flow that enters the described bottom product in first azeotropy rectification column, represents with weight or weight rate;
X1 is the quality percentage composition of sec-butyl acetate in the described bottom product that enters in first azeotropy rectification column;
X2 is C in the described bottom product that enters in first azeotropy rectification column
8The quality percentage composition of alkene;
X3 is the quality percentage composition of sec-butyl alcohol in the described bottom product that enters in first azeotropy rectification column.
Adopt above-mentioned formula 1 and 2 amounts of being calculated that enter water described in first azeotropy rectification column to carry out azeotropic distillation and can more accurately control the water yield, make this water be enough to the sec-butyl acetate in the reaction product, C
8Alkene and sec-butyl alcohol from the cat head extraction, and can make the acetate at the bottom of the tower only contain very a spot of water or not contain water with the form of azeotrope, and the purity of resulting acetate can be up to more than 99%.Therefore can isolate acetate effectively, and need not subsequent step the acetate that obtains directly can be got back to carry out sec-butyl acetate in the reactive system preparation with recycle.
According to method provided by the invention, in the preferred case, in step (5), the amount W2 that enters water described in described second azeotropy rectification column adopts following formula 3 and 4 to calculate:
W2＝W2’×K(3)
Wherein, W2 is amount or the flow that enters water described in described second azeotropy rectification column in the step (5), comprises the total amount of the water that water, round-robin water of adding and the oil phase that enters tower may have, and represents that with weight or weight rate dimension is identical with W2 ';
K is 1-2;
W2’＝F2×[X22×15/85+X33×32/45](4)
F2 is amount or the flow that enters the oil-phase product in second azeotropy rectification column, represents with weight or weight rate;
X22 is C in the oil-phase product that enters in second azeotropy rectification column
8The quality percentage composition of alkene;
X33 is the quality percentage composition that enters the sec-butyl alcohol in second azeotropy rectification column.
The water yield in second azeotropy rectification column of entering that adopts that above-mentioned formula 3 and 4 calculated is carried out azeotropic distillation and can more accurately be controlled the water yield, makes this water be enough to the C in the reaction product
8Alkene, sec-butyl alcohol from the cat head extraction, and can make the sec-butyl acetate at the bottom of the tower only contain very a spot of water or not contain water with the form of azeotrope, and the purity of resulting sec-butyl acetate can be up to more than 99%.Therefore can isolate sec-butyl acetate effectively, and need not subsequent step and can obtain the sec-butyl acetate product, thereby simplify operation.
According to method provided by the invention, in the preferred case, each position between opening for feed to the first block column plate of described first azeotropy rectification column and second azeotropy rectification column of water that enters described first azeotropy rectification column and second azeotropy rectification column enters, can enter from each position between opening for feed to the first block column plate of described first azeotrope column and second azeotrope column, more preferably enter with the opening for feed of reaction product from the middle part of tower.
According to method provided by the invention, the operational condition of described azeotropic distillation can be determined according to the azeotropic point of each composition formation azeotrope in the required isolating reaction product, generally speaking, the operational condition of described azeotropic distillation comprises that the temperature of cat head is 60-200 ℃, temperature at the bottom of the tower is 60-300 ℃, working pressure can be 0.05-0.5MPa, and reflux ratio is 0.5-200: 1.In the preferred case, the temperature of cat head is 60-100 ℃ in described first azeotropy rectification column, and the temperature at the bottom of the tower is 100-300 ℃, described reflux ratio is 0.5-100: 1, and 2-5 more preferably: 1, described working pressure position 0.05-0.5MPa, more preferably normal pressure, i.e. 0.1MPa.The temperature of cat head is 60-200 ℃ in described second azeotropy rectification column, is preferably 70-90 ℃, and the temperature at the bottom of the tower is 100-300 ℃, described reflux ratio is 1-200: 1, be preferably 5-50: and 1, described working pressure is 0.05-0.5MPa, be preferably normal pressure, i.e. 0.1MPa.
According to method provided by the invention, described first azeotropy rectification column and second azeotropy rectification column can be packing tower, can be tray column, also can be filler and board-like compound tower.
The filler that is loaded in the described packing tower can be for well known to a person skilled in the art various fillers, and for example this filler can be selected from one or more in Raschig ring, Pall ring, cascade ring, saddle type ring, arc saddle type, square saddle type, Dixon ring, Cannon ring, Lamb wave line and the net corrugated regular filler.
In bubble-cap, sieve plate, inclined hole, the float valve one or more can be installed in described tray column.
In order to obtain the ideal separating effect, described first azeotropy rectification column and second azeotropy rectification column preferably have certain theoretical plate number or stage number, for example the 10-200 piece, be preferably 20-100 piece, 40-80 piece more preferably.
