CN113845402B - Method for preparing 1, 4-butanediol and derivatives thereof from tetrahydrofuran compounds - Google Patents
Method for preparing 1, 4-butanediol and derivatives thereof from tetrahydrofuran compounds Download PDFInfo
- Publication number
- CN113845402B CN113845402B CN202111192935.0A CN202111192935A CN113845402B CN 113845402 B CN113845402 B CN 113845402B CN 202111192935 A CN202111192935 A CN 202111192935A CN 113845402 B CN113845402 B CN 113845402B
- Authority
- CN
- China
- Prior art keywords
- acid
- tetrahydrofuran
- butanediol
- derivatives
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical class C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 title claims abstract description 71
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 21
- 238000007142 ring opening reaction Methods 0.000 claims abstract description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 42
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 30
- 239000003054 catalyst Substances 0.000 claims description 30
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 28
- 239000000126 substance Substances 0.000 claims description 28
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 27
- 238000002390 rotary evaporation Methods 0.000 claims description 22
- 239000002253 acid Substances 0.000 claims description 21
- OXMIDRBAFOEOQT-UHFFFAOYSA-N 2,5-dimethyloxolane Chemical compound CC1CCC(C)O1 OXMIDRBAFOEOQT-UHFFFAOYSA-N 0.000 claims description 18
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 16
- -1 tetrahydrofuran compound Chemical class 0.000 claims description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 14
- 235000019260 propionic acid Nutrition 0.000 claims description 14
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 11
- 239000003456 ion exchange resin Substances 0.000 claims description 11
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 11
- 238000005809 transesterification reaction Methods 0.000 claims description 11
- 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 claims description 10
- 238000005886 esterification reaction Methods 0.000 claims description 9
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 7
- 235000019253 formic acid Nutrition 0.000 claims description 7
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- NGCDGPPKVSZGRR-UHFFFAOYSA-J 1,4,6,9-tetraoxa-5-stannaspiro[4.4]nonane-2,3,7,8-tetrone Chemical compound [Sn+4].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O NGCDGPPKVSZGRR-UHFFFAOYSA-J 0.000 claims description 5
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 5
- 239000000292 calcium oxide Substances 0.000 claims description 5
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 5
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 2
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 2
- 150000004692 metal hydroxides Chemical group 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 239000001119 stannous chloride Substances 0.000 claims description 2
- 235000011150 stannous chloride Nutrition 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims 2
- 238000010025 steaming Methods 0.000 claims 1
- 238000004064 recycling Methods 0.000 abstract description 7
- 229920006395 saturated elastomer Polymers 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 55
- 239000000047 product Substances 0.000 description 31
- 238000009835 boiling Methods 0.000 description 18
- 239000000203 mixture Substances 0.000 description 17
- 239000012295 chemical reaction liquid Substances 0.000 description 13
- 238000001914 filtration Methods 0.000 description 13
- 229920003023 plastic Polymers 0.000 description 12
- 239000004033 plastic Substances 0.000 description 12
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 6
- 229920006238 degradable plastic Polymers 0.000 description 6
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 6
- 229940017219 methyl propionate Drugs 0.000 description 6
- 239000002699 waste material Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 5
- HAIVWDGLCRYQMC-UHFFFAOYSA-N 4-methylpentane-1,4-diol Chemical compound CC(C)(O)CCCO HAIVWDGLCRYQMC-UHFFFAOYSA-N 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- OHMBHFSEKCCCBW-UHFFFAOYSA-N hexane-2,5-diol Chemical compound CC(O)CCC(C)O OHMBHFSEKCCCBW-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- GLOBUAZSRIOKLN-UHFFFAOYSA-N pentane-1,4-diol Chemical compound CC(O)CCCO GLOBUAZSRIOKLN-UHFFFAOYSA-N 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 3
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 3
- YJGJRYWNNHUESM-UHFFFAOYSA-J triacetyloxystannyl acetate Chemical compound [Sn+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O YJGJRYWNNHUESM-UHFFFAOYSA-J 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 2
- 229920000704 biodegradable plastic Polymers 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 150000004292 cyclic ethers Chemical group 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- KTAAIIQKTKSULG-UHFFFAOYSA-H dichlorozinc tetrachlorostannane Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Zn+2].Cl[Sn+2]Cl KTAAIIQKTKSULG-UHFFFAOYSA-H 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/128—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by alcoholysis
- C07C29/1285—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by alcoholysis of esters of organic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing 1, 4-butanediol and derivatives thereof from tetrahydrofuran compounds, belonging to the technical field of circular economy. Aiming at the problems that the tetrahydrofuran compounds used in the prior solution are saturated, the direct utilization is limited, the ring opening is difficult, the recycling way is few, and the like, the invention provides a method for preparing the 1, 4-butanediol and the derivatives thereof from the tetrahydrofuran compounds. Provides a new way for recycling tetrahydrofuran compounds.
