CN1224621C - Tetrahydrofuran refining process - Google Patents
Tetrahydrofuran refining process Download PDFInfo
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- CN1224621C CN1224621C CN 02128234 CN02128234A CN1224621C CN 1224621 C CN1224621 C CN 1224621C CN 02128234 CN02128234 CN 02128234 CN 02128234 A CN02128234 A CN 02128234A CN 1224621 C CN1224621 C CN 1224621C
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- tetrahydrofuran
- thf
- water
- dihydrofuran
- cat head
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 title claims abstract description 595
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 title claims abstract description 298
- 238000000034 method Methods 0.000 title claims abstract description 34
- 238000007670 refining Methods 0.000 title abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 116
- JKTCBAGSMQIFNL-UHFFFAOYSA-N 2,3-dihydrofuran Chemical compound C1CC=CO1 JKTCBAGSMQIFNL-UHFFFAOYSA-N 0.000 claims abstract description 66
- 238000006703 hydration reaction Methods 0.000 claims abstract description 38
- 150000001299 aldehydes Chemical class 0.000 claims abstract description 37
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 27
- JNODDICFTDYODH-UHFFFAOYSA-N 2-hydroxytetrahydrofuran Chemical compound OC1CCCO1 JNODDICFTDYODH-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 18
- 239000007864 aqueous solution Substances 0.000 claims abstract description 14
- 239000000243 solution Substances 0.000 claims abstract description 14
- 230000036571 hydration Effects 0.000 claims abstract description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 65
- 238000004821 distillation Methods 0.000 claims description 57
- 241000282326 Felis catus Species 0.000 claims description 47
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 25
- 229910052799 carbon Inorganic materials 0.000 claims description 23
- 239000002253 acid Substances 0.000 claims description 22
- 239000003729 cation exchange resin Substances 0.000 claims description 20
- 230000018044 dehydration Effects 0.000 claims description 18
- 238000006297 dehydration reaction Methods 0.000 claims description 18
- 239000012295 chemical reaction liquid Substances 0.000 claims description 17
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 12
- 238000000746 purification Methods 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- 229920000728 polyester Polymers 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 239000008213 purified water Substances 0.000 claims description 2
- 239000006227 byproduct Substances 0.000 claims 1
- 239000003456 ion exchange resin Substances 0.000 abstract description 8
- 229920003303 ion-exchange polymer Polymers 0.000 abstract description 8
- 238000009835 boiling Methods 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 5
- 230000002378 acidificating effect Effects 0.000 abstract description 2
- 125000004432 carbon atom Chemical group C* 0.000 abstract 1
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 26
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 24
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 20
- 239000007788 liquid Substances 0.000 description 15
- 238000010992 reflux Methods 0.000 description 15
- 239000012530 fluid Substances 0.000 description 14
- 239000000463 material Substances 0.000 description 14
- 239000000203 mixture Substances 0.000 description 14
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 12
- KKEYFWRCBNTPAC-UHFFFAOYSA-N benzene-dicarboxylic acid Natural products OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 8
- 230000032050 esterification Effects 0.000 description 7
- 238000005886 esterification reaction Methods 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 6
- 238000011049 filling Methods 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- -1 terephthalic acid ester Chemical class 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 5
- 230000032696 parturition Effects 0.000 description 5
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 3
- 239000000052 vinegar Substances 0.000 description 3
- 235000021419 vinegar Nutrition 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 2
- AIJULSRZWUXGPQ-UHFFFAOYSA-N Methylglyoxal Chemical compound CC(=O)C=O AIJULSRZWUXGPQ-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 2
- JJHPQGFGFRPCCH-UHFFFAOYSA-N acetic acid;butane Chemical compound CCCC.CC(O)=O JJHPQGFGFRPCCH-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 150000002240 furans Chemical class 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920001083 polybutene Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000003190 augmentative effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 229940023913 cation exchange resins Drugs 0.000 description 1
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 1
- 238000006210 cyclodehydration reaction Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
There is disclosed a refining process for recovering highly pure tetrahydrofuran (THF) from a hydrous tetrahydrofuran containing dihydrofuran and aldehydes having carbon atoms less than 3. This method for purifying the tetrahydrofuran (THF) comprises bringing the hydrous tetrahydrofuran into contact with a strongly acidic ion exchange resin to transform dihydrofuran contained therein into hydroxytetrahydrofuran, higher boiling separation distilling and lower boiling separation distilling the hydration product solution to form a tetrahydrofuran aqueous solution, and then distilling the hydrogenation product to remove water by an azeotrope together with THF and simultaneously obtain the purified THF as a bottom product.
Description
Technical field
The present invention relates to contain the process for purification of the water-containing tetrahydrofuran of dihydrofuran and the aldehydes of carbon number below 3.Especially the present invention relates to by 1,4-butyleneglycol and aromatic dicarboxylic acid or its reactive derivatives are made in the process of polyester, the method for effectively refining secondary water-containing tetrahydrofuran of giving birth to.
