CN115960058A - Method for preparing tetrahydrofuran by catalyzing 1,4-butanediol cyclodehydration with inorganic iron salt - Google Patents
Method for preparing tetrahydrofuran by catalyzing 1,4-butanediol cyclodehydration with inorganic iron salt Download PDFInfo
- Publication number
- CN115960058A CN115960058A CN202310051846.7A CN202310051846A CN115960058A CN 115960058 A CN115960058 A CN 115960058A CN 202310051846 A CN202310051846 A CN 202310051846A CN 115960058 A CN115960058 A CN 115960058A
- Authority
- CN
- China
- Prior art keywords
- reaction
- ionic liquid
- butanediol
- ferric salt
- inorganic
- 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.)
- Pending
Links
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 title claims abstract description 90
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 title claims abstract description 79
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 33
- 238000006210 cyclodehydration reaction Methods 0.000 title claims abstract description 7
- 150000002505 iron Chemical class 0.000 title claims description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 62
- 239000002608 ionic liquid Substances 0.000 claims abstract description 42
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- 150000003839 salts Chemical class 0.000 claims abstract description 23
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 20
- 229910052742 iron Inorganic materials 0.000 claims abstract description 4
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 claims abstract description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 3
- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 claims description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 5
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 claims description 4
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 17
- 230000018044 dehydration Effects 0.000 abstract description 17
- -1 halogen ions Chemical class 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 8
- 239000002904 solvent Substances 0.000 abstract description 7
- 239000012298 atmosphere Substances 0.000 abstract description 4
- 229910052736 halogen Inorganic materials 0.000 abstract description 3
- RMYXXJKVVYQPLG-UHFFFAOYSA-N 1h-imidazol-1-ium;sulfate Chemical compound [NH2+]1C=CN=C1.[NH2+]1C=CN=C1.[O-]S([O-])(=O)=O RMYXXJKVVYQPLG-UHFFFAOYSA-N 0.000 abstract 1
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- 239000000047 product Substances 0.000 description 14
- 238000007363 ring formation reaction Methods 0.000 description 14
- 239000002994 raw material Substances 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 8
- 238000004445 quantitative analysis Methods 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 6
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 4
- 239000002638 heterogeneous catalyst Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000002815 homogeneous catalyst Substances 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000007172 homogeneous catalysis Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 159000000014 iron salts Chemical class 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- DLDJFQGPPSQZKI-UHFFFAOYSA-N but-2-yne-1,4-diol Chemical compound OCC#CCO DLDJFQGPPSQZKI-UHFFFAOYSA-N 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000011335 coal coke Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 150000008050 dialkyl sulfates Chemical class 0.000 description 1
- DENRZWYUOJLTMF-UHFFFAOYSA-N diethyl sulfate Chemical compound CCOS(=O)(=O)OCC DENRZWYUOJLTMF-UHFFFAOYSA-N 0.000 description 1
- 229940008406 diethyl sulfate Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000004029 oxacyclic compounds Chemical class 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
Classifications
-
- 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
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a method for preparing tetrahydrofuran by catalyzing 1,4-butanediol cyclodehydration through inorganic ferric salt, which obviously improves the catalytic activity of a system after adding sulfate ionic liquid into the reaction system and promotes the forward reaction. The inorganic ferric salt is FeCl 2 ,FeCl 3 ,FeBr 3 ,Fe 2 (SO 4 ) 3 ,Fe(NO 3 ) 3 ·9H 2 O or Fe (OTf) 3 The ionic liquid is quaternary ammonium salt or imidazolium sulfate ionic liquid which does not contain halogen ions and has small corrosivity, and has structures of a formula (I) and a formula (II) respectively. The invention relates to a reaction for preparing tetrahydrofuran by catalyzing 1,4-butanediol dehydration with inorganic ferric salt or inorganic ferric salt and ionic liquid as catalysts. The invention has the advantages that: (1) The reaction condition is mild, no solvent is added, and no inert atmosphere protection is needed; (2) The addition of the sulfate ionic liquid can improve the catalytic activity and promote the reactionCarrying out the process; (3) The sulfate ionic liquid is cheap and easy to obtain, and can be spontaneously separated when being immiscible with a product, so that the cyclic utilization of the catalyst is realized.