Description
Technical Field
The invention belongs to the technical field of circular economy, and particularly relates to a method for preparing 1, 4-butanediol and derivatives thereof from tetrahydrofuran compounds.
Background
With the development of social economy, plastic products bring great convenience to the life of people. At present, only once plastic products are recycled for 1.2 hundred million tons every year in the world, only 10 percent of plastic products are recycled, the other 12 percent of plastic products are burnt, and more than 70 percent of plastic products are discarded into soil, air and ocean. The waste plastics are not reasonably, correctly and timely treated, so that serious environmental pollution is brought, and the waste plastics become one of the environmental problems which are important attention in the world.
Nowadays, people have higher environmental protection consciousness, and countries around the world gradually recognize the importance of the application of environmental protection materials and increase the investment for research and development of the environmental protection materials. Biodegradable plastics have been developed. Biodegradable plastics are plastics which meet the use requirements of each property in the storage period, and can be degraded into substances harmless to the environment under the natural environment condition after being used, and are currently accepted as an effective means for solving the problem of the environment caused by the plastics. With the intensive research of degradable plastics and the development and application of degradable plastic products, the degradable plastics are expected to replace common plastics without degradation function in the near future.
The global and Chinese plastic limiting and even plastic forbidden policies fall to the ground step by step, and the degradable plastic market is hopeful to open more than ten times of space to reach the tens of millions of tons of markets. The degradable plastic industry in China starts to develop late, but market consumption is very high. Only 2012-2018, the capacity of the degradable material in China is increased from 23 ten thousand tons to 45 ten thousand tons, and the annual compound speed increase is 11.84%. In 2019, the capacity of the degradable material in China reaches 62 ten thousand tons, and the same ratio increases by about 37.8 percent. To date, the yield is steadily increasing. During the production process, about 10% of tetrahydrofuran is by-produced, and the amount thereof is considerable. Tetrahydrofuran currently used as a solution is saturated so that direct recycling thereof is limited, so that some scientists have studied open-loop recycling thereof, but the current open-loop study of tetrahydrofuran still stays in the stage of open-loop autopolymerization thereof. Under the action of the corresponding acid catalyst, tetrahydrofuran is prepared by ring-opening self-polymerization of tetrahydrofuran, and the reutilization route is less. The direct hydrolytic ring-opening reaction of tetrahydrofuran is extremely difficult due to thermodynamic limitations. Tetrahydrofuran compounds and tetrahydrofuran have similar structures and have cyclic ether structures, are also extremely difficult to open the ring, and few reports on the open ring recycling are provided at present, so that new applications of the tetrahydrofuran compounds are urgently needed to be developed. The tetrahydrofuran compounds are derived from biomass, can be used as raw materials for synthesizing degradable plastics, and can be reasonably recycled, so that resources can be saved and the environment can be protected. The environmental protection policy of national carbon neutralization and carbon arrival peak is actively responded.
Disclosure of Invention
Aiming at the problem of recycling tetrahydrofuran compounds, the invention provides a method for preparing 1, 4-butanediol and derivatives thereof from tetrahydrofuran compounds.
The invention aims to provide a method for preparing 1, 4-butanediol and derivatives thereof from tetrahydrofuran compounds, which is used for preparing corresponding esterified substances through ring opening of the tetrahydrofuran compounds under the action of a catalyst and monoacid; separating to obtain a crude product; the product is subjected to transesterification reaction with low-carbon alcohol in the presence of a catalyst; separating to obtain the target product 1, 4-butanediol and the derivatives thereof. Provides a new way for recycling tetrahydrofuran compounds.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a method for preparing 1, 4-butanediol and derivatives thereof from tetrahydrofuran compounds, which is characterized in that: the method comprises the following steps: under the action of a class A catalyst and monoacid, ring opening of tetrahydrofuran compounds is carried out to generate esterification reaction to obtain corresponding esterified substances; separating and removing unreacted raw materials and a class A catalyst; the treated esterified substance is subjected to transesterification reaction with low-carbon alcohol under the condition of a class B catalyst; and separating and removing unreacted raw materials and the B-type catalyst to obtain a target product 1, 4-butanediol and derivatives thereof.