Technical background
As the method for making of tetrahydrofuran (THF), the known shortening, 1 that furans is arranged, the cyclodehydration of 4-butyleneglycol, two acetic acid butane take off several methods such as ester cyclisation.Utilize these methods to obtain generally containing in the tetrahydrofuran (THF) aldehydes etc. of dihydrofuran, so only the method for these foreign material is removed in research.For example, put down in writing in the special fair 6-29280 communique and utilize the ester cyclisation of taking off of two acetic acid butane to obtain the PURIFICATION OF TETRAHYDROFURAN method.Contain foreign material such as dihydrofuran, butyraldehyde and acetic acid, water in this tetrahydrofuran (THF),, make dihydrofuran convert hydroxyl tetrahydrofuran and acetoxy group tetrahydrofuran (THF) to so it is contacted with storng-acid cation exchange resin.Conversion reaction liquid is distilled, and the hydroxyl tetrahydrofuran of generation and acetoxy group tetrahydrofuran (THF) go out from tower bottom flow with water and acetic acid.From cat head and less water while distilled tetrahydrofuran (THF), in the presence of ruthenium catalyst, carry out hydrogenation, after the butyraldehyde that will contain converted butanols to, distillation made water and tetrahydrofuran (THF) azeotropic, distillates from cat head, and the tetrahydrofuran (THF) that contains butanols goes out from tower bottom flow.With this tetrahydrofuran (THF) distillation, distillate the purified tetrahydrofuran (THF) at last from cat head.Thinking this method, when main foreign material are dihydrofuran and butyraldehyde, is a kind of good process for purification.
Recently, widely know as polybutene terephthalic acid ester, with 1, the 4-butyleneglycol as main carboxylic acid, can increase the production of polyester with terephthalic acid as main pure composition, follows secondary tetrahydrofuran aqueous solution amount of giving birth to also to increase therewith.In this secondary tetrahydrofuran aqueous solution of giving birth to, contain the dihydrofuran of a great deal of, in addition, also contain carbon numbers such as acetaldehyde, pyruvic aldehyde, propenal at the aldehydes below 3.Contain the tetrahydrofuran (THF) of these foreign material, purposes significantly is restricted.For example, during the poly-tetramethylene ether ethylene glycol of the manufacturing of one of main application of tetrahydrofuran (THF), use when containing the tetrahydrofuran (THF) of above-mentioned aldehydes, can cause that acid value rises and painted etc., can not be used as the raw material of resin and fiber.Therefore, the method for these aldehydes is removed in research always for many years.For example, the spy opens and has put down in writing in the clear 56-104881 communique with behind the secondary living tetrahydrofuran aqueous solution of alkalimetal oxide processing, carries out the distillatory method again.The spy opens and has put down in writing with behind the secondary living tetrahydrofuran aqueous solution of alkali metal borohydride processing redistilled method in the clear 57-154179 communique.Yet these chemical treatments are quite complicated, so require a kind of these chemically treated secondary PURIFICATION OF TETRAHYDROFURAN methods of giving birth to that do not need.Therefore, the invention provides a kind of from polybutene terephthalic acid ester manufacturing processed secondary give birth to, contain in the water-containing tetrahydrofuran of dihydrofuran and the aldehydes of carbon number below 3, do not carry out the processing of alkali metal hydroxide and alkali metal borohydride, just can remove the method for these foreign material.
Summary of the invention
According to the present invention,, after carrying out following operation (I) and operation (II),, can make with extra care out water-containing tetrahydrofuran at an easy rate by carrying out operation (III) for the water-containing tetrahydrofuran that contains dihydrofuran and the aldehydes of carbon number below 3.
Operation (I): water-containing tetrahydrofuran is contacted with storng-acid cation exchange resin, after converting the dihydrofuran in the tetrahydrofuran (THF) to hydroxyl tetrahydrofuran, with the distillation of conversion reaction liquid, the aqueous solution that contains hydroxyl tetrahydrofuran goes out from tower bottom flow, and tetrahydrofuran (THF) distillates from cat head with water.
Operation (II): with water-containing tetrahydrofuran distill, the aldehydes of carbon number below 3 heat up in a steamer from cat head with a part of tetrahydrofuran (THF), remaining tetrahydrofuran (THF) goes out from tower bottom flow with water.
Operation (III): the water-containing tetrahydrofuran that will reduce dihydrofuran and carbon number 3 following aldehydes concentration distills, and water and tetrahydrofuran (THF) distillate from cat head with azeotrope, and the tetrahydrofuran (THF) of dehydration goes out from tower bottom flow.
In the present invention, preferably carry out operation (I) after, carry out operation (II) again, if requirement is arranged, also can order transposing.By the reaction of dihydrofuran to hydroxyl tetrahydrofuran conversion, owing to be balanced reaction from dihydrofuran to the conversion reaction of hydroxyl tetrahydrofuran, institute preferably carries out several operation (I) when containing a large amount of dihydrofuran in the purified water-containing tetrahydrofuran.This situation also can be carried out operation (I) continuously, also can carry out operation (I) after, carry out operation (II), carry out operation (I) again.In operation (I),, can return in the distillation tower of operation (I) with after storng-acid cation exchange resin contacts from cat head distilled water-containing tetrahydrofuran to major general's part, rest parts is fed in the operation (II).At this moment, when carrying out operation (I) repeatedly, preferably directly return to the distillation of operation (I).Dehydration tetrahydrofuran (THF) redistillation with obtaining in the operation (III) can distillate more purified tetrahydrofuran (THF) from cat head.
According to the present invention, between above-mentioned operation (I) and operation (II) and operation (III), utilization contains the process for purification of each operation of following operation (IV) and operation (V), by by containing, 1, the water-containing tetrahydrofuran that takes off acetic acid cyclisation generation and the water-containing tetrahydrofuran (A) that contains dihydrofuran and carbon number 3 following aldehyde of the solution of 4-butyleneglycol monoacetate can be obtained highly purified tetrahydrofuran (THF) at an easy rate.