Description
Technical Field
The invention belongs to the technical field of transition metal iron salt catalysis, and particularly relates to a method for preparing tetrahydrofuran by catalyzing 1,4-butanediol cyclodehydration through inorganic iron salt.
Background
O-heterocyclic compounds such as tetrahydrofuran are basic chemical substances and have wide applications as solvents, environmentally friendly alternative fuels for diesel engines, fragrances for the cosmetic industry, synthetic intermediates for pharmaceuticals and fine chemicals, and the like. Tetrahydrofuran, also known as oxolane, is colorless, transparent, volatile, pungent liquid at normal temperature and pressure, is one of ethers with very strong polarity, is used as an organic synthesis raw material, and is called as a universal solvent because of its wide dissolving capacity for polar and nonpolar compounds.
At present, the international production methods of tetrahydrofuran are more, and the industrial production is mainly realized by four processes of a furfural method, a butadiene method, a maleic anhydride hydrogenation method and a Reppe method (Reppe method) (Green Chemistry24 (2022) 6450-6466). The furfural process is one of the earliest industrial processes for producing tetrahydrofuran, and was developed by a company of Yongpo and subjected to technical research, development and improvement. The production method has high raw material consumption, more byproducts and serious pollution, is difficult to obtain high-purity products, is not beneficial to large-scale production, and is gradually eliminated. The butadiene chlorination process was successfully developed and built into a production plant in 1971. The method has the advantages of simple operation, less catalyst consumption, good tetrahydrofuran selectivity and higher yield, but the raw material butadiene exists in a gaseous state at normal temperature and is a flammable substance, and the process has long flow and high energy consumption and is not suitable for being adopted under the influence of the co-production of chloroprene rubber. The process route of the maleic anhydride method comprises liquid-phase hydrogenation and gas-phase hydrogenation, and in most areas, maleic anhydride and hydrogen are prepared by taking coal coke as a basic raw material. Therefore, the method is difficult to scale up and extend, subject to energy and environmental aspects.
The Reppe method is also called as a 1,4-butanediol (1, 4-butandiol, BDO) catalytic dehydration cyclization method, comprises three main reactions of ethynylation, hydrogenation and dehydration, and is successfully developed by I.G. Farben company in Germany and Reppe doctor in 1931. The method specifically comprises the steps of taking acetylene and formaldehyde as raw materials to generate 1, 4-butynediol, then reacting with hydrogen under the action of traditional hydrogenation catalysts such as raney nickel to prepare 1,4-butanediol, and finally performing cyclodehydration reaction under an acidic condition to obtain tetrahydrofuran.
In comparison, the 1,4-butanediol dehydration method (Reppe method) is the main route for preparing tetrahydrofuran at present, the process technology is more mature, the application is wider, and the process technology is further optimized and promoted in the field of modern chemical industry. To date, different catalytic systems have been reported for intramolecular dehydrative cyclization of glycols to give oxacyclic compounds (Science Advances7 (2021) 0396). (1) homogeneous catalytic system:acid (e.g. H) 2 SO 4 ,H 3 PO 4 And H 3 PO 2 ) Lewis acids (e.g.: zn (OAc) 2 ,CuBr 2 ) Ionic liquid ([ HO-EtMIm)][OTf]) Etc.; (2) heterogeneous catalytic system: solid acid (H) 3 PW 12 O 40 SnP), metal oxide (. Gamma. -Al) 2 O 3 ,t-ZrO 2 ) Supported catalyst (Cu) 8 Pd 2 /γ-Al 2 O 3 (Applied Catalysis B: environmental 282 (2021) 119619), cuO/ZSM-5 (Science China-Chemistry 60 (2017) 964-969)), sulfonic acid resin, and the like. The homogeneous catalysis system has mild reaction conditions, less catalyst consumption and higher yield of main products, but most of the homogeneous catalysis system has the problems of corrosivity, difficulty in separating from the products and the like. Although the heterogeneous catalyst system solves the problem of separation of the catalyst and the product, the catalytic activity of the heterogeneous catalyst system is generally lower than that of the homogeneous catalyst due to the low contact degree of the active components and the reaction substrate. Therefore, the development of a novel efficient green acid catalyst for the reaction of preparing tetrahydrofuran by dehydrating 1,4-butanediol becomes a main research direction of researchers.