Further, the tetrahydrofuran compound is: tetrahydrofuran, methyltetrahydrofuran, 2' -dimethyltetrahydrofuran and 2, 5-dimethyltetrahydrofuran. The compound is a precursor compound of 1, 4-butanediol and derivatives thereof, and can react with monoacid to open a loop under the condition of corresponding catalysts to generate esterification reaction. And then the target product 1, 4-butanediol and the derivatives thereof can be obtained through transesterification.
Further, the 1, 4-butanediol and the derivatives thereof are as follows: 1, 4-pentanediol, 2, 5-hexanediol, and 2-methyl-2, 5-pentanediol. The compound is a corresponding product obtained by certain reaction of the corresponding tetrahydrofuran compound.
Further, the A-type catalyst is L acid or B acid, specifically: any one of tin oxalate, stannous octoate, zinc chloride, stannous chloride, phosphotungstic acid, silicotungstic acid, phosphomolybdic acid, acid ion exchange resin and modified PDS, and the addition amount is 0.1-20% wt of tetrahydrofuran compound. The L acid or the B acid can be combined with oxygen atoms in tetrahydrofuran compounds to shift electrons, so that carbon-oxygen bonds are more easily broken, and esterification reaction is promoted. It was tested that when the amount of catalyst was less than 0.1% by weight, the reaction could not be catalyzed. When the amount of the catalyst is more than 20% by weight, the conversion of the tetrahydrofuran compound is not increased, and the amount of the catalyst is excessive, resulting in unnecessary waste.
The monoacid is any one of formic acid, acetic acid and propionic acid, and the monoacid and the tetrahydrofuran compound are mixed according to the mol ratio of (0.2-5): 1. The monoacids used herein need to have two properties, one of which is highly reactive and the other of which has a relatively low boiling point. The high reactivity makes tetrahydrofuran compound easier to open loop reaction, and the low boiling point is favorable for subsequent rotary evaporation removal. As proved by experiments, when the ratio of the two is lower than 0.2:1, the conversion rate of tetrahydrofuran is very low, and the reaction does not basically occur. The conversion of tetrahydrofuran gradually increased with the addition of the amount of acid, but when the molar ratio of the two was higher than 5:1 due to the influence of the equilibrium of the esterification reaction, the conversion of the reaction did not increase any more even if the amount of acid was increased again. If the ratio is higher, the acid content becomes excessive, resulting in unnecessary waste.
Further, the temperature of the esterification reaction is 150-220 ℃, and the reaction time is 0.5-5 h. It was tested that when the reaction temperature was below 150 ℃, the esterification reaction did not substantially occur, whereas when the reaction was above 220 ℃, the product blackened and other side reactions occurred.
Further, the method for separating and removing unreacted raw materials and the A-type catalyst is that the temperature is 80-100 ℃ and the spin evaporation is carried out for 0.5-3 h. And (3) selecting corresponding temperature according to the boiling point of the reaction raw materials to carry out rotary evaporation separation. The starting materials used were experimentally separable and removable at this temperature and time. The solvent component is changed by removing the excessive raw material, and at this time, the solubility of the class A catalyst is reduced, and the class A catalyst can be enriched at the bottom of the flask and removed by filtration.
Further, the B-type catalyst is a metal hydroxide, a metal oxide or a B-acid. The method comprises the following steps: one of sodium hydroxide, potassium hydroxide, calcium oxide, phosphotungstic acid, silicotungstic acid, phosphomolybdic acid and acid ion exchange resin, and the addition amount thereof is 0.1-30% wt of the esterified substance. Transesterification reactions may occur under acid or base catalysis. It was tested that when the amount of catalyst was less than 0.1% wt, the reaction could not be catalyzed. When the amount of the catalyst is more than 30% by weight, the conversion of the ester is not increased, and the amount of the catalyst is excessive, resulting in unnecessary waste.
Further, the low carbon number alcohol is: methanol or ethanol. The mol ratio of the catalyst to the esterified compound is (6-15): 1. the condition of low carbon number alcohol is that the activity is high and the boiling point is low. The low carbon number alcohol with high activity is easier to carry out transesterification reaction with the esterified substance; the boiling point is low, and the waste water can be removed by simple rotary evaporation, thereby being convenient for subsequent separation. Through experiments, when the ratio of the two is lower than 6:1, the conversion rate of the esterified substance is lower, and as the amount of the low-carbon alcohol is increased, the conversion rate of the esterified substance is increased, and when the ratio of the two is higher than 15:1, the conversion rate is not increased any more due to the balance influence of transesterification, and the low-carbon alcohol is excessive, so that unnecessary waste is caused.