Operation (IV): by containing 1, the solution of 4-butyleneglycol list second vinegar ester take off the acetic acid cyclisation, the water-containing tetrahydrofuran that obtains containing acetic acid etc. is distilled, will be moisture and the tetrahydrofuran (THF) (water-containing tetrahydrofuran (B)) of acetic acid and mix through the water-containing tetrahydrofuran that operation (I) and operation (II) obtain from the cat head distilled, contact with storng-acid cation exchange resin, make contained dihydrofuran and hydroxyl tetrahydrofuran carry out hydration, the hydration reaction liquid that obtains is distilled, distillate tetrahydrofuran (THF) from cat head.
Operation (V): the water-containing tetrahydrofuran that operation (IV) is obtained is fed in the hydrogenation reaction, converts the butyraldehyde-n in the tetrahydrofuran (THF) to propyl carbinol.
The working of an invention form
Among the present invention, as refining to as if contain dihydrofuran and carbon number 3 following aldehydes water-containing tetrahydrofuran (A) as foreign material.For example making 1, the 4-butyleneglycol as secondary water-containing tetrahydrofuran of giving birth in the polyester process of main dicarboxylic acid composition, is best object of the present invention with terephthalic acid one class aromatic dicarboxylic acid as main diol component.This water-containing tetrahydrofuran, according to reaction conditions, but tetrahydrofuran (THF) concentration is that 10～50% (weight % when % and ppm do not have specified otherwise in this manual, is benchmark with weight.) as foreign material.According to circumstances, contain the dihydrofuran of 10～thousands of ppm, aldehydes and the alcohols of carbon number below 3 of 10～1000ppm.
Among the present invention, for dihydrofuran, being to convert thereof into hydroxyl tetrahydrofuran, again with the tetrahydrofuran (THF) fractionation by distillation, for aldehydes, is the distillation by high reflux ratio, with the tetrahydrofuran (THF) fractionation by distillation.Usually, after carrying out removing dihydrofuran 1 time at least, remove aldehydes again.Why is it?, this is because when removing dihydrofuran, has the water of a great deal of also to remove simultaneously, can reduce the amount of supplying with the water-containing tetrahydrofuran of removing aldehydes.
Operation (I) (removing the operation of dihydrofuran)
Water-containing tetrahydrofuran is contacted with storng-acid cation exchange resin, after converting the dihydrofuran in the tetrahydrofuran (THF) to hydroxyl tetrahydrofuran, conversion reaction liquid is distilled, and the aqueous solution of hydroxyl tetrahydrofuran (THF) is gone out by tower bottom flow, and tetrahydrofuran (THF) heats up in a steamer from cat head with water.
The removal of dihydrofuran, according to the method for putting down in writing in the fair 6-29289 communique of spy, water-containing tetrahydrofuran is contacted with storng-acid cation exchange resin,, preferably use the sulfonated bodies of general vinylbenzene-divinylbenzene crosslink multipolymer as storng-acid cation exchange resin.For example can use (Di Aweng ion exchange resin are the registered trademarks of Mitsubishi chemical Co., Ltd) such as the Di Aweng ion exchange resin SKIB that buys easily on the market, SK104, SK112, PK208, PK212, PK228.Usually, by making under 20～80 ℃ of the water-containing tetrahydrofurans with LHSV (liquid superficial velocity) 0.01～5hr
-1By having filled the reaction tower of these storng-acid cation exchange resins, make dihydrofuran convert hydroxyl tetrahydrofuran to.
Conversion reaction liquid is distilled, and the hydroxyl tetrahydrofuran of most of water and generation goes out from tower bottom flow, and the tetrahydrochysene furan food in one's mouth is made azeotrope with water and distillated from cat head.The distillation tower of 20～40 grades of theoretical stages is used in this distillation, and under the normal pressure, 90～110 ℃ of column bottom temperatures distill with 0.5～3.0 reflux ratio.
Utilizing the reaction of the hydration generation hydroxyl tetrahydrofuran of dihydrofuran is balanced reaction, so, when the dihydrofuran amount is a lot of in the water-containing tetrahydrofuran of supply hydration reaction, the water-containing tetrahydrofuran that obtains from cat head, contain the above dihydrofuran of allowance sometimes.In this case, carry out above-mentioned storng-acid cation exchange resin processing and distillation repeatedly.Supply with the moisture concentration of the water-containing tetrahydrofuran of storng-acid cation exchange resin processing, even 5%, conversion reaction still can fully carry out, but usually, in above-mentioned distillation, to be taken as 10% from the water content of cat head distilled water-containing tetrahydrofuran, preferably, distill again by behind the reaction tower of having filled storng-acid cation exchange resin.If requirement to some extent, this storng-acid cation exchange resin is once more handled and/or distillation, also can carry out after utilizing following distillation to remove aldehydes again.
In operation (I), make two distillation tower cat head distilled water-containing tetrahydrofurans, contact with storng-acid cation exchange resin, when the conversion reaction liquid foldback that obtains being returned in the distillation tower of operation (I), return ratio, can set arbitrarily according to the concentration that contacts dihydrofuran in the reaction solution that obtains with storng-acid cation exchange resin.Usually return 20～80 weight % of reaction solution, best 30～70 weight %.When this returns ratio and is less than 20 weight %, utilize the effect of implementing this processing to be easy to become insufficient, on the other hand, when surpassing 80 weight %, the distillation tower of operation (I) load increases, and is very uneconomical.
Operation (II) (removing the operation of aldehyde)
Water-containing tetrahydrofuran is distilled, and carbon number 3 following aldehydes and a part of tetrahydrofuran (THF) distillate from cat head simultaneously, and the tetrahydrofuran (THF) of water and other parts goes out from tower bottom flow together.