The inorganic ferric salt has rich sources, low price and low toxicity; the sulfate ionic liquid has the unique advantages of simple synthesis method, cheap raw materials, no halogen ions, small corrosivity and the like, has potential application prospects in the aspects of solvents, extracting agents, lubricating materials, gas adsorption separation, composite materials and the like, and is less in application as a catalyst. The preparation of tetrahydrofuran by the dehydration reaction of 1,4-butanediol has the advantages of high atom economy and simple reaction system, but the prior reaction still has the problems of harsh reaction conditions, large catalyst dosage, more byproducts and the like. Therefore, it is still a challenge to develop a high selectivity, simple, low cost catalytic system for the dehydration and cyclization reaction of 1, 4-butanediol.
Disclosure of Invention
The invention aims to provide a method for preparing tetrahydrofuran by catalyzing 1,4-butanediol cyclodehydration through inorganic iron salt. Under the catalysis of inorganic ferric salt, after the sulfate ionic liquid is added into the system, the catalytic activity is obviously improved, and the forward progress of the reaction can be promoted. Firstly, inorganic iron salt is used as a catalyst to catalyze dehydration cyclization reaction of 1,4-butanediol to prepare tetrahydrofuran under the protection condition of no solvent and no inert atmosphere, and high-efficiency conversion of the reaction can be realized. Then taking dialkyl sulfate and N-alkyl imidazole as raw materials, obtaining sulfate ionic liquid through simple alkylation reaction, and adding the sulfate ionic liquid into a reaction system to improve the catalytic activity of the reaction. The catalytic activity of the inorganic ferric salt catalytic system provided by the invention is similar to that of a homogeneous catalyst and a heterogeneous catalyst reported in the literature, the dosage of the catalyst is lower, the reaction condition is milder, and in addition, the ionic liquid added in the reaction is immiscible as the catalyst and the product and can be recycled.
The specific technical scheme for realizing the purpose of the invention is as follows:
a method for preparing tetrahydrofuran by catalyzing 1,4-butanediol dehydration cyclization reaction with inorganic iron salt adopts inorganic iron salt or sulfate ionic liquid and inorganic iron salt as catalysts for catalyzing dehydration reaction of 1,4-butanediol, and can improve catalytic activity after adding sulfate ionic liquid into a reaction system, thereby being beneficial to forward reaction. Is characterized in that: the reaction does not need a solvent and inert atmosphere protection, and the reaction condition is mild; the inorganic ferric salt has rich sources, low price, easy obtainment and low toxicity; the sulfate ionic liquid has cheap raw materials and simple preparation process. The method specifically comprises the following steps: adding 1,4-butanediol, inorganic ferric salt or sulfate ionic liquid and inorganic ferric salt into a reaction system in sequence, stirring and reacting for 10-1440 minutes at the reaction temperature of 40-130 ℃, and obtaining a target product tetrahydrofuran after the reaction is finished; wherein:
the inorganic ferric salt is independently used as a catalyst, or the inorganic ferric salt and the sulfate ionic liquid are jointly used as the catalyst;