Further, the temperature of the transesterification reaction is 80-150 ℃ and the reaction time is 0.5-5 h. It was tested that when the reaction temperature was below 80 ℃, the transesterification reaction did not substantially occur, whereas when the reaction was above 150 ℃, the color of the solution became dark and side reactions occurred.
Further, the method for separating and removing unreacted raw materials and the B-type catalyst is that the temperature is 45-80 ℃ and the time is 0.5-5 h. And (3) selecting corresponding temperature according to the boiling point of the reaction raw materials to carry out rotary evaporation separation. The starting materials used were experimentally separable and removable at this temperature and time. The solvent component is changed by removing the excessive raw material, and at this time, the solubility of the B-type catalyst is reduced, and the B-type catalyst can be enriched at the bottom of the flask and removed by filtration.
Compared with the prior art, the invention has the following advantages:
the invention applies the esterification reaction and the transesterification reaction to the ring opening of tetrahydrofuran compounds for the first time, and successfully recovers and obtains the 1, 4-butanediol and the derivatives thereof.
Drawings
FIG. 1 shows the structure of an esterified product obtained by ring opening of tetrahydrofuran and acetic acid;
FIG. 2 shows the nuclear magnetic pattern of the finally produced 1, 4-butanediol.
Detailed Description
Example 1:
2.16g of tetrahydrofuran, 0.36g of acetic acid and 0.2g of phosphotungstic acid are weighed and mixed, and then the mixture is placed in a blast oven for reaction for 3 hours at 150 ℃. And then, the obtained reaction solution is subjected to rotary evaporation at 80 ℃ for 1h to remove unreacted acetic acid and tetrahydrofuran, at this time, phosphotungstic acid is enriched at the bottom of a flask, 1.01g of corresponding esterified substance is obtained after the phosphotungstic acid is removed by filtration, 1.15g of methanol and 0.1g of sodium hydroxide are sequentially added into the treated esterified substance, the mixture is placed in a blast oven for reaction at 85 ℃ for 3h after being mixed, the obtained reaction solution is subjected to rotary evaporation at 50 ℃ for 1h to remove low-boiling methyl acetate, and 0.5g of target product 1, 4-butanediol is obtained.
Example 2:
0.72g of tetrahydrofuran, 3.0g of acetic acid and 0.14g of phosphomolybdic acid are weighed and mixed, and then the mixture is placed in a blast oven for reaction for 2 hours at 170 ℃. And then, the obtained reaction liquid is subjected to rotary evaporation at 90 ℃ for 0.5h to remove unreacted acetic acid and tetrahydrofuran, at this time, phosphotungstic acid is enriched at the bottom of a flask, 1.7g of corresponding esterified substance is obtained after the phosphotungstic acid is removed by filtration, 4.8g of methanol and 0.17g of potassium hydroxide are sequentially added into the treated esterified substance, the mixture is placed in a blast oven for reaction at 90 ℃ for 2.5h after being mixed, the obtained reaction liquid is subjected to rotary evaporation at 65 ℃ for 1h to remove low-boiling methyl acetate, and 1.0g of target product 1, 4-butanediol is obtained.
Example 3:
1.0g of tetrahydrofuran, 3.0g of acetic acid and 0.3g of silicotungstic acid are weighed and mixed, and then the mixture is placed in a blast oven for reaction for 1h at 180 ℃. And then, carrying out rotary evaporation on the obtained reaction liquid for 1h at 85 ℃ to remove unreacted acetic acid and tetrahydrofuran, at the moment, enriching phosphotungstic acid at the bottom of a flask, filtering to remove the phosphotungstic acid to obtain 1.78g of corresponding esterified substance, sequentially adding 3.0g of methanol and 0.17g of calcium oxide into the treated esterified substance, mixing, placing the mixed esterified substance into a blast oven for reaction for 1h at 120 ℃, carrying out rotary evaporation on the obtained reaction liquid for 0.5h at 80 ℃, and removing low-boiling methyl acetate to obtain 1.3g of target product 1, 4-butanediol.