According to the present invention, described first azeotropy rectification column and second azeotropy rectification column all can adopt and well known to a person skilled in the art various azeotropy rectification columns, for example, described azeotropy rectification column can be made of body of the tower, tower still, tower still reboiler, cat head water cooler and return tank of top of the tower (phase-splitting). under the preferable case, lower side at first azeotropy rectification column can also be provided with at least one side line extraction mouth, so that extract acetate out in different positions; In the bottom of second azeotropy rectification column (for example, the middle and lower part of stripping section) side offers at least one side line extraction mouth, so that extract sec-butyl acetate out in different positions. the number of described bottom side line extraction mouth can be offered as required, being preferably 1-5. the ratio of described side line produced quantity can change between 0-100%, can be all by extraction at the bottom of the tower to all by regulating the side line extraction. from second azeotropy rectification column, the concentration of the sec-butyl acetate acid of tower bottom and/or the extraction of tower bottom side line generally is higher than 99%.
Can reach 99% from the acetate concentration of the first azeotropic distillation tower bottom and/or the extraction of bottom side line, but the high boiling material that wherein may contain trace, in addition, owing to causing, the reasons such as corrosion that contain impurity or tower in the charging also contain the trace metal positively charged ion in the acetate that obtains, therefore, under the preferable case, the present invention comprises that also the positively charged ion that removes in the acetate that step (3) obtains and/or high boiling material and circulation are used for step (1).
The described method that removes positively charged ion in the acetate and/or high boiling material can adopt the method for various routines, for example distill, method such as absorption, also can adopt extraction part acetate to carry out the mode of neutralizing treatment, to prevent the metallic cation and the accumulation of high boiling material in system of trace with diluted alkaline.
When adopting the distillatory method to remove the acetate of extracting out by the first azeotropic distillation tower bottom, can under the rectifying condition, in acetate decationized Y sieve and high boiling material tower, carry out rectifying, this acetate decationized Y sieve and high boiling material tower can be packing tower and/or tray column.Described packing tower filling filler, described filler can be selected from one or more in Raschig ring, Pall ring, cascade ring, saddle type ring, arc saddle type, square saddle type, Dixon ring, Cannon ring, Lamb wave line and the net corrugated regular filler, and described tray column can be equipped with one or more in bubble-cap, sieve plate, inclined hole, the float valve.The theoretical plate number of described packing tower or the stage number of described tray column can be the 1-50 piece, are preferably the 3-30 piece, more preferably the 5-20 piece.The operational condition of described rectifying can be the condition of routine, and for example, the operational condition of described rectifying comprises: tower top temperature can be 100-150 ℃, and column bottom temperature can be 125-200 ℃.Reflux ratio can be 0-20: 1, be preferably 0.5-2: 1.Working pressure (absolute pressure) can be 0.05-0.5MPa, is preferably normal pressure, i.e. 0.1MPa.
When the method that adopts absorption removes the acetate of being extracted out by the first azeotropic distillation tower bottom, can adsorption tower, the various sorbent materials that can adsorb positively charged ion and high boiling material are housed, as gac, ion exchange resin, molecular sieve etc. in the adsorption tower.The operational condition of described absorption can be the condition of routine, and for example, described adsorption conditions comprises: temperature is 20-100 ℃, and air speed is 0.2-100h
-1, pressure is 0.1-10MPa.
Below with reference to Fig. 1 method of the present invention being carried out flow process describes.
Referring to Fig. 1,, whole acetate is directly fed among the first reactor a1, with described C by pipeline 1 according to the flow direction of material of acetate
4Alkene be divided into several strands by pipeline 2 be passed into this first reactor a1 and with the placed in-line successively second reactor a2 of this first reactor a1, the 3rd reactor a3 and the 4th reactor a4 in; In four reactors catalyzer is housed respectively;
Feed among the rectifying tower T1 by pipeline 3 as raw material from the reaction product of pipeline 3 and to carry out rectifying separation, from cat head extraction C
4Light constituent, this portion C
4The preferred part of light constituent is returned in the tower as refluxing remaining C along pipeline
4Light constituent is discharged by pipeline 4; At the bottom of the tower and/or bottom survey line extraction bottom product, contain sec-butyl acetate, C in this bottom product
8Alkene and unreacted acetate;
Enter azeotropic distillation, sec-butyl acetate, C with the water inlet of pipeline 6 and with the fresh acetic acid raw material of pipeline 1 from the middle part of azeotropy rectification column T2 along pipeline 5 by the bottom product of rectifying tower T1 extraction
8Alkene and sec-butyl alcohol from the cat head extraction, carry out oily water separation through entering phase splitter after the cooling of cat head water cooler with the form of azeotrope, and resulting part water-phase product and part oil-phase product are returned in the tower as refluxing along pipeline by the azeotropic proportion of composing; Remaining water-phase product is with the water inlet azeotropy rectification column T2 of fresh supplemented water as azeotropy rectification column T2, and remaining oil-phase product is extracted out.