the iron salt is selected from FeCl 2 ,FeCl 3 ,FeBr 3 ,Fe 2 (SO 4 ) 3, Fe(NO 3 ) 3 ·9H 2 O or Fe (OTf) 3 ;
The sulfate ionic liquid is selected from imidazolium or quaternary ammonium salt ionic liquid, and specifically comprises the following components:
[MMIm][MeSO 4 ],[EMIm][MeSO 4 ],[PMIm][MeSO 4 ],[BMIm][MeSO 4 ],[EMIm][EtSO 4 ],
[EEIm][EtSO 4 ],[PEIm][EtSO 4 ],[BEIm][EtSO 4 ],[PMIm][PrSO 4 ],[PEIm][PrSO 4 ],[BMIm][BuSO 4 ]or [ BEIm][BuSO 4 ]The chemical structural formula is as follows:
in the formula: r, R 1 And R 2 Are respectively H, CH 3 ,C 2 H 5 ,C 3 H 7 ,C 4 H 9 ,C 5 H 11 Or C 6 H 12 ;
The molar amount of the ferric salt catalyst accounts for 0.5-50% of the molar amount of the 1, 4-butanediol;
the molar usage of the sulfate ionic liquid catalyst accounts for 5-200% of the molar usage of 1, 4-butanediol;
the molar ratio of the sulfate ionic liquid to the inorganic ferric salt is 0.1-400.
The invention has the following advantages: the catalyst has rich inorganic ferric salt source, low cost, easy obtaining and high catalytic activity. The sulfate ionic liquid has simple synthesis method, no halogen ion, cheap raw materials and little corrosiveness. After the sulfate ionic liquid is added into the reaction system, the reaction of preparing tetrahydrofuran by dehydrating and cyclizing 1,4-butanediol catalyzed by iron salt can be promoted, and the catalytic activity is similar to that of a homogeneous catalyst and a heterogeneous catalyst reported in the known literature. In addition, the reaction does not need a solvent and inert atmosphere protection, and the reaction condition is mild.
Detailed Description
The present invention will be described in further detail with reference to the following specific examples, but the present invention is not limited to the following examples. Variations and advantages that may occur to those skilled in the art may be incorporated into the invention without departing from the spirit and scope of the inventive concept, and the scope of the appended claims is intended to be protected. The procedures, conditions, reagents, experimental methods and the like for carrying out the present invention are general knowledge and common general knowledge in the art except for the contents specifically mentioned below, and the present invention is not particularly limited.
Example 1: preparation of sulfate Ionic liquid catalyst (to [ EMIm)][EtSO 4 ]Example of the design reside in
Adding N-methylimidazole (200mmol, 16.4212g) into a 250mL three-neck reaction flask with magnetons, slowly dropwise adding diethyl sulfate (200mmol, 30.8370g) by using a constant-pressure dropping funnel under the conditions of nitrogen atmosphere and ice bath, stirring for 4-10 hours after the addition is finished, and keeping the temperature below 70 ℃ all the time in the reaction process. Through simple alkylation reaction, colorless to light yellow viscous ionic liquid [ EMIm ] is obtained][EtSO 4 ]。[EMIm][EtSO 4 ]The structure of (A) is determined by nuclear magnetic resonance spectroscopy, 1H NMR (400MHz, CDCl3, TMS) delta (ppm) 9.50 (s, 1H), 7.46-7.43 (m, 2H), 4.29 (q, J =7.2Hz, 2H), 4.08 (q, J =7.2Hz, 2H), 3.99 (s, 3H), 1.54 (t, J =7.2Hz, 3H), 1.26 (t, J =7.2Hz, 3H); 13C NMR (100MHz, CDCl3, TMS) delta (ppm) 137.31,123.68,121.84,63.35,45.16,36.37,15.46,15.23.