Example 4:
2.58g of methyltetrahydrofuran, 0.28g of formic acid and 0.25g of acid ion exchange resin are weighed, mixed and placed in a blast oven for reaction for 3 hours at 200 ℃. Then, the obtained reaction solution was distilled off at 100℃for 2 hours to remove unreacted acetic acid and methyltetrahydrofuran, and at this time, the acidic ion-exchange resin was concentrated in the bottom of the flask, and the resultant was filtered to remove the acidic ion-exchange resin, whereby 1.43g of the corresponding ester was obtained. Adding 4.0g of methanol and 0.14g of phosphotungstic acid into the treated esterified substance in sequence, mixing, placing the mixture into a blast oven for reaction at 100 ℃ for 2 hours, and removing low-boiling methyl formate by rotary evaporation of the obtained reaction liquid at 80 ℃ for 0.5 hour to obtain 1.3g of target product 1, 4-pentanediol.
Example 5:
0.86g of methyltetrahydrofuran, 2.3g of formic acid and 0.25g of modified PDS are weighed, mixed and placed in a blast oven for reaction for 3 hours at 220 ℃. The resulting reaction solution was then distilled off at 100℃for 2 hours to remove unreacted formic acid and methyltetrahydrofuran, and at this time, modified PDS was concentrated in the bottom of the flask, and 2.13g of the corresponding ester was obtained after removal of the modified PDS by filtration. 3.8g of methanol and 0.5g of acid ion exchange resin are sequentially added into the treated esterified substance, the mixture is placed in a blast oven for reaction for 1h at 150 ℃, and the obtained reaction liquid is subjected to rotary evaporation at 80 ℃ for 0.5h to remove low-boiling methyl formate, so that 1.9g of target product 1, 4-pentanediol is obtained.
Example 6:
1.26g of methyltetrahydrofuran, 2.3g of formic acid and 0.01g of stannic chloride are weighed, mixed and placed in a blast oven for reaction for 3 hours at 220 ℃. Then, the obtained reaction solution was distilled off at 100℃for 2 hours to remove unreacted formic acid and methyltetrahydrofuran, at this time, tin chloride was concentrated in the bottom of the flask, and 1.7g of a corresponding esterified product was obtained by removing tin chloride by filtration. 3.0g of methanol and 0.5g of acid ion exchange resin are sequentially added into the treated esterified substance, the mixture is placed in a blast oven for reaction for 2 hours at 150 ℃, and the obtained reaction liquid is subjected to rotary evaporation at 80 ℃ for 0.5 hour to remove low-boiling methyl formate, so that 1.6g of target product 1, 4-pentanediol is obtained.
Example 7:
3.0g of 2, 5-dimethyl tetrahydrofuran, 2.0g of propionic acid and 0.3g of tin acetate are weighed, mixed and placed in a blast oven for reaction for 5 hours at 220 ℃. Then, the obtained reaction solution was distilled off at 100℃for 3 hours to remove unreacted propionic acid and 2, 5-dimethyltetrahydrofuran, and at this time, tin acetate was concentrated in the bottom of the flask, and 2.7g of the corresponding ester was obtained by removing tin acetate by filtration. 3.2g of methanol and 0.5g of phosphomolybdic acid are sequentially added into the treated esterified substance, the mixture is placed into a blast oven for reaction at 100 ℃ for 5 hours, the obtained reaction liquid is subjected to rotary evaporation at 80 ℃ for 3 hours, and the methyl propionate with low boiling point is removed, so that 1.87g of target product 2, 5-hexanediol is obtained.
Example 8:
3.0g of 2, 5-dimethyl tetrahydrofuran, 3.7g of propionic acid and 0.5g of tin oxalate are weighed, mixed and placed in a blast oven for reaction for 4 hours at 220 ℃. The resulting reaction solution was then distilled off at 100℃for 3 hours to remove unreacted propionic acid and 2, 5-dimethyltetrahydrofuran, and at this time, tin oxalate was concentrated in the bottom of the flask, and 3.1g of the corresponding esterified product was obtained by filtration to remove tin oxalate. Adding 4.3g of methanol and 0.7g of silicotungstic acid into the treated esterified substance in sequence, mixing, placing the mixture into a blast oven for reaction at 100 ℃ for 5 hours, and performing rotary evaporation on the obtained reaction liquid at 80 ℃ for 3 hours to remove low-boiling methyl propionate to obtain 2.01g of target product 2, 5-hexanediol.