Among the present invention, from water-containing tetrahydrofuran, remove carbon number 3 following aldehydes, undertaken by distillation.Aldehydes distillates from cat head with the azeotrope of a small amount of tetrahydrofuran (THF)-water in this distillation, and remaining most of tetrahydrofuran (THF) and water go out from tower bottom flow.The distillation tower of 20～50 grades of theoretical stages is used in this distillation, is preferably in normal pressure, carries out under 60～90 ℃ of the column bottom temperatures.In this distillation,,, preferably distill with the high reflux ratio more than 100 so aldehydes can fully be removed because a spot of tetrahydrofuran (THF) distillates.Usually distill with 100～200 reflux ratio.
The tetrahydrofuran aqueous solution (A) that contains dihydrofuran and carbon number 3 following aldehydes, in above-mentioned operation (I) and operation (II), most of foreign material are removed, but still contain the water of a great deal of and the foreign material of trace.
Operation (III) (dehydration procedure)
To remove the water-containing tetrahydrofuran of dihydrofuran and carbon number 3 following aldehydes, infeed in the dehydration distillation tower, water and tetrahydrofuran (THF) distillate from cat head with azeotrope, and the tetrahydrofuran (THF) of dehydration goes out from tower bottom flow.As this dehydration distillation tower, use 10～20 grades of theoretical stages, and, be to add fortunately to depress operation, the tetrahydrofuran (THF)-water azeotrope of big flood ratio is distillated from cat head.For example, with 0.5～1.5Mpz, column bottom temperature 130-180 ℃, reflux ratio 0.1～1.0 is distilled.From cat head distilled tetrahydrofuran (THF)-water azeotrope,, also can be fed to dihydrofuran and remove in the distillation tower of operation if requirement is arranged.From the dehydration tetrahydrofuran (THF) that tower bottom flow goes out, can intactly supply with various uses usually.If when requiring more highly purified tetrahydrofuran (THF),, distillate from cat head and to obtain more purified tetrahydrofuran (THF) hydrogen furans with its further distillation.The not pure tetrahydrofuran that goes out from tower bottom flow for example, is also capable of circulationly removed distillation tower in the operation to dihydrofuran.For the distillation of high purityization, use theoretical stage 15-30 level, can be 60～120 ℃ of pressure 0.1～0.13Mpa, column bottom temperatures, reflux ratio is distilled for 0.1～1.5 time.
From the water-containing tetrahydrofuran (A) that contains dihydrofuran and carbon number 3 following aldehydes, reclaiming high-purity tetrahydrofuran, to contain 1 from containing simultaneously, 4-butyleneglycol monoacetate solution takes off when reclaiming high-purity tetrahydrofuran in the water-containing tetrahydrofuran of acetic acid cyclisation gained acetic acid, between operation (I) and operation (II) and operation (III), preferably carry out following operation (IV) and operation (V).
Operation (IV): will contain to containing 1, the water-containing tetrahydrofuran that 4-butyleneglycol list acetate fat liquid carries out depickling cyclisation gained acetic acid etc. distills, will be moisture and the tetrahydrofuran (THF) (water-containing tetrahydrofuran (B)) of acetic acid from the cat head distilled, mix with process operation (I) and operation (IV) gained water-containing tetrahydrofuran, contact with storng-acid cation exchange resin, make contained dihydrofuran and hydroxyl tetrahydrofuran carry out hydration, the hydration reaction liquid that obtains is distilled, and tetrahydrofuran (THF) distillates from cat head.
Operation (V): the water-containing tetrahydrofuran that obtains in the operation (IV) is infeeded in the hydrogenation reaction, make the n-butyraldehyde in the tetrahydrofuran (THF) convert the n-butanols to.
Operation (IV): in operation (IV), use 1,4-butyleneglycol list second vinegar ester takes off in the acetic acid cyclisation gained water-containing tetrahydrofuran, butyraldehyde-n and dihydrofuran contain 100～5000ppm and 10～500ppm respectively for tetrahydrofuran (THF).
Among the present invention, as operation (IV), the water-containing tetrahydrofuran that will contain this acetic acid etc. distills, and tetrahydrofuran (THF) is distillated by cat head with water and acetic acid, and 1, other high boiling product of 4-two acetoxy group butane goes out from tower bottom flow.In water-containing tetrahydrofuran (water-containing tetrahydrofuran (B)), contain other foreign material of acetic acid, dihydrofuran and butyraldehyde-n by recovered overhead.That is, this distillation is simple.
After the water-containing tetrahydrofuran that will reclaim through operation (I) and operation (II) and water-containing tetrahydrofuran (B) merging, contact, make contained dihydrofuran hydration become tetrahydrofuran (THF) with storng-acid cation exchange resin.This hydration reaction is with the same the carrying out of hydration reaction in the operation (I).This moisture tetrahydrochysene furan that reclaims through operation (I), (II) is fed, in operation (IV), carry out hydration reaction once more, its reason is, even the hydration reaction in operation (I) does not proceed to desired degree, as goods, stop the dihydrofuran of in the gained tetrahydrofuran (THF), sneaking into more than the allowance.Hydration reaction liquid is distilled, and tetrahydrofuran (THF) and a part of water distillate from cat head, and the remainder water that contains acetic acid and hydroxyl tetrahydrofuran goes out from tower bottom flow.
Operation (V):
In the distillation of hydration reaction liquid, the water-containing tetrahydrofuran that obtains from cat head, contain the unsaturated foreign material such as dihydrofuran of aldehyde and denier.Wherein main a kind of be n-butyraldehyde from water-containing tetrahydrofuran (B).Among the present invention, as operation (V), with the unsaturated link(age) of foreign material in this water-containing tetrahydrofuran, it is saturated to carry out hydrogenation.This hydrogenation reaction is with the reactor of aqueous tetrahydrofuran (THF) by the filling noble metal catalyst, to wherein infeeding hydrogen, is easy to carry out.As noble metal catalyst, the most handy is with precious metal carrier bands such as ruthenium, palladium, platinum to carriers such as activated carbon silica gel, sial, magnesium oxide, diatomite.Temperature of reaction is generally 30～200 ℃, and tetrahydrofuran (THF) is easy to the hydrogenation decomposition under the high temperature, and under the low temperature, speed of response is slow, so be preferably in 50～120 ℃ of following hydrogenation.Hydrogen pressure more than 0.1Mpa (gauge pressure), best 0.5～2Mpa (gauge pressure).As hydrogen, except pure hydrogen, also can use to contain rare gas element.Because supply with the tetrahydrofuran (THF) of hydrogenation reaction, be present in unsaturated compositions such as dihydrofuran in the tetrahydrofuran aqueous solution of raw material and carbon number 3 following aldehyde, major part is removed, so the main body of hydrogenation reaction is the propyl carbinol that butyraldehyde-n generates by hydrogenation, reaction is carried out easily.
Hydrogenation reaction solution distills in operation (III) after gas-liquid separation, and water that contains and part tetrahydrofuran (THF) distillate from cat head with azeotrope, obtains the high-purity tetrahydrofuran of dehydration at the bottom of the tower.In this tetrahydrofuran (THF), owing to contain the propyl carbinol that generates in the operation (V), so when the more highly purified tetrahydrofuran (THF) of needs, the tetrahydrofuran (THF) that obtains in the operation (III) is distilled, recovery is from cat head distilled tetrahydrofuran (THF), and the tetrahydrofuran (THF) that contains propyl carbinol goes out from tower bottom flow.
Description of drawings
Fig. 1, Fig. 2, Fig. 3 are the flow chart illustration of implementing when of the present invention.
Embodiment
Following flow chart according to Fig. 1-3 utilizes the embodiment that carries out purified tetrahydrofuran, more particularly Bright the present invention, but the present invention is not limited by following examples.
Analysis among the embodiment is carried out as follows.
(1) moisture concentration in the water-containing tetrahydrofuran
Accurately take by weighing about 30 μ l water-containing tetrahydrofurans, utilize Ka Er Brigit Fischer (Schmidt) moisture meter (Mitsubishi Chemical's (strain) System) measures amount of moisture (μ g), calculate the percentage of relative test portion amount.
(2) contain composition in the water-containing tetrahydrofuran
Utilize gas chromatography, capillary column (Agilent Te Chnologles society system) DB-WAX is used as Pillar, the peak area corresponding according to each composition obtained the ratio that contains of each composition with the correction area percentage method Rate (A%) according to the moisture concentration of obtaining in (1) (W%), is revised by following formula, calculates to contain The amount of having (C%). (" % " of usefulness also can be converted into " ppm " according to the composition water content herein. )
Several 1
C(％)＝100-W/100×A(％)
In the correction area percentage method, the augmenting factor of each composition of use, with oxolane as benchmark, Obtained by effective carbon number, can use following value.
Table 1
Coefficient with respect to oxolane
Acetaldehyde 1.833
Propionic aldehyde 1.208
Methacrylaldehyde 1.228
Dihydrofuran 1.006
Hydroxyl tetrahydrofuran 1.629
Isopropyl alcohol 1.111
N-butanol 0.907
Hutanal 1.000
Embodiment 1 (with reference to Fig. 1)
Terephalic acid and BDO are mixed with 1: 1.8 (mol ratio), be modulated into slurries. Should Slurries and be fed in the esterification groove with respect to four-n-butyltitanate of slurries 0.0474% stir lower to 230 ℃, 0.1Mpa reacted 3 hours, obtained the oligomer of esterification yield 95%, will be by the gas of esterification groove generation Body import to be paid in the destilling tower of establishing, and distills with 90～100 ℃ of 0.1Mpa, tower top temperature, distillates moisture Oxolane, the quantity of distillate of water-containing tetrahydrofuran is 18.8% of slurries in the infeed esterification groove, this tetrahydrochysene The concentration of furans is 32.6%, contains dihydrofuran 350ppm, acetaldehyde 10ppm, propionic aldehyde 20ppm, propylene Aldehyde 20ppm.
With superficial linear velocity in a column (LHSV) 0.2/hr, it is strong that above-mentioned water-containing tetrahydrofuran is fed to filling fourth sulfonic acid type Enlightening father-in-law's ion exchange resin SKIB (Mitsubishi chemical Co., Ltd's goods, the Di A of acid cation exchange resin The father-in-law is the registration mark of Mitsubishi Chemical society) the hydration reaction tower in, reaction tower remains under 50 ℃, 0.2Mpa, Hydration reaction tower efflux composed as follows.
Oxolane 32.6%
Dihydrofuran＜10ppm
Acetaldehyde 10ppm
Propionic aldehyde 20ppm
Propenal 20ppm
Hydroxyl tetrahydrofuran 0.19%
Other are 1.21% years old
Water 66.0%
Overhead distillate with above-mentioned hydration reaction tower effluent liquid and dehydration distillation tower 4, be fed in the distillation tower 2 of 30 grades of theoretical stages, under normal pressure, distill with about 100 ℃ of column bottom temperature, reflux ratio 2.9, go out based on liquid at the bottom of the tower of water from tower bottom flow, distillate the water-containing tetrahydrofuran of tetrahydrofuran (THF) concentration 94.7% from cat head.The weight ratio of tower bottom flow fluid and overhead distillate is that 67: 54. these cats head are reserved in the liquid, contains second wine aldehyde 19ppm, propionic aldehyde 37ppm, propenal 37ppm.
This overhead distillate is infeeded in the distillation tower 3 that gently boils of 25 grades of theoretical stages, with column bottom temperature is that 68 ℃, reflux ratio 150 distill, aldehydes distillates from cat head with the azeotrope of tetrahydrofuran (THF)-water, and the tetrahydrofuran (THF)-water mixed liquid of tetrahydrofuran (THF) 94.7% goes out from tower bottom flow.The weight ratio of overhead distillate and tower bottom flow fluid is 1: 53.The content of the acetaldehyde in the tower bottom flow fluid, propionic aldehyde, propenal is all less than 10ppm.
Distillate at the bottom of the tower of the distillation tower 3 that gently boils is infeeded in the dehydration distillation tower 4 of 14 grades of theoretical stages, distill with tower top pressure 0.84Mpa, about 150 ℃ of column bottom temperature, reflux ratio 0.5, distillate the water-containing tetrahydrofuran of tetrahydrofuran (THF) 87.2%, water 12.6% from cat head, go out the tetrahydrofuran (THF) of dehydration from tower bottom flow.Purity is more than 99.95%, and dihydrofuran and the aldehyde of carbon number below 3 are all below 10ppm.The Virahol that contains 20ppm.The weight ratio of overhead distillate and tower bottom flow fluid is 21: 32.
Embodiment 2 (with reference to Fig. 2)
Except the dihydrofuran amount is 0.3%, use the water-containing tetrahydrofuran identical with embodiment 1, the same with embodiment 1, when handling with 1 hydration reaction tower, reaction tower effluent liquid composed as follows.
[table 3]
Tetrahydrofuran (THF) 32.3%
Dihydrofuran 300ppm
Acetaldehyde 10ppm
Propionic aldehyde 20ppm
Propenal 20ppm
Hydroxyl tetrahydrofuran 0.68%
Other are 1.02% years old
Water 66%
In this liquid, add following overhead distillate, with embodiment 1 the same the distillation from the 2nd hydration reaction tower 5 a reaction solution part that obtains and the distillation tower 4 that dewaters.At this moment, the weight ratio of tower bottom flow fluid and overhead distillate is 67: 104, contains acetaldehyde 19ppm, propionic aldehyde 37ppm, propenal 37ppm, dihydrofuran 29ppm in the overhead distillate.
With this water-containing tetrahydrofuran, infeed in the 2nd hydration reaction tower 5 of filling Ding Diaweng ion exchange resin SKIB with superficial velocity (LHSV) 0.2/hr.This 50 ℃ of temperature of reaction tower protection, 0.2Mpa.The concentration of dihydrofuran is less than 10ppm from the 2nd hydration reaction tower 5 effusive reaction solutions.
To flow out 50% of reaction solution from the 2nd hydration reaction tower and return the above-mentioned distillation tower 2, rest part infeeds in the distillation tower 3 that gently boils of 40 grades of theoretical stages.Gently boil distillation tower 68 ℃ of column bottom temperatures, move under the condition of reflux ratio 150, aldehydes distillates from cat head with the azeotropic mixture of tetrahydrofuran (THF)-water, obtains the water-containing tetrahydrofuran of content of tetrahydrofuran 94.7% at the bottom of the tower.The weight ratio of overhead distillate and tower bottom flow fluid is 1: 53.The amount of the acetaldehyde in the tower bottom flow fluid, propionic aldehyde, propenal is all less than 5ppm.
Tower bottom flow fluid of distillation tower 3 of gently boiling and embodiment 1 the same infeeding in the dehydration distillation tower 4 with the distillation of dewatering under the condition, obtain and the overhead distillate of embodiment 1 same composition and the tetrahydrofuran (THF) that dewaters.The purity of gained tetrahydrofuran (THF) is more than 99.95%, and dihydrofuran and the aldehyde of carbon number below 3 are all below 5ppm.The amount of Virahol is 20ppm.The weight ratio of overhead distillate and tower bottom flow fluid is 21: 32.
With terephthalic acid and 1, the 4-butyleneglycol mixes the formation slurries with 1: 1.8 (mol ratio).Infeed in the esterification groove with these slurries with respect to the tetrabutyl titanate ester of these slurries 0.0474 (weight) %, stirring, the reaction 3 hours down of 230 ℃, 0.1Mpa obtains the oligopolymer of esterification yield 95%.The gas that is produced by the esterification groove imports in pair distillation tower of establishing, and in 0.1Mpa, 90～100 ℃ of distillations down of tower top temperature, distillates tetrahydrofuran aqueous solution from cat head.The tetrahydrofuran (THF) concentration of this aqueous solution is 32.6 weight %, contains hydroxyl tetrahydrofuran 3000ppm, dihydrofuran 3000ppm, acetaldehyde 10ppm, propionic aldehyde 20ppm and propenal 20ppm.
With the tetrahydrofuran aqueous solution of above-mentioned recovery, under 50 ℃, the condition of 0.2Mpa, with liquid superficial velocity 0.2hr
-1Send in the 1st hydration reactor of filling fourth sulfonic acid ion exchange resin (Di Aweng ion exchange resin SKIB, Di Aweng are the registered trademarks of Mitsubishi Chemical society), make the dihydrofuran hydration become hydroxyl tetrahydrofuran, the concentration of tetrahydrofuran (THF) is 32.2 weight % from the hydration reaction liquid that reactor flows out, and contains dihydrofuran 30ppm, acetaldehyde 10ppm, propionic aldehyde 20ppm, propenal 20ppm, hydroxyl tetrahydrofuran 6800ppm, other foreign material 1.02 weight %.
Use the distillation tower of 30 grades of theoretical stages, with the circulation fluid from following the 2nd hydration reactor 5,100 ℃ of column bottom temperatures, reflux ratio is distilled for 2.9 times with this hydration reaction liquid, and wherein whole tetrahydrofuran (THF)s distillate from cat head.Tetrahydrofuran (THF) concentration in the distilled water-containing tetrahydrofuran is 94.7 weight %, contains acetaldehyde 30ppm, propionic aldehyde 59ppm, propenal 59ppm and dihydrofuran 50ppm.Go out based on water from tower bottom flow, contain hydroxyl tetrahydrofuran, the aqueous solution of other high boiling point foreign material.
With the above-mentioned water-containing tetrahydrofuran that obtains, at 50 ℃, 0.2Mpa, liquid air tower speed 0.2hr
-1Condition under send in the 2nd hydration reactor 5 of filling Di Aweng ion exchange resin SKIB, make remaining dihydrofuran carry out hydration, reduce to below the 10ppm by the concentration of dihydrofuran in the reactor 5 effusive hydration reaction liquid.
Half amount of this hydration reaction liquid is looped back in the distillation tower 2 of front, and remaining half amount infeeds in the distillation tower 3 that gently boils of 40 grades of the anti-theoretical stages that continues.Gently boil distillation tower 3 about 68 ℃ of normal pressure, column bottom temperature, move under reflux ratio 150 conditions, carbon number 3 following aldehyde distillate from cat head with the azeotrope of tetrahydrofuran (THF) one water, and the water-containing tetrahydrofuran of tetrahydrofuran (THF) concentration 94.7 weight % goes out from tower bottom flow.The weight ratio of overhead distillate and tower bottom flow fluid is 1: 53.The amount of the acetaldehyde the water-containing tetrahydrofuran that reclaims at the bottom of the tower, propionic aldehyde, propenal, dihydrofuran is all less than 5ppm.
With divinyl ester acidic groupization, repeated hydrogenation, with obtain 1,4-two acetoxy group butane add water decomposition, generate to contain 1,4-butyleneglycol, 1,4-butyleneglycol list second vinegar ester and diacetate esters add water decomposition liquid, this decomposed solution dewatered in the presence of acid catalyst or take off acetic acid, generate tetrahydrofuran (THF), reaction solution is distilled in distillation tower 6, obtain containing the distillate of tetrahydrofuran (THF) 59.1 weight %, acetic acid 36.7 weight % and water 4.1 weight % from cat head.This distillate contains dihydrofuran 20ppm and butyraldehyde-n 550ppm.With this distillate and the water-containing tetrahydrofuran that at the bottom of the tower of the above-mentioned distillation tower 3 that gently boils, reclaims, and the following tetrahydrofuran (THF) that reclaims at the bottom of tetrahydrofuran (THF) treating tower 11 towers mix (weight ratio of mixture 167: 53: 19), at 50 ℃, 0.2Mpa, 0.2hr
-1Condition under send in the 3rd hydration reactor 7 of filling Ding Diaweng SKIB, make dihydrofuran carry out hydration reaction.Gained hydration reaction liquid composed as follows, acetaldehyde, propionic aldehyde, propenal and dihydrofuran are all less than 10ppm.
Tetrahydrofuran (THF) 70.3 weight %
Acetic acid 25.6 weight %
Water 2.0 weight %
Butyraldehyde-n 380ppm
Hydroxyl tetrahydrofuran 30ppm
This hydration reaction liquid is mixed with the overhead distillate of following dehydration tower 4, in distillation tower 8, distill, distillate the azeotrope of tetrahydrofuran (THF)-water, go out aqueous acetic acid from tower bottom flow from cat head with normal pressure, about 107 ℃ of tower top temperature, reflux ratio 1.4.The weight ratio of overhead streams fluid and tower bottom flow fluid is 281: 70.Butyraldehyde-n content is than being 320ppm in the overhead product.
Then, this overhead distillate is sent in the hydrogenator 9 of the hydrogenation catalyst of having filled gac carrier band ruthenium with hydrogen, hydrogenation of n-butyraldehyde is formed propyl carbinol.The overhead distillate that infeeds to hydrogenator and the ratio of hydrogen are 281: 0.3 (weight ratio), at 100 ℃, 0.94Mpa, liquid air tower speed 0.5hr
-1Condition under carry out hydrogenation reaction.By the effusive hydrogenation reaction solution of hydrogenator, in gas-liquid separation groove 10, carry out gas-liquid separation under the normal pressure.Propyl carbinol is below 330ppm in the liquid phase, and butyraldehyde-n is below 10ppm.
With liquid phase in the dehydration distillation tower 4 of 21 grades of theoretical progression, distill with tower top pressure 0.84Mpa, about 150 ℃ of column bottom temperature, reflux ratio 0.5, distillate the water-containing tetrahydrofuran of tetrahydrofuran (THF) 87.3 weight %, water 12.7 weight % from cat head, and circulation adds in the distillation tower 8, reclaims the tetrahydrofuran (THF) of dehydration at the bottom of the tower.The weight ratio of overhead distillate and tower bottom flow fluid is 112: 169.
The tetrahydrofuran (THF) that reclaims at the bottom of the tower of dehydration distillation tower 4, in the treating tower 11 of 19 grades of theoretical progression, with about 67 ℃ of normal pressure, column bottom temperature, reflux ratio 0.5 is distilled, and distillates the purified tetrahydrofuran (THF) from cat head.Go out to contain the tetrahydrofuran (THF) of propyl carbinol from tower bottom flow, recirculation is returned in the 3rd hydration reactor 7.The weight ratio of overhead product and bottom stream is 150: 19.From the tetrahydrofuran (THF) purity of recovered overhead is more than 99.95%, and dihydrofuran and carbon number aldehyde and the alcohol below 3 all is lower than 5ppm.
Claims (8)
1. PURIFICATION OF TETRAHYDROFURAN method, it is made with extra care at the water-containing tetrahydrofuran (A) of the aldehydes below 3 containing dihydrofuran and carbon number, it is characterized in that, is carrying out carrying out operation (III) after following operation (I) and the operation (II),
Operation (I): water-containing tetrahydrofuran is contacted with storng-acid cation exchange resin, after converting the dihydrofuran in the tetrahydrofuran (THF) to hydroxyl tetrahydrofuran, conversion reaction liquid is distilled, the aqueous solution that contains hydroxyl tetrahydrofuran is gone out from tower bottom flow, and tetrahydrofuran (THF) is distillated from cat head with water;
Operation (II):, carbon number is distillated from cat head with a part of tetrahydrofuran (THF) at the aldehydes below 3, and the tetrahydrofuran (THF) of rest part is gone out from tower bottom flow with water with the water-containing tetrahydrofuran distillation;
Operation (III): with dihydrofuran and carbon number in the density loss of the aldehydes below 3 water-containing tetrahydrofuran distill, make water as and the azeotrope of tetrahydrofuran (THF) distillate from cat head, the tetrahydrofuran (THF) of dehydration is gone out from tower bottom flow.
2. according to the method for claim 1 record, it is characterized in that, after operation (I), carry out operation (II).
3. according to the method for claim 1 record, it is characterized in that, carry out after 2 times, carry out operation (II) in operation (I).
4. according to the method for claim 1 record, it is characterized in that, after operation (I), carry out operation (II), carry out operation (I) again.
5. according to the method for claim 1 record, it is characterized in that, make in operation (I) from cat head distilled water-containing tetrahydrofuran with after storng-acid cation exchange resin contacts, its at least a portion is sent in the distillation tower of the preface of doing over again (I), rest part is sent in the operation (II).
6. according to the method for claim 1 record, it is characterized in that, operation (I) and operation (II) afterwards, operation (III) before, carry out following operation (IV) and operation (V),
Operation (IV): will be by to containing 1, the solution of 4-butyleneglycol monoacetate takes off acetic acid, cyclisation and the water-containing tetrahydrofuran that contains acetic acid etc. that obtains distills, and the tetrahydrofuran (THF) (water-containing tetrahydrofuran (B)) that will contain water and acetic acid from the cat head distilled with through operation (I) and operation (II) and the water-containing tetrahydrofuran that obtains mixes, it is contacted with storng-acid cation exchange resin, make contained dihydrofuran hydration become hydroxyl tetrahydrofuran, the hydration reaction liquid that obtains is distilled, distillate tetrahydrofuran (THF) from cat head.
Operation (V): the water-containing tetrahydrofuran that will obtain in operation (IV) infeeds in the hydrogenation reaction, makes the butyraldehyde-n in the tetrahydrofuran (THF) convert propyl carbinol to.
7. according to the method for each record among the claim 1-6, it is characterized in that the tetrahydrofuran (THF) of the dehydration that will obtain distills in operation (III), further refined tetrahydrofuran (THF) is distillated from cat head.
8. according to the method for claim 1 record, it is characterized in that, is by 1 for the purified water-containing tetrahydrofuran, and 4-butyleneglycol and aromatic dicarboxylic acid or its reactive derivatives are made the by product in the process of polyester.
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| CN101723922B (en) * | 2009-11-18 | 2011-07-20 | 天津市康科德科技有限公司 | Method for purifying high-purity organic solvent tetrahydrofuran for scientific research |
| CN101962373A (en) * | 2010-10-09 | 2011-02-02 | 宜兴市创新精细化工有限公司 | Quick high dehydration method for tetrahydrofuran |
| CN104736529B (en) * | 2012-10-18 | 2017-09-05 | 三菱化学株式会社 | The manufacture method of tetrahydrofuran |
| CN106543111B (en) * | 2016-11-01 | 2018-11-30 | 南京生命能科技开发有限公司 | A kind of method of isobutylaldehyde in removing tetrahydrofuran |
| CN107746394A (en) * | 2017-12-06 | 2018-03-02 | 成都化润药业有限公司 | The polishing purification method of water-containing tetrahydrofuran |
| CN111170968B (en) * | 2020-01-13 | 2020-10-27 | 北京笃敬科技有限公司 | System and method for preparing tetrahydrofuran |
| CN114315764A (en) * | 2020-09-27 | 2022-04-12 | 太仓沪试试剂有限公司 | Method for refining and purifying tetrahydrofuran containing water |
| CN116041285A (en) * | 2022-12-08 | 2023-05-02 | 杰特(宁夏)科技有限公司 | Novel tetrahydrofuran dehydration process |
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