Acetate can be at the bottom of the tower of azeotropy rectification column T2 and/or bottom side line extraction. owing to from the acetate that azeotropy rectification column T2 extracts out, may contain the high boiling material of trace, and it is because that bring in the charging or former thereby contain the trace metal positively charged ion because of the corrosion of tower etc., therefore, preferably will enter the acetate decationized Y sieve as charging by pipeline 8 and high boiling material tower T4 carries out rectifying by the acetate of extraction at the bottom of the tower, extraction high boiling material at the bottom of the tower, the acetate that removes positively charged ion and high boiling material is by the cat head extraction, this part removes the preferred part of acetate of positively charged ion and high boiling material and returns conduct backflow in the tower along pipeline, and remaining acetate that removes positively charged ion and high boiling material is recycled as raw material by pipeline 9 Returning reactors; Therefore, under the preferable case, method provided by the invention comprises that also the positively charged ion that removes in the acetate that step (3) obtains and/or high boiling material and circulation are used for step (1).
Enter azeotropic distillation T3 with the water inlet of pipeline 11 from the middle part of azeotropy rectification column T3 by pipeline 7 as charging by remaining oil-phase product of azeotropy rectification column T2 cat head extraction; At the bottom of the tower and/or the sec-butyl acetate of bottom survey line extraction discharge by pipeline 14 and/or pipeline 15; Sec-butyl alcohol and C
8Alkene with the form of azeotrope from the cat head extraction, carry out oily water separation through entering phase splitter after the cooling of cat head water cooler, resulting part water-phase product and part oil-phase product are returned in the tower as refluxing along pipeline by the azeotropic proportion of composing, all the other cat head water-phase product are discharged by pipeline 13, and all the other cat head oil-phase product are discharged by pipeline 12.
Among the present invention, although not shown among Fig. 1, those skilled in the art are appreciated that fully from the water-phase product of the remainder of azeotropy rectification column T2 cat head extraction and also can recycle as the water inlet of azeotropy rectification column T3; Can recycle from the water-phase product of the remainder of azeotropy rectification column T3 cat head extraction, be used as the water inlet of azeotropy rectification column T2 and/or azeotropy rectification column T3.The water inlet of the first azeotropy rectification column T2 and/or the second azeotropy rectification column T3 can all be this recirculated water, can partly be this recirculated water also, and remainder is a fresh water.
In the mode of embodiment the present invention is described in further detail below.
In following examples, the reaction unit that embodiment 1-4 is adopted comprises four placed in-line fixed-bed reactor, the size of each fixed-bed reactor is φ 32 * 4 * 1000mm, the stainless steel tube (manufacturing of 316L stainless steel) that has the recirculated water chuck outward, and six logical sampling valves all are equipped with in the outlet of each fixed-bed reactor, can online sampling analysis, its preparation flow figure is as shown in fig. 1; In the said apparatus, according to the flow direction of material, each fixed-bed reactor number consecutively is the first fixed-bed reactor a1, the second fixed-bed reactor a2, the 3rd fixed-bed reactor a3, the 4th fixed-bed reactor a4;
The tripping device that embodiment 1-4 is adopted comprises and the placed in-line C of taking off of fixed-bed reactor
4Rectifying tower T1 and takes off C
4The placed in-line first azeotropy rectification column T2 of rectifying tower T1 is respectively with the placed in-line second azeotropic treating tower T3 of the first azeotropy rectification column T2 and acetate decationized Y sieve and high boiling material tower T4; The diameter that described tower TI, T2, T3 and T4 are the manufacturing of 316L stainless steel is the packing tower of 50mm, wherein T1 and T4 are equipped with φ 3 glass spring fillers, T2 and T3 are equipped with φ 3 stainless steel Dixon ring fillers, and each tower all is furnished with cat head water cooler, return tank (phase splitter), tower still and tower kettle heater.
In following examples, unless stated otherwise, composition in the table and content obtain by Agilent 6890 gas chromatograph analyses, and hydrogen flame detector/thermal conductivity detector, calibration peak area normalization standard measure are adopted in stratographic analysis.
Embodiment 1
Present embodiment is used to illustrate the preparation method of sec-butyl acetate provided by the invention.
100 gram resin assembling Tricesium dodecatungstophosphate salt catalysts in four fixed-bed reactor, respectively pack into (according to the method preparation of the disclosed embodiment 1 of CN1781598A, the assembling amount of phospho-wolframic acid cesium salt is 19.8 weight %), acetate is fed among the first fixed-bed reactor a1 C so that the speed of 1093 Grams Per Hours is continuous
4(quality group becomes alkene mixture: normal butane 36.2%, anti-butylene 39.5%, n-butene 4.2%, maleic 20.1%) divide four stocks not enter among the first fixed-bed reactor a1, the second fixed-bed reactor a2, the 3rd fixed-bed reactor a3 and the 4th fixed-bed reactor a4 C with the speed of 240 Grams Per Hours, 240 Grams Per Hours, 160 Grams Per Hours, 160 Grams Per Hours
4The total feed of alkene mixture is 800 Grams Per Hours, acetate and C
4The total mol ratio of alkene is that 2. to feed temperature in reactor jacket be 80 ℃ of recirculated water control reaction temperature, by the pressure 1.5MPa. question response situation of back pressure valve Controlling System stablize constant after, the vertex temperature of fixed-bed reactor bed is respectively: a1:86 ℃, a2:85 ℃, a3:83 ℃, a4:82 ℃. and the result calculates according to the 4th fixed-bed reactor a4 outlet product analysis: the total conversion rate of butylene is 80.2%, the selectivity that butylene is converted into 2-butyl acetate is 96.2%, and butylene is converted into C
8The selectivity of superimposed alkene is 1.3%, and the selectivity that is converted into sec-butyl alcohol is 2.5%, does not detect greater than C
8Heavy hydrocarbon.