Example 9:
1.5g of 2, 5-dimethyltetrahydrofuran, 3.7g of propionic acid and 0.1g of zinc chloride are weighed and mixed, and then the mixture is placed in a blast oven for reaction for 1h at 220 ℃. The resulting reaction solution was then distilled off at 100℃for 3 hours to remove unreacted propionic acid and 2, 5-dimethyltetrahydrofuran, and at this time, zinc chloride tin was enriched in the bottom of the flask, and 1.9g of the corresponding esterified product was obtained by filtration to remove zinc chloride. 2.7g of methanol and 0.3g of acid ion exchange resin are sequentially added into the treated esterified substance, the mixture is placed in a blast oven for reaction at 100 ℃ for 3 hours, the obtained reaction liquid is subjected to rotary evaporation at 80 ℃ for 2 hours, and the methyl propionate with low boiling point is removed, so that 1.62g of target product 2, 5-hexanediol is obtained.
Example 10:
2.0g of 2,2' -dimethyltetrahydrofuran, 4.0g of propionic acid and 0.4g of stannous octoate are weighed, mixed and placed in a blast oven for reaction for 3 hours at 220 ℃. The resulting reaction solution was then distilled off at 100℃for 3 hours to remove unreacted propionic acid and 2, 5-dimethyltetrahydrofuran, at this time, stannous octoate was concentrated in the bottom of the flask, and 2.6g of the corresponding esterified product was obtained by filtration to remove stannous octoate. Adding 4.2g of methanol and 0.3g of sodium hydroxide into the treated esterified substance in sequence, mixing, placing the mixture into a blast oven for reaction at 100 ℃ for 2 hours, and performing rotary evaporation on the obtained reaction liquid at 80 ℃ for 2 hours to remove low-boiling methyl propionate to obtain 2.0g of target product 2-methyl-2, 5-pentanediol.
Example 11:
1.5g of 2,2' -dimethyltetrahydrofuran, 3.7g of propionic acid and 0.1g of phosphotungstic acid are weighed and mixed, and then the mixture is placed in a blast oven for reaction for 3 hours at 220 ℃. The resulting reaction solution was then subjected to rotary evaporation at 100℃for 3 hours to remove unreacted propionic acid and 2,2' -dimethyltetrahydrofuran, and at this time, phosphotungstic acid was concentrated in the bottom of the flask, and 2.3g of the corresponding esterified product was obtained after the phosphotungstic acid was removed by filtration. 3.6g of methanol and 0.5g of potassium hydroxide are sequentially added into the treated esterified substance, the mixture is placed in a blast oven for reaction at 100 ℃ for 2 hours after being mixed, the obtained reaction liquid is subjected to rotary evaporation at 80 ℃ for 2 hours, and the methyl propionate with low boiling point is removed, so that 1.8g of target product 2-methyl-2, 5-pentanediol is obtained.
Example 12:
1.5g of 2,2' -dimethyl tetrahydrofuran, 3.7g of propionic acid and 0.1g of silicotungstic acid are weighed and mixed, and then the mixture is placed in a blast oven for reaction for 3 hours at 220 ℃. The resulting reaction solution was then subjected to rotary evaporation at 100℃for 3 hours to remove unreacted propionic acid and 2,2' -dimethyltetrahydrofuran, and at this time, silicotungstic acid was concentrated in the bottom of the flask, and 2.6g of the corresponding esterified product was obtained by filtration to remove silicotungstic acid. Sequentially adding 5.1g of methanol and 0.5g of calcium oxide into the treated esterified substance, mixing, placing the mixture into a blast oven for reaction at 100 ℃ for 2 hours, and performing rotary evaporation on the obtained reaction liquid at 80 ℃ for 2 hours to remove low-boiling methyl propionate to obtain 1.6g of target product 2-methyl-2, 5-pentanediol.
What is not described in detail in the present specification belongs to the prior art known to those skilled in the art. While the foregoing describes illustrative embodiments of the present invention to facilitate an understanding of the present invention by those skilled in the art, it should be understood that the present invention is not limited to the scope of the embodiments, but is to be construed as protected by the accompanying claims insofar as various changes are within the spirit and scope of the present invention as defined and defined by the appended claims.