Example 2: sulfuric acid ester ionic liquid promoted FeCl 2 Preparation of tetrahydrofuran by catalyzing 1,4-butanediol dehydration cyclization reaction
1,4-butanediol (5mmol, 0.4506 g) and [ EMIm ] were added in this order to a 25mL pressure vessel containing magnetons][EtSO 4 ](5mmol, 1.1804g) and FeCl 2 (2.5mmol, 0.3169g), heated to 120 ℃ and stirred to react for 24 hours. After the reaction is finished, cooling to room temperature, adding an internal standard substance 1, 4-dioxane into the reaction solution, and carrying out quantitative analysis on the reaction solution by using Shimadzu gas chromatograph GC-2014 to determine that the yield of the target product tetrahydrofuran is 65%.
Example 3: feCl 3 Preparation of tetrahydrofuran by catalyzing 1,4-butanediol dehydration cyclization reaction
1,4-butanediol (5mmol, 0.4506 g), feCl were added in this order to a 25mL pressure vessel containing magnetons 3 (0.5mmol, 0.0811g), heated to 120 ℃ and stirred for reaction for 6 hours. After the reaction is finished, cooling to room temperature, adding an internal standard 1, 4-dioxane into the reaction solution, and carrying out quantitative analysis on the reaction solution by using Shimadzu gas chromatograph GC-2014 to determine that the yield of the target product tetrahydrofuran is 69%.
Example 4: sulfuric acid ester ionic liquid promoted FeCl 3 Preparation of tetrahydrofuran by catalyzing 1,4-butanediol dehydration cyclization reaction
To a 25mL pressure-resistant bottle containing magnetons were added 1,4-butanediol (5mmol, 0.4506g) and [ EMIm ] in this order][EtSO 4 ](0.5mmol, 0.1180g) and FeCl 3 (0.5 mmol, 0.0811g) was heated to 120 ℃ and then stirred for 10 minutes. After the reaction is finished, cooling to room temperature, adding an internal standard substance 1, 4-dioxane into the reaction liquid, and carrying out quantitative analysis on the internal standard substance by using a Shimadzu gas chromatograph GC-2014 to determine that the yield of the target product tetrahydrofuran is 5%. Further prolonging the reaction time to 6 hours, the other conditions were not changed, and the yield of the target product tetrahydrofuran was increased to 89%.
Example 5: feBr promotion by sulfate ionic liquid 3 Catalytic 1,4-butanediol dehydration ringPreparation of tetrahydrofuran by chemical reaction
To a 25mL pressure-resistant bottle containing magnetons were added 1,4-butanediol (5mmol, 0.4506g) and [ EMIm ] in this order][EtSO 4 ](0.25mmol, 0.0590g) and FeBr 3 (2.5mmol, 0.7389g), heated to 130 ℃ and stirred for 24 hours. After the reaction is finished, cooling to room temperature, adding an internal standard substance 1, 4-dioxane into the reaction solution, and carrying out quantitative analysis on the reaction solution by using Shimadzu gas chromatograph GC-2014 to determine that the yield of the target product tetrahydrofuran is 95%.
Example 6: sulfate ionic liquid promoted Fe 2 (SO 4 ) 3 Method for preparing tetrahydrofuran by catalyzing dehydration cyclization reaction of 1,4-butanediol
To a 25mL pressure-resistant bottle containing magnetons were added 1,4-butanediol (5mmol, 0.4506g) and [ EMIm ] in this order][EtSO 4 ](0.5mmol, 0.1180g) and Fe 2 (SO 4 ) 3 (0.5mmol, 0.1999g), heated to 120 ℃, stirred and reacted for 6 hours. After the reaction is finished, cooling to room temperature, adding an internal standard 1, 4-dioxane into the reaction solution, and carrying out quantitative analysis on the reaction solution by using Shimadzu gas chromatograph GC-2014 to determine that the yield of the target product tetrahydrofuran is 78%.
Example 7: sulfate ionic liquid promoting Fe (NO) 3 ) 3 ·9H 2 Preparation of tetrahydrofuran by O-catalyzed dehydration cyclization reaction of 1,4-butanediol
To a 25mL pressure-resistant bottle containing magnetons were added 1,4-butanediol (5mmol, 0.4506g) and [ EMIm ] in this order][EtSO 4 ](10mmol, 2.3608g) and Fe (NO) 3 ) 3 ·9H 2 O (2.5mmol, 1.0099g), was heated to 130 ℃ and reacted with stirring for 24 hours. After the reaction is finished, cooling to room temperature, adding an internal standard 1, 4-dioxane into the reaction solution, and carrying out quantitative analysis on the reaction solution by using Shimadzu gas chromatograph GC-2014 to determine that the yield of the target product tetrahydrofuran is 52%.
Example 8: sulfate ionic liquids promote Fe (OTf) 3 Method for preparing tetrahydrofuran by catalyzing dehydration cyclization reaction of 1,4-butanediol
To a 25mL pressure-resistant bottle containing magnetons were added 1,4-butanediol (5mmol, 0.4506g) and [ EMIm ] in this order][EtSO 4 ](10mmol, 2.3608g) and Fe (OTf) 3 (0.025mmol, 0.0126 g) was heated to 130 ℃ and the reaction was stirred for 24 hours. After the reaction is finished, cooling to room temperature, adding an internal standard substance 1, 4-dioxane into the reaction solution, and carrying out quantitative analysis on the reaction solution by using Shimadzu gas chromatograph GC-2014 to determine that the yield of the target product tetrahydrofuran is 85%.
Example 9: comparative example
A method for preparing tetrahydrofuran by catalyzing 1,4-butanediol dehydration cyclization reaction by adopting different metal iron salts and sulfate ionic liquids. 1,4-butanediol (5mmol, 0.4506g), inorganic ferric salt catalyst and ionic liquid [ EMIm ] are added into a 25ml pressure-resistant bottle filled with magnetons in sequence][EtSO 4 ]Heating to the temperature required by the reaction, and stirring for reaction for 10 minutes to 24 hours. After the reaction, the reaction mixture was cooled to room temperature, and the internal standard 1, 4-dioxane was added to the reaction mixture, which was then subjected to quantitative analysis by Shimadzu gas chromatograph GC-2014, and the results are shown in Table 1.
TABLE 1 preparation of tetrahydrofuran by dehydration cyclization reaction of 1,4-butanediol catalyzed by different inorganic iron salts and sulfuric acid ester ionic liquids
As shown in Table 1, under the reaction conditions, the inorganic iron salt and the sulfate ionic liquid have good catalytic effects on the preparation of tetrahydrofuran by the dehydration cyclization reaction of 1,4-butanediol, which is probably because the iron atom and the oxygen atom on the hydroxyl group on the raw material 1,4-butanediol have certain coordination effect, and the sulfate ionic liquid has certain activation effect on the hydrogen atom on the hydroxyl group on the 1,4-butanediol, so that the reaction can be promoted.
Claims (1)
1. A method for preparing tetrahydrofuran by catalyzing 1,4-butanediol cyclodehydration with inorganic ferric salt is characterized in that inorganic ferric salt or sulfate ionic liquid and inorganic ferric salt are used as catalysts for catalyzing dehydration reaction of 1,4-butanediol, and the reaction specifically comprises the following steps: adding 1,4-butanediol, inorganic ferric salt or sulfate ionic liquid and inorganic ferric salt into a reaction system in sequence, stirring and reacting for 10-1440 minutes at the reaction temperature of 40-130 ℃, and obtaining a target product tetrahydrofuran after the reaction is finished;
the inorganic iron salt is FeCl 2 ,FeCl 3 ,FeBr 3 ,Fe 2 (SO 4 ) 3 ,Fe(NO 3 ) 3 ·9H 2 O or Fe (OTf) 3 ;
The sulfate ionic liquid is selected from imidazolium or quaternary ammonium salt ionic liquid, and specifically comprises the following components:
[MMIm][MeSO 4 ],[EMIm][MeSO 4 ],[PMIm][MeSO 4 ],[BMIm][MeSO 4 ],[EMIm][EtSO 4 ],
[EEIm][EtSO 4 ],[PEIm][EtSO 4 ],[BEIm][EtSO 4 ],[PMIm][PrSO 4 ],[PEIm][PrSO 4 ],[BMIm][BuSO 4 ]or [ BEIm][BuSO 4 ]The chemical structural formula is as follows:
in the formula: r, R 1 And R 2 Are respectively H, CH 3 ,C 2 H 5 ,C 3 H 7 ,C 4 H 9 ,C 5 H 11 Or C 6 H 12 ;
The molar amount of the inorganic ferric salt catalyst accounts for 0.5-50% of the molar amount of the 1, 4-butanediol;
the molar usage of the sulfate ionic liquid catalyst accounts for 5-200% of the molar usage of 1, 4-butanediol;
the molar ratio of the sulfate ionic liquid to the inorganic ferric salt is 0.1-400.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202310051846.7A CN115960058A (en) | 2023-02-02 | 2023-02-02 | Method for preparing tetrahydrofuran by catalyzing 1,4-butanediol cyclodehydration with inorganic iron salt |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202310051846.7A CN115960058A (en) | 2023-02-02 | 2023-02-02 | Method for preparing tetrahydrofuran by catalyzing 1,4-butanediol cyclodehydration with inorganic iron salt |
Publications (1)
Publication Number | Publication Date |
---|---|
CN115960058A true CN115960058A (en) | 2023-04-14 |
Family
ID=87361796
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202310051846.7A Pending CN115960058A (en) | 2023-02-02 | 2023-02-02 | Method for preparing tetrahydrofuran by catalyzing 1,4-butanediol cyclodehydration with inorganic iron salt |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN115960058A (en) |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101245054A (en) * | 2007-02-16 | 2008-08-20 | 株式会社晓星 | Method of preparing tetrahydrofuran |
CN101298444A (en) * | 2008-05-30 | 2008-11-05 | 中化国际(苏州)新材料研发有限公司 | Method for preparing tetrahydrofuran by dehydration and cyclization of 1,4-butanediol |
JP2009046429A (en) * | 2007-08-20 | 2009-03-05 | Kyoto Univ | Method for producing ether |
CN101386610A (en) * | 2007-09-11 | 2009-03-18 | 株式会社晓星 | Method for preparing tetrahydrofuran from 1,4-butanediol |
CN104072448A (en) * | 2014-06-13 | 2014-10-01 | 中国科学院山西煤炭化学研究所 | Method for producing tetrahydrofuran by catalyzing dehydration of 1,4-butanediol through L acid |
CN106831675A (en) * | 2015-12-04 | 2017-06-13 | 中国科学院大连化学物理研究所 | A kind of method that iron catalysis dihydroxylic alcohols intramolecular cyclization prepares lactone |
CN108126749A (en) * | 2018-01-23 | 2018-06-08 | 中国科学院过程工程研究所 | A kind of porous alkaline loaded ionic liquid body catalyst and its preparation method and application |
CN113277996A (en) * | 2021-06-03 | 2021-08-20 | 上海贯新科技有限公司 | Method for flexibly producing tetrahydrofuran and gamma-butyrolactone |
CN114437000A (en) * | 2020-11-05 | 2022-05-06 | 中国科学院化学研究所 | Method for preparing cyclic ether by dehydrating and cyclizing diol |
-
2023
- 2023-02-02 CN CN202310051846.7A patent/CN115960058A/en active Pending
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101245054A (en) * | 2007-02-16 | 2008-08-20 | 株式会社晓星 | Method of preparing tetrahydrofuran |
JP2009046429A (en) * | 2007-08-20 | 2009-03-05 | Kyoto Univ | Method for producing ether |
CN101386610A (en) * | 2007-09-11 | 2009-03-18 | 株式会社晓星 | Method for preparing tetrahydrofuran from 1,4-butanediol |
CN101298444A (en) * | 2008-05-30 | 2008-11-05 | 中化国际(苏州)新材料研发有限公司 | Method for preparing tetrahydrofuran by dehydration and cyclization of 1,4-butanediol |
CN104072448A (en) * | 2014-06-13 | 2014-10-01 | 中国科学院山西煤炭化学研究所 | Method for producing tetrahydrofuran by catalyzing dehydration of 1,4-butanediol through L acid |
CN106831675A (en) * | 2015-12-04 | 2017-06-13 | 中国科学院大连化学物理研究所 | A kind of method that iron catalysis dihydroxylic alcohols intramolecular cyclization prepares lactone |
CN108126749A (en) * | 2018-01-23 | 2018-06-08 | 中国科学院过程工程研究所 | A kind of porous alkaline loaded ionic liquid body catalyst and its preparation method and application |
CN114437000A (en) * | 2020-11-05 | 2022-05-06 | 中国科学院化学研究所 | Method for preparing cyclic ether by dehydrating and cyclizing diol |
CN113277996A (en) * | 2021-06-03 | 2021-08-20 | 上海贯新科技有限公司 | Method for flexibly producing tetrahydrofuran and gamma-butyrolactone |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN102070448B (en) | Method for preparing dimethyl succinate | |
KR101125853B1 (en) | Process for preparing of n-methyl pyrrolidone | |
CN112044450B (en) | Acid-base bifunctional biomass carbon-based catalyst and preparation method thereof | |
Guarinos et al. | Conversion of levulinic acid to γ-valerolactone over Zr-containing metal-organic frameworks: Evidencing the role of Lewis and Brønsted acid sites | |
KR20110058002A (en) | Process for preparing of n-methyl pyrrolidone from 1,4-butanediol | |
KR100835476B1 (en) | Production of tetrahydrofuran from 1,4-butanediol | |
AU2013409375B2 (en) | Method for preparing polyoxymethylene dimethyl ether carbonyl compound and methyl methoxyacetate | |
Kumar et al. | Synthesis of an oxygenated fuel additive from a waste biomass derived aldehyde using a green catalyst: an experimental and DFT study | |
CN102757346A (en) | Preparation method of dimethyl fumarate | |
CN108976183B (en) | Method for preparing gamma-valerolactone by furfural gas phase hydrogenation | |
CN115960058A (en) | Method for preparing tetrahydrofuran by catalyzing 1,4-butanediol cyclodehydration with inorganic iron salt | |
CN104788408B (en) | A kind of method that γ valerolactones are produced by hemicellulose | |
EP0030397A1 (en) | Process for the preparation of methyl polyethers and methyl polyethers prepared by this process | |
CN110003150A (en) | A method of utilizing Furfural Production from Xylose | |
CN101070282B (en) | Process for room-temperature ion liquid-catalytic preparation of ethyl linoleate | |
JP6015169B2 (en) | Method for producing tetrahydrofuran | |
CN102219679A (en) | Method for producing oxalic acid ester through CO gas phase coupling | |
WO2015095999A1 (en) | Method for preparing polyoxymethylene dimethyl ether carbonyl compound and methyl methoxyacetate | |
CN111153794A (en) | Method for synthesizing ethyl palmitate by using dodecyl trimethyl ammonium chloride-based eutectic solvent catalyst | |
CN115504952B (en) | Preparation method of 6-methyldihydro-2H-pyran-3 (4H) -one | |
CN114085128B (en) | Method for separating and purifying 1,2,4-butanetriol based on difunctional ionic liquid | |
CN101328132B (en) | Continuous production method of N,N-dimethylacetamide | |
KR101947243B1 (en) | Method of manufacturing muconate including recovery and recycling of spent catalyst | |
CN109694313B (en) | Method for preparing medium-chain aliphatic carboxylic acid | |
CN108752188B (en) | Method for producing valeric acid by hydrogenating biological-based platform compound levulinic acid |
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 |