The reaction product of the outlet extraction of the 4th fixed-bed reactor a4 is fed first rectifying tower (take off C
4Rectifying tower) carry out rectifying separation among the T1, the operational condition of T1 comprises working pressure 0.5MPa, and tower top temperature is 40 ℃, and tower still temperature is 180 ℃, and reflux ratio is 0.8, and the theoretical plate number of T1 is 20.From cat head extraction C
4Light constituent.
First rectifying tower (takes off C
4Rectifying tower) bottom product of extraction feeds continuously among the first azeotropy rectification column T2 with the water as entrainer and carries out azeotropic distillation at the bottom of the T1 tower, the operational condition of T2 comprises that working pressure is normal pressure (0.1MPa), tower top temperature is 85 ℃, and tower still temperature is 135 ℃, and reflux ratio is 3.The first azeotropy rectification column T2 total filler height 2.5m, theoretical plate number is 50, feed entrance point: 1.5m (apart from the filler bottom), survey line position, bottom: 0.4m (apart from the filler bottom).
Feeding second azeotropy rectification column (thick ester azeotropic treating tower) T3 by the overhead product of the first azeotropy rectification column T2 cat head extraction continuously with the water as entrainer, to carry out azeotropic distillation refining, the operational condition of T3 comprises that working pressure is normal pressure (0.1MPa), tower top temperature is 82 ℃, tower still temperature is 132 ℃, and reflux ratio is 20.Obtain light constituent by cat head, obtain the sec-butyl acetate product by the tower still.The second azeotropy rectification column T3 total filler height 3m, theoretical plate number is 60, feed entrance point: 2m (apart from the filler bottom), bottom side line position: 0.5m (apart from the filler bottom).
Enter among acetate decationized Y sieve and the high boiling material tower T4 by the bottom product of extraction at the bottom of the first azeotropy rectification column T2 tower and to carry out rectifying, the operational condition of T4 comprises working pressure normal pressure (0.1MPa), and tower top temperature is 117 ℃, and tower still temperature is 150 ℃, reflux ratio is 0.5, and theoretical plate number is 20.Behind the system stability, each logistics is formed as shown in table 2.In the table 2, the total amount that T2 tower water inlet expression enters the recirculated water and the fresh supplemented water of first azeotropy rectification column; T3 tower water inlet expression enters the total amount of recirculated water and the fresh supplemented water of the second azeotropy rectification column T3, but does not comprise the water of bringing in the discharging of T2 cat head oil phase among the second azeotropy rectification column T3.In following embodiment and the Comparative Examples too.
Table 2
Comparative Examples 1
The preparation method of the sec-butyl acetate of prior art is adopted in this Comparative Examples explanation
Method according to embodiment 1 prepares sec-butyl acetate, different is, adopt different reactive systems: (method according to the disclosed embodiment 1 of CN1781598A prepares with 400 gram resin assembling Tricesium dodecatungstophosphate salt catalysts, the assembling amount of phospho-wolframic acid cesium salt is 19.8 weight %) among the first fixed-bed reactor a1 that packs into, and other fixed-bed reactor are broken from reactive system with other pipe, be equivalent to four fixed-bed reactor like this and only use first fixed-bed reactor, and the total amount of the catalyzer of packing into is constant.Acetate is fed among the first fixed-bed reactor a1 C so that the speed of 1093 Grams Per Hours is continuous
4Alkene mixture (quality group becomes: normal butane 36.2%, anti-butylene 39.5%, n-butene 4.2%, maleic 20.1%) enters among the first fixed-bed reactor a1 acetate and C with the speed of 800 Grams Per Hours
4The mol ratio of the total amount of alkene mixture is 2.Feeding temperature in the fixed-bed reactor chuck is 80 ℃ of recirculated water control reaction temperature, is 1.5MPa by back pressure valve with the pressure-controlling of system.The question response situation stablize constant after, analyze by the six-way valve on-line sampling.Reaction was carried out 1000 hours continuously.
Operation result shows that behind system stability, the vertex temperature of fixed-bed reactor bed reaches 98 ℃.The result calculates according to fixed-bed reactor outlet product analysis: the total conversion rate of alkene is 75.5%, and conversion of olefines is that the selectivity of second 2-butyl acetate is 96.5%, and butylene is converted into C
8The selectivity of hydrocarbon is 3.1%, and conversion of olefines is greater than C
8The heavy hydrocarbon selectivity be 0.4%.Turned round 1000 hours, olefin conversion drops to 65.3%.
Comparing result explanation by this step, adopt the single fixed-bed reactor of prior art, alkene is sectional feeding not, the fixed-bed reactor temperature rise is big, is easy to generate focus, causes the generation of superimposed product, reaction preference is poor, catalyst activity reduction is very fast, and under the carboxylic acid situation identical with the ratio of alkene, olefin conversion reduces by 10% than the present invention.
Comparative Examples 2
The preparation method of the sec-butyl acetate of prior art is adopted in this Comparative Examples explanation
Method according to embodiment 1 prepares sec-butyl acetate, adopts the tripping device identical with embodiment 1, and the identical tower T2 of employing and embodiment 1, and different is to have only tower T2 as azeotropy rectification column, but only consider the azeotropic of sec-butyl acetate and water, and do not consider C
8The azeotropic of alkene, and tower T3 is as rectifying tower, and do not add entry among the rectifying tower T3. flow, composition and the content that enters the charging of tower T2 and water inlet all with embodiment 1 in identical .T4 tower do not put into operation.
Under the stable operational condition shown in the table 3, charging and water inlet are carried out continuous azeotropic distillation in the first azeotropy rectification column T2.Obtain acetate from the bottom of the first azeotropy rectification column T2, obtain sec-butyl acetate from the bottom of rectifying tower T3, the material of each sampling point of sampling analysis is formed, and the results are shown in Table 3.
Under the stable azeotropic operational condition shown in the table 3, continuous azeotropic distillation is carried out in charging and water inlet in azeotropy rectification column T2.Obtain acetate from the bottom of azeotropy rectification column T2, obtain sec-butyl acetate from the bottom of rectifying tower T3, the material of each sampling point of sampling analysis is formed, and the results are shown in Table 4.
Table 3
Table 4
From above-mentioned correlated sepn process and test result as can be seen, compared with prior art, adopt the purity of resulting acetate of method of the present invention and sec-butyl acetate higher, and isolating efficient is higher.
Embodiment 2
Present embodiment is used to illustrate the preparation method of sec-butyl acetate provided by the invention
Respectively packing in four fixed-bed reactor, (sulfonated phenylethylene-Vinylstyrene type resin, total exchange capacity is 5.0mmolH to 100 gram strongly acidic ion-exchange resin catalysts
+/ g, bulk density are 700g/L, specific surface area 40m
2/ g, mean pore size 30nm, pore volume 0.4mL/g), acetate is fed among the first fixed-bed reactor a1 C so that the speed of 893 Grams Per Hours is continuous
4(quality group becomes alkene mixture: Trimethylmethane 38.5%, normal butane 9.4%, anti-butylene 20.1%, n-butene 17.5%, iso-butylene 0.5%, maleic 13.7%, divinyl 0.3%) divide four stocks not enter among the first fixed-bed reactor a1, the second fixed-bed reactor a2, the 3rd fixed-bed reactor a3 and the 4th fixed-bed reactor a4 C with the speed of 240 Grams Per Hours, 240 Grams Per Hours, 160 Grams Per Hours, 160 Grams Per Hours
4The total feed of alkene mixture is 800 Grams Per Hours, acetate and C
4The mol ratio of the total amount of alkene mixture is 2.Feeding temperature in reactor jacket is 80 ℃ of recirculated water control reaction temperature, by the pressure 1.5MPa of back pressure valve Controlling System.The question response situation stablize constant after, the vertex temperature of fixed-bed reactor bed is respectively: a1:84 ℃, a2:83 ℃, a3:82 ℃, a4:82 ℃.The result calculates according to the 4th fixed-bed reactor a4 outlet product analysis: the total conversion rate of butylene is 76.8%, and the selectivity that butylene is converted into sec-butyl acetate is 95.8%, and butylene is converted into C
8The selectivity of superimposed alkene is 2.5%, and the selectivity that is converted into sec-butyl alcohol is 1.5%, is converted into greater than C
8The selectivity of heavy hydrocarbon be 0.2%.
The reaction product of the outlet extraction of the 4th fixed-bed reactor a4 is fed first rectifying tower (take off C
4Rectifying tower) carry out rectifying separation among the T1, the operational condition of T1 comprises working pressure 0.5MPa, and tower top temperature is 50 ℃, and tower still temperature is 160 ℃, and reflux ratio is 1, and theoretical plate number is 20.From cat head extraction C
4Light constituent.
First rectifying tower (takes off C
4Rectifying tower) bottom product of extraction feeds continuously among the first azeotropy rectification column T2 with the water as entrainer and carries out azeotropic distillation at the bottom of the T1 tower, the operational condition of T2 comprises that working pressure is normal pressure (0.1MPa), tower top temperature is 84 ℃, and tower still temperature is 150 ℃, and reflux ratio is 3.The first azeotropy rectification column T2 total filler height 2.5m, theoretical plate number is 50, feed entrance point: 1.5m (apart from the filler bottom), bottom side line position: 0.4m (apart from the filler bottom).
Feeding second azeotropy rectification column (thick ester azeotropic treating tower) T3 by the overhead product of the first azeotropy rectification column T2 cat head extraction continuously with the water as entrainer, to carry out azeotropic distillation refining, the operational condition of T3 comprises that working pressure is normal pressure (0.1MPa), tower top temperature is 80 ℃, tower still temperature is 135 ℃, and reflux ratio is 25.Obtain light constituent by cat head, (the second azeotropy rectification column T3 total filler height 3m, theoretical plate number is 60, feed entrance point: 2m (apart from the filler bottom), survey line position, bottom: 0.5m (apart from the filler bottom) to obtain the sec-butyl acetate product by the tower still.
Enter among acetate decationized Y sieve and the high boiling material tower T4 by the bottom product of extraction at the bottom of the first azeotropy rectification column T2 tower and to carry out rectifying, the operational condition of T4 comprises working pressure normal pressure (0.1MPa), and tower top temperature is 118 ℃, and tower still temperature is 154 ℃, reflux ratio is 0.8, and the theoretical plate number of T4 is 20.Behind the system stability, each logistics is formed as shown in table 5.
Table 5
Embodiment 3
Present embodiment is used to illustrate the preparation method of sec-butyl acetate provided by the invention
The silicon dioxide carried phospho-wolframic acid cesium salt (Cs of 100 grams respectively packs in four fixed-bed reactor
2.5H
0.5PW
12O
40/ SiO
2) catalyzer (Cs
2.5H
0.5PW
12O
40Content be 40 weight % of catalyzer total amount), acetate is added to first fixed-bed reactor, C continuously with the speed of 1093 Grams Per Hours
4(quality group becomes alkene mixture: Trimethylmethane 38.5%, normal butane 9.4%, anti-butylene 20.1%, n-butene 17.5%, iso-butylene 0.5%, maleic 13.7%, divinyl 0.3%) divide four stocks not enter among the first fixed-bed reactor a1, the second fixed-bed reactor a2, the 3rd fixed-bed reactor a3 and the 4th fixed-bed reactor a4 C with the speed of 117 Grams Per Hours, 118 Grams Per Hours, 78 Grams Per Hours, 78 Grams Per Hours
4The total feed of alkene mixture is 391 Grams Per Hours, acetate and C
4The total mol ratio of alkene is 5.Feeding temperature in the fixed-bed reactor chuck is 100 ℃ of circulating heat conductions oil control reaction temperature, is 2MPa by back pressure valve with the pressure-controlling of system.The question response situation is stablized constant back (about 10 hours), analyzes by the six-way valve on-line sampling.Behind system stability, the vertex temperature of fixed-bed reactor bed is respectively: a1 is that 103 ℃, a2 are that 102 ℃, a3 are that 101 ℃, a4 are 101 ℃.The result calculates according to the 4th fixed-bed reactor outlet product analysis: the total conversion rate of butylene is 90.5%, and the selectivity that butylene is converted into sec-butyl acetate is 96.4%, and butylene is converted into C
8The selectivity of superimposed hydrocarbon is 0.7%, and the selectivity that is converted into sec-butyl alcohol is 2.9%, does not detect greater than C
8Heavy hydrocarbon.
The reaction product of the outlet extraction of the 4th fixed-bed reactor a4 is fed first rectifying tower (take off C
4Rectifying tower) carry out rectifying separation among the T1, the operational condition of T1 comprises working pressure 0.25MPa, and tower top temperature is 40 ℃, and tower still temperature is 180 ℃, and reflux ratio is 0.8, and theoretical plate number is 20.From cat head extraction C
4Light constituent.
First rectifying tower (takes off C
4Rectifying tower) bottom product of extraction feeds continuously among the first azeotropy rectification column T2 with the water as entrainer and carries out azeotropic distillation at the bottom of the T1 tower, the operational condition of T2 comprises that working pressure is normal pressure (0.1MPa), tower top temperature is 94 ℃, and tower still temperature is 135 ℃, and reflux ratio is 2.The first azeotropy rectification column T2 total filler height 2.5m, theoretical plate number is 50, feed entrance point: 1.5m (apart from the filler bottom), bottom side line position: 0.4m (apart from the filler bottom).
Feeding second azeotropy rectification column (thick ester azeotropic treating tower) T3 by the overhead product of the first azeotropy rectification column T2 cat head extraction continuously with the water as entrainer, to carry out azeotropic distillation refining, the operational condition of T3 comprises that working pressure is normal pressure (0.1MPa), tower top temperature is 83 ℃, tower still temperature is 122 ℃, reflux ratio is 10. to obtain light constituent by cat head, obtain the sec-butyl acetate product by the tower still. the second azeotropy rectification column T3 total filler height 3m, theoretical plate number is 60, feed entrance point: 2m (apart from the filler bottom), bottom side line position: 0.5m (apart from the filler bottom).
Enter among acetate decationized Y sieve and the high boiling material tower T4 by the bottom product of extraction at the bottom of the first azeotropy rectification column T2 tower and to carry out rectifying, the operational condition of T4 comprises working pressure normal pressure (0.1MPa), and tower top temperature is 117 ℃, and tower still temperature is 150 ℃, reflux ratio is 0.5, and theoretical plate number is 20.Behind the system stability, each logistics is formed as shown in table 6.
Table 6
Embodiment 4
Present embodiment is used to illustrate the preparation method of sec-butyl acetate provided by the invention
Method according to embodiment 1 prepares sec-butyl acetate, and different is, in reactive system:
Respectively packing in four fixed-bed reactor, (sulfonated phenylethylene-Vinylstyrene type resin, total exchange capacity is 5.0mmolH to 100 gram strongly acidic ion-exchange resin catalysts
+/ g, bulk density are 700g/L, specific surface area 40m
2/ g, mean pore size 30nm, pore volume 0.4mL/g), Glacial acetic acid is added in first fixed-bed reactor C continuously with the speed of 476 Grams Per Hours
4(quality group becomes mixture: normal butane 36.2 weight %, anti-butylene 39.5 weight %, n-butene 4.2 weight %, maleic 20.1 weight %) divide four stocks not enter among the first fixed-bed reactor a1, the second fixed-bed reactor a2, the 3rd fixed-bed reactor a3 and the 4th fixed-bed reactor a4 C with the speed of 275 Grams Per Hours, 275 Grams Per Hours, 161 Grams Per Hours, 161 Grams Per Hours
4The total feed of alkene mixture is 872 Grams Per Hours, acetate and C
4The total mol ratio of alkene is that to feed temperature in the fixed-bed reactor chuck be 90 ℃ of recirculated water control reaction temperature to 0.8., by back pressure valve with the pressure-controlling of system be 2MPa. question response situation stablize constant after, analyze by the six-way valve on-line sampling. behind system stability, the vertex temperature of fixed-bed reactor bed is respectively: first fixed-bed reactor are 92 ℃, second fixed-bed reactor are 91 ℃, the 3rd fixed-bed reactor are 90 ℃, the 4th fixed-bed reactor are 90 ℃. the result calculates according to the 4th fixed-bed reactor outlet product analysis: the total conversion rate of alkene is 72.0%, conversion of olefines is that the selectivity of sec-butyl acetate is 97.0%, and conversion of olefines is C
8The selectivity of hydrocarbon is 2.5%, and conversion of olefines is greater than C
8The selectivity of heavy hydrocarbon be 0.5%.
Claims (9)
1. the preparation method of a sec-butyl acetate, this method comprises:
(1) in the presence of catalyzer and under the addition reaction condition, with C
4Alkene contacts, reacts with acetate several times;
(2) under the rectifying condition, step (1) gained reaction product is carried out rectifying separation in first rectifying tower, from cat head extraction C
4Light constituent, extraction bottom product at the bottom of the tower, this bottom product contains sec-butyl acetate, C
8Alkene and unreacted acetate;
(3) under the azeotropic distillation condition, what make that step (2) obtains contains sec-butyl acetate, C
8The bottom product of alkene and unreacted acetate and water enter and carry out azeotropic distillation in first azeotropy rectification column, and the amount that enters the described water in first azeotropy rectification column can make sec-butyl acetate and C
8Alkene with the form of azeotrope from the cat head extraction, acetate extraction at the bottom of the tower;
(4) azeotrope that step (3) is obtained carries out oily water separation after condensation, obtains water-phase product and contains C
8The oil-phase product of alkene and sec-butyl acetate;
(5) under the azeotropic distillation condition, oil-phase product that step (4) is obtained and water enter and carry out azeotropic distillation in second azeotropy rectification column, and the amount that enters the described water in second azeotropy rectification column can make C
8Alkene with the form of azeotrope from the cat head extraction, sec-butyl acetate extraction at the bottom of the tower;
Described C
4The method that alkene contacts with acetate several times comprises acetate and portion C
4Alkene contact, reaction are then with rest part C
4Alkene once or several times again with acetate and portion C
4Product contact, the reaction of alkene contact, reaction back gained.
2. method according to claim 1, wherein, described C
4The adjacent time that contacts for twice with acetate of alkene is 5-200 minute.
3. method according to claim 1, wherein, described C
4The number of times that alkene contacts, reacts with acetate is 2-10 time, at every turn the C that contacts, reacts with acetate
4The consumption of alkene and described C
4The weight ratio of total consumption of alkene is 0.05-0.9.
4. method according to claim 1 wherein, also contains sec-butyl alcohol in the bottom product that step (2) obtains; The amount that enters the described water in first azeotropy rectification column in the step (3) can also make sec-butyl alcohol with the cat head extraction from first azeotropy rectification column of the form of azeotrope, this azeotrope is carried out also contain sec-butyl alcohol in the oil-phase product of gained after the oily water separation after condensation; The amount that enters the described water of second azeotropy rectification column in the step (5) can also make sec-butyl alcohol with the form of azeotrope from the second azeotropic distillation cat head extraction.
5. according to claim 1 or 4 described methods, wherein, in step (3), the amount that enters the described water in first azeotropy rectification column makes the water content of the acetate that obtains at the bottom of the tower not be higher than 1 weight %.
6. according to claim 1 or 4 described methods, wherein, in the step (3), the amount that enters the described water in first azeotropy rectification column adopts following formula to calculate:
W1＝W1’×(1±A)
Wherein, W1 is amount or the flow that enters the described water in first azeotropy rectification column in the step (3), represents that with weight or weight rate dimension is identical with W1 ';
A is 0-10%;
W1’＝F1×[X2×15/85+X3×32/45+(X1-X3×23/45)×19.5/80.5]，
F1 is amount or the flow that enters the described bottom product in first azeotropy rectification column, represents with weight or weight rate;
X1 is the quality percentage composition of sec-butyl acetate in the described bottom product that enters in first azeotropy rectification column;
X2 is C in the described bottom product that enters in first azeotropy rectification column
8The quality percentage composition of alkene;
X3 is the quality percentage composition of sec-butyl alcohol in the described bottom product that enters in first azeotropy rectification column.
7. according to claim 1 or 4 described methods, wherein, in the described step (5), the amount that enters the described water in second azeotropy rectification column adopts following formula to calculate:
W2＝W2’×K
Wherein, W2 is amount or the flow that enters water described in described second azeotropy rectification column in the step (5), represents that with weight or weight rate dimension is identical with W2 ';
K is 1-2;
W2’＝F2×[X22×15/85+X33×32/45]，
F2 is amount or the flow that enters the oil-phase product in second azeotropy rectification column, represents with weight or weight rate;
X22 is C in the oil-phase product that enters in second azeotropy rectification column
8The quality percentage composition of alkene;
X33 is the quality percentage composition of sec-butyl alcohol in the oil-phase product that enters in second azeotropy rectification column.
8. according to claim 1 or 4 described methods, wherein, entering each position between opening for feed to the first block column plate of described first azeotropy rectification column and second azeotropy rectification column of water that enters described second azeotropy rectification column in the water of described first azeotropy rectification column and the step (5) in the step (3) enters.
9. method according to claim 1, wherein, this method comprises that also the positively charged ion that removes in the acetate that step (3) obtains and/or high boiling material and circulation are used for step (1).
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| CN102234230A (en) * | 2010-05-05 | 2011-11-09 | 北京石油化工学院 | Process method for synthesizing sec-butyl acetate from C4 fractions |
| CN103420831B (en) * | 2012-05-23 | 2015-12-16 | 北京安耐吉能源工程技术有限公司 | A kind of production method of acetic ester |
| CN103508884B (en) * | 2012-06-15 | 2015-09-16 | 中国石油化工股份有限公司 | One utilizes C after ether 4cut prepares the method for 2-butyl acetate |
| CN103724194A (en) * | 2012-10-16 | 2014-04-16 | 中国石油化工股份有限公司 | Method for preparing acetic acid sec-pentyl ester |
| CN102964243B (en) * | 2012-11-16 | 2017-07-11 | 北京石油化工学院 | The preparation method of sec-Butyl Acetate |
| CN104649902B (en) * | 2013-11-19 | 2016-05-11 | 中国石油天然气股份有限公司 | Production method of sec-butyl acetate |
| CN103980115B (en) * | 2014-06-03 | 2015-08-19 | 湖南瑞源石化股份有限公司 | A kind of method reclaiming sec-butyl acetate with high yield from the reaction product preparing sec-butyl acetate |
| CN104109088B (en) * | 2014-06-23 | 2016-08-17 | 山东胜通集团股份有限公司 | Sec-Butyl Acetate production line |
| CN105985239B (en) * | 2015-01-27 | 2019-03-12 | 中国石油天然气股份有限公司 | Method and device for synthesizing sec-butyl acetate |
| CN106631801B (en) * | 2015-10-31 | 2019-07-05 | 湖南中创化工股份有限公司 | A kind of method and device for using methanol as impurity in the secondary butyl ester of entrainer separating acetic acid |
| CN106631798B (en) * | 2015-10-31 | 2019-07-05 | 湖南中创化工股份有限公司 | It is a kind of to use methanol as the method and device of impurity in the secondary butyl ester of entrainer separating acetic acid with solvent recovering system |
| CN105693513B (en) * | 2016-04-13 | 2018-03-30 | 岳阳富和科技有限公司 | A kind of method of the secondary butyl ester of three-phase azeotropic distillation separating acetic acid and C8 hydrocarbon mixtures |
| CN109485548B (en) * | 2017-09-13 | 2022-01-07 | 湖南中创化工股份有限公司 | Method and device for preparing and separating sec-butyl alcohol by hydrolyzing sec-butyl acetate |
| CN113717051B (en) * | 2021-09-16 | 2023-08-04 | 泰兴金江化学工业有限公司 | Preparation method of butyl acetate |
| CN113880712B (en) * | 2021-09-16 | 2023-08-04 | 泰兴金江化学工业有限公司 | Preparation method of ethyl acetate |
| CN114917607B (en) * | 2022-06-06 | 2024-04-19 | 大连理工大学成都研究院 | A purification system and method for ethyl tetrahydrofurfuryl ether |
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