Claims (6)
1. A method for preparing 1, 4-butanediol and derivatives thereof from tetrahydrofuran compounds, which is characterized in that: the method comprises the following steps: under the action of a class A catalyst and monoacid, ring opening of tetrahydrofuran compounds is carried out to generate esterification reaction to obtain corresponding esterified substances; separating and removing unreacted raw materials and a class A catalyst; the treated esterified substance is subjected to transesterification reaction with low-carbon alcohol under the condition of a class B catalyst; separating and removing unreacted raw materials and a B-type catalyst to obtain a target product 1, 4-butanediol and derivatives thereof;
the tetrahydrofuran compound is as follows: any one of tetrahydrofuran, methyltetrahydrofuran, 2' -dimethyltetrahydrofuran and 2, 5-dimethyltetrahydrofuran;
the A-type catalyst is L acid or B acid, and specifically comprises the following components: any one of tin oxalate, stannous octoate, zinc chloride, stannous chloride, phosphotungstic acid, silicotungstic acid, phosphomolybdic acid, acid ion exchange resin and modified PDS, and the addition amount is 0.1-20% of tetrahydrofuran compound;
the B-type catalyst is metal hydroxide, metal oxide and B acid, and specifically comprises the following components: one of sodium hydroxide, potassium hydroxide, calcium oxide, phosphotungstic acid, silicotungstic acid, phosphomolybdic acid and acid ion exchange resin, and the addition amount of the sodium hydroxide, the potassium hydroxide, the calcium oxide, the phosphotungstic acid, the silicotungstic acid, the phosphomolybdic acid and the acid ion exchange resin is 0.1-30% of the weight of the esterified substance;
the low carbon number alcohol is as follows: any one of methanol and ethanol;
the temperature of the transesterification reaction is 80-150 ℃, and the reaction time is 0.5-h-5 h.
2. The process for preparing 1, 4-butanediol and derivatives thereof from tetrahydrofuran compounds according to claim 1, wherein: the monoacid is any one of formic acid, acetic acid and propionic acid, and the molar ratio of the monoacid to the tetrahydrofuran compound is (0.2-5): 1.
3. A process for the preparation of 1, 4-butanediol and derivatives thereof from tetrahydrofuran compounds according to claim 2, characterized in that: the temperature of the esterification reaction is 150-220 ℃, and the reaction time is 0.5-h-5 h.
4. A process for the preparation of 1, 4-butanediol and derivatives thereof from tetrahydrofuran compounds according to claim 3, wherein: the method for separating and removing unreacted raw materials and the A-type catalyst is carried out at 80-100 ℃ by rotary evaporation at 0.5-h-3 h.
5. The method for preparing 1, 4-butanediol and derivatives thereof from tetrahydrofuran compounds according to claim 4, wherein the method comprises the steps of: the molar ratio of the low-carbon alcohol to the esterified substance is (6-15): 1.
6. The method for preparing 1, 4-butanediol and derivatives thereof from tetrahydrofuran compounds according to claim 5, wherein the steps of: the method for separating and removing unreacted raw materials and the B-type catalyst comprises the steps of rotary steaming at 45-80 ℃ to 0.5-h-5 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111192935.0A CN113845402B (en) | 2021-10-13 | 2021-10-13 | Method for preparing 1, 4-butanediol and derivatives thereof from tetrahydrofuran compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111192935.0A CN113845402B (en) | 2021-10-13 | 2021-10-13 | Method for preparing 1, 4-butanediol and derivatives thereof from tetrahydrofuran compounds |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113845402A CN113845402A (en) | 2021-12-28 |
| CN113845402B true CN113845402B (en) | 2024-02-06 |
Family
ID=78978169
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111192935.0A Active CN113845402B (en) | 2021-10-13 | 2021-10-13 | Method for preparing 1, 4-butanediol and derivatives thereof from tetrahydrofuran compounds |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113845402B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1819999A (en) * | 2003-07-08 | 2006-08-16 | 巴斯福股份公司 | Method for obtaining oligomers of polytetrahydrofurane or tetrahydrofurane copolymers |
| CN101679157A (en) * | 2007-06-06 | 2010-03-24 | 宇部兴产株式会社 | Method of producing 1,5-pentanediol and/or 1,6-hexanediol |
| CN105461666A (en) * | 2016-01-07 | 2016-04-06 | 华东师范大学 | Preparation method of 2-substituted tetrahydrofuran compounds |
| CN106554331A (en) * | 2016-11-07 | 2017-04-05 | 中国科学院山西煤炭化学研究所 | A kind of method that degraded PolyTHF reclaims tetrahydrofuran |
| CN108821967A (en) * | 2018-08-07 | 2018-11-16 | 中国天辰工程有限公司 | A kind of synthesis technology of high-purity Ester |
| CN110343078A (en) * | 2018-04-04 | 2019-10-18 | 中国科学院宁波材料技术与工程研究所 | A kind of preparation method of furans ether compound |
| CN113024350A (en) * | 2021-03-19 | 2021-06-25 | 中国科学院兰州化学物理研究所 | Method for preparing 1, 5-pentanediol or 1, 6-hexanediol by utilizing bio-based furan compound |
-
2021
- 2021-10-13 CN CN202111192935.0A patent/CN113845402B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1819999A (en) * | 2003-07-08 | 2006-08-16 | 巴斯福股份公司 | Method for obtaining oligomers of polytetrahydrofurane or tetrahydrofurane copolymers |
| CN101679157A (en) * | 2007-06-06 | 2010-03-24 | 宇部兴产株式会社 | Method of producing 1,5-pentanediol and/or 1,6-hexanediol |
| CN105461666A (en) * | 2016-01-07 | 2016-04-06 | 华东师范大学 | Preparation method of 2-substituted tetrahydrofuran compounds |
| CN106554331A (en) * | 2016-11-07 | 2017-04-05 | 中国科学院山西煤炭化学研究所 | A kind of method that degraded PolyTHF reclaims tetrahydrofuran |
| CN110343078A (en) * | 2018-04-04 | 2019-10-18 | 中国科学院宁波材料技术与工程研究所 | A kind of preparation method of furans ether compound |
| CN108821967A (en) * | 2018-08-07 | 2018-11-16 | 中国天辰工程有限公司 | A kind of synthesis technology of high-purity Ester |
| CN113024350A (en) * | 2021-03-19 | 2021-06-25 | 中国科学院兰州化学物理研究所 | Method for preparing 1, 5-pentanediol or 1, 6-hexanediol by utilizing bio-based furan compound |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113845402A (en) | 2021-12-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108299358B (en) | Process for the selective oxidation of furan alcohols or aldehydes | |
| CN102872878B (en) | Catalyst for preparing ethanol from acetic ester hydrogenation, preparation method and application thereof | |
| CN1298696C (en) | Process for synthesizing methyl carbonate by alcoholysis of urea with aliphatic diol as cyclic agent | |
| CN101314131A (en) | Preparation for modified hydrotalcite solid base catalyst for preparing biological diesel oil | |
| CN107556186A (en) | A kind of method that adipic acid is prepared by glucaric acid | |
| CN114272932B (en) | Nickel-cerium biochar catalyst and preparation method and application thereof | |
| CN114656684A (en) | Method for preparing high-purity recycled PET (polyethylene terephthalate) polyester by using waste PET polyester | |
| CN113845402B (en) | Method for preparing 1, 4-butanediol and derivatives thereof from tetrahydrofuran compounds | |
| Jaiswal et al. | Ni modified distillation waste derived heterogeneous catalyst utilized for the production of glycerol carbonate from a biodiesel by-product glycerol: Optimization and green metric studies | |
| CN102093183A (en) | Method for preparing 2-ethyl-2-hexenoicaldehyde by condensing n-butanal under catalysis of solid base catalyst | |
| CN111499661A (en) | Preparation method of tin oxide complex diisooctanoate | |
| CN104829559A (en) | Method of preparing Nu-valerolactone from methyl levulinate | |
| CN111825549A (en) | Synthesis method of n-butyl glycolate | |
| CN107540520B (en) | Method for preparing pyromellitic acid or trimellitic acid from pinacol | |
| CN112279758B (en) | Method for preparing and separating levulinic acid from glucose | |
| CN106890652B (en) | A kind of one step selective oxidation of methanol prepares the catalyst of dimethoxym ethane and methyl formate | |
| NL2024500B1 (en) | Method for preparing 4-(3-hydroxyphenyl)-4-oxobutanoic acid from lignin | |
| CN107954952B (en) | Preparation method of 2-methyl-5, gamma-dioxotetrahydrofuran-2-pentanoic acid | |
| CN108047172B (en) | Method for preparing 2-methyl-5, gamma-dioxotetrahydrofuran-2-pentanoic acid by catalyzing levulinic acid | |
| CN111039863B (en) | Preparation method of rubber antioxidant TMQ | |
| CN113929574B (en) | Method for preparing butanediol ester compound from tetrahydrofuran compound | |
| CN111233796A (en) | Preparation method of 2, 5-furandimethanol | |
| TW202039409A (en) | Method for depolymerizing lignin and composition of phenolic compound | |
| CN107266301A (en) | A kind of isolation and purification method of acetylacetonate and its solvent used | |
| CN107417523B (en) | Preparation method of cyclohexane-1, 2-diformate plasticizer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |