CN1485322A - A kind of preparation method of tetrahydrofuran - Google Patents
A kind of preparation method of tetrahydrofuran Download PDFInfo
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- CN1485322A CN1485322A CNA021307806A CN02130780A CN1485322A CN 1485322 A CN1485322 A CN 1485322A CN A021307806 A CNA021307806 A CN A021307806A CN 02130780 A CN02130780 A CN 02130780A CN 1485322 A CN1485322 A CN 1485322A
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- Prior art keywords
- catalyzer
- tetrahydrofuran
- described preparation
- noble metal
- hydrogen
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 title claims abstract description 100
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims description 21
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 39
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 19
- 239000010970 precious metal Substances 0.000 claims abstract description 17
- 239000010949 copper Substances 0.000 claims abstract description 15
- 229910052802 copper Inorganic materials 0.000 claims abstract description 13
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 13
- 239000011701 zinc Substances 0.000 claims abstract description 13
- 239000001257 hydrogen Substances 0.000 claims abstract description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 12
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims abstract description 12
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 12
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 12
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 11
- 239000002243 precursor Substances 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052742 iron Inorganic materials 0.000 claims abstract description 4
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 4
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 4
- 229910052702 rhenium Inorganic materials 0.000 claims abstract description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 3
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims abstract description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract 2
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 239000010953 base metal Substances 0.000 claims description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 7
- 238000007598 dipping method Methods 0.000 claims description 5
- 238000005470 impregnation Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- 150000002736 metal compounds Chemical class 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 17
- 239000007791 liquid phase Substances 0.000 abstract description 8
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 abstract 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 abstract 1
- 229930188620 butyrolactone Natural products 0.000 abstract 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 239000011976 maleic acid Substances 0.000 abstract 1
- 239000001384 succinic acid Substances 0.000 abstract 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 abstract 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 15
- 239000011572 manganese Substances 0.000 description 14
- 229910052748 manganese Inorganic materials 0.000 description 13
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 10
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 8
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 8
- 239000002250 absorbent Substances 0.000 description 7
- 230000002745 absorbent Effects 0.000 description 7
- 239000003610 charcoal Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 230000002829 reductive effect Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- XUPYJHCZDLZNFP-UHFFFAOYSA-N butyl butanoate Chemical compound CCCCOC(=O)CCC XUPYJHCZDLZNFP-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241001099111 Hibiscus latent Singapore virus Species 0.000 description 1
- 206010020852 Hypertonia Diseases 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 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 description 1
- 230000004044 response Effects 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
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- Catalysts (AREA)
Abstract
一种四氢呋喃的制备方法，包括：在加氢催化剂的存在下，使选自马来酸、琥珀酸和γ－丁内酯中的一种可氢化前体或其中一种以上的混合物与氢气接触，分离并收集四氢呋喃，其中的加氢催化剂是由负载于无机载体上的选自钯、铂、钌、铼中的一种贵金属和选自铜、锌、锰、铝、铁和镍中的一种或一种以上的非贵金属组成。本发明的优点在于，加氢催化剂使用一种贵金属组分和几种非贵金属组合负载于无机载体上，贵金属使用量少，含量低；在中等压力条件下实现对马来酸、琥珀酸、γ－丁内酯等可氢化前体直接液相加氢制备四氢呋喃，显著降低了液相加氢的压力条件。A method for preparing tetrahydrofuran, comprising: in the presence of a hydrogenation catalyst, making a hydrogenatable precursor selected from maleic acid, succinic acid and γ-butyrolactone or a mixture of more than one thereof contact with hydrogen , separate and collect tetrahydrofuran, wherein the hydrogenation catalyst is a noble metal selected from palladium, platinum, ruthenium, rhenium and a noble metal selected from copper, zinc, manganese, aluminum, iron and nickel supported on an inorganic carrier One or more non-precious metals. The advantage of the present invention is that the hydrogenation catalyst uses a combination of noble metal components and several non-noble metals to load on the inorganic carrier, and the amount of noble metal used is small and the content is low; - Butyrolactone and other hydrogenatable precursors are directly hydrogenated in liquid phase to prepare tetrahydrofuran, which significantly reduces the pressure conditions of liquid phase hydrogenation.
Description
Technical field
The present invention relates to the preparation method that the tetrahydrochysene furan is fed.
Technical background
Tetrahydrofuran (THF) is lower boiling (66 a ℃) solvent, is particularly suitable for dissolving polyvinyl chloride, polypropylene and polyvinylidene chloride, is commonly used for accurate tape clean-out system or as the protective material of aluminium electroplating bath; Tetrahydrofuran (THF) also is the valuable intermediate of a series of pharmaceutical chemicalss of preparation and plastics, be mainly used in and produce poly-tetramethylene glycol ether, poly-tetramethylene glycol ether is used to make polyurethane elastomeric fiber, and the increasing sharply of polyurethane elastomeric fiber demand promoted increasing sharply to the demand of tetrahydrofuran (THF) indirectly.
In the prior art, the patent of relevant preparation tetrahydrofuran (THF) is a lot, and wherein most patent is from the cis-butenedioic anhydride or derivatives thereof, uses loaded noble metal catalyst, carries out high-pressure liquid phase hydrogenation preparing tetrahydrofuran (THF).US4,550,185 and US4,609,636, be hydrogenation catalyst with 3%wtPd/3%wtRe/C, in 180 ℃ to 230 ℃ temperature range, toxilic acid aqueous solution hydrogenation under greater than the pressure of 17.0MPa is generated tetrahydrofuran (THF) and 1, the mixture of multiple materials such as 4-butyleneglycol; US5,478,952 to disclose with 1%wtRu/4%wtRe/C be hydrogenation catalyst, under the reaction conditions of 250 ℃ and 13.0～17.0MPa from succsinic acid aqueous solution preparation tetrahydrofuran (THF), gamma-butyrolactone and 1, the mixture of 4-butyleneglycol etc.; US5,473,086, JP08141396, JP06157490 etc. disclose the method for working load type noble metal catalyst high-pressure liquid phase hydrogenation preparing tetrahydrofuran (THF).The described catalyzer of these patents all is two or more a precious metal element of load on absorbent charcoal carrier, and the precious metal total content is higher, and is general greater than 5% of catalyzer total mass, makes that the catalyzer manufacturing cost is higher; And use these many noble metal catalysts under very high pressure condition, generally to be higher than 15.0MPa, and tetrahydrofuran (THF) just can be obtained yield preferably, and high top pressure operation has not only increased facility investment but also has increased operation easier.And when pressure was lower than 10.0MPa, product was based on gamma-butyrolactone, and the tetrahydrofuran (THF) yield is low, generally was lower than 40%.US4 in addition, 965,387 have introduced and have used CuO/Cr
2O
3/ ZnO/Al
2O
3Being catalyzer, under the pressure of 4.2MPa, be that the raw material gas phase hydrogenation prepares the tetrahydrochysene furan food in one's mouth and gamma-butyrolactone with the fused cis-butenedioic anhydride, but catalyzer contains great toxicity Cr
2O
3Composition, and need at first raw material to be vaporized, complicated cis-butenedioic anhydride gasification process increased.
Summary of the invention
The purpose of this invention is to provide a kind ofly under lower pressure, adopt non-toxic catalyst to prepare the method for tetrahydrofuran (THF), solve the prior art hypertonia or use the problem of toxic component catalyst by liquid phase catalytic hydrogenation.
Tetrahydrofuran (THF) preparation method provided by the invention comprises: in the presence of hydrogenation catalyst, one or more mixture in the hydrogenatable precursors such as being selected from toxilic acid, succsinic acid and gamma-butyrolactone is contacted with hydrogen, separate and the collection tetrahydrofuran (THF), hydrogenation catalyst wherein is made up of one or more base metals that are selected from a kind of precious metal among palladium Pd, platinum Pt, ruthenium Ru, the rhenium Re and are selected from copper Cu, zinc Zn, manganese Mn, aluminium Al, iron Fe, the nickel that are carried on the inorganic carrier.
The invention is characterized in that catalyzer is to load on the inorganic carrier simultaneously with a kind of precious metal and one or more base metal, described precious metal is selected from a kind of in the metals such as Pd, Pt, Ru, Re, described base metal is selected from one or more in the metals such as Cu, Zn, Mn, Al, Fe, Ni, and described carrier is selected from a kind of in gac, aluminum oxide and the titanium oxide etc.Wherein the charge capacity (with catalyzer gross weight is benchmark) of precious metal element on catalyzer is about 0.1～10%, and preferably 1～6%; The charge capacity of base metal element is about 0.1～30%, and preferably 3～10%.This catalyst composition can also the further modification by sneaking into one or more metals that are selected from IA family or IIA group.
The catalyzer that the present invention uses can be used immersion process for preparing, with solution that contains a kind of precious metal chemical complex and the solution that contains one or more non-noble metal compounds, is divided into one or more impregnation steps, the incipient impregnation inorganic carrier that is:.After each step dipping, the gained catalyzer all is dried and desolvates to remove.Drying temperature is between 30～200 ℃, preferably between about 60～150 ℃.Dried catalyzer need be preferably under about 200～400 ℃ temperature condition at about 150～800 ℃, carries out roasting.Roasting process can carry out under the protection of rare gas element (as nitrogen).
Described catalyzer before use can be in 150～500 ℃ temperature range, preferably in 200～300 ℃ temperature range, reduces with the mixed gas of pure hydrogen or hydrogen and rare gas element (as nitrogen).
The reaction raw materials that the present invention uses is taken from one or more the mixture in the hydrogenatable precursors such as toxilic acid, succsinic acid, gamma-butyrolactone.Wiring solution-forming when toxilic acid, succsinic acid use, solvent can be water, low-carbon alcohol or gamma-butyrolactone, and concentration range can be from the dilute solution to the saturated solution, and general weight percent concentration is about 20～40%.Directly charging of gamma-butyrolactone.The stoichiometry of general hydrogen need surpass the metering that participates in reaction, and unreacted hydrogen can be recycled.Hydrogen gas space velocity is 200～20000hr
-1, preferred 800～15000hr
-1, the liquid hourly space velocity of hydrogenatable precursor is 0.1～20hr
-1, preferred 0.2～15hr
-1
Liquid phase hydrogenation reaction of the present invention can be carried out in batch reactor (as stirred autoclave) and flow reactor multiple reactors such as (as fluidized-bed reactor and fixed-bed reactor).About 150～300 ℃ of temperature of reaction, preferred 200～280 ℃, reaction pressure can be 1～15MPa, preferred 2～10MPa.The hydrogen and the toxilic acid aqueous solution or hydrogenatable precursor such as succsinic acid, gamma-butyrolactone pass through hydrogenation catalyst together in the same way.The reaction product tetrahydrofuran (THF) can effectively be separated by fractionation with by products such as gamma-butyrolactone, succsinic acid, butanols, butyric acid.Wherein succsinic acid and gamma-butyrolactone can optionally be returned hydrotreating stage.
The invention has the advantages that hydrogenation catalyst uses a kind of noble metal component and several base metal combination load on inorganic carrier, the precious metal usage quantity is few, and content is low; Under the middle pressure condition, realize the direct liquid-phase hydrogenatins of hydrogenatable precursor such as toxilic acid, succsinic acid, gamma-butyrolactone are prepared tetrahydrofuran (THF), significantly reduced the pressure condition of liquid-phase hydrogenatin.
Embodiment
The following examples are for composition and catalyzer of the present invention to catalyzer of the present invention are applicable to the response characteristic of middle pressure condition, and never are limitations of the present invention.
In these embodiments, its selectivity is with mole C
4What calculate for the basis (is that selectivity is the C that is converted to product
4The molecular fraction of charging).Charging air speed HLSV and gas space velocity GHSV are that the volume (comprising carrier bulk) with catalyzer calculates.Wherein THF is a tetrahydrofuran (THF), and BDO is 1, and 4-butyleneglycol, GBL are gamma-butyrolactones, and BuOH is a butanols, and BuAC is a butyric acid, and " Others " comprises as by products such as butyl butyrate, propionic acid, propyl alcohol, methane, methyl alcohol.
Embodiment 1
Prepare a kind of precious metal and a kind of base metal and load on catalyzer on the absorbent charcoal carrier: 2%Pd/0.3～1.5%M/C simultaneously, wherein M represents a kind of in the base metal elements such as Cu, Zn, Mn and Al.
Absorbent charcoal carrier is the gac GH-15 that is produced by brilliance timber mill, Beijing.Commercially available GH-15 is a Ф 1.5mm granular active carbon, 40 orders is got in its grinding sieved to 26 purposes.
The preparation of Pd solution is with 12.7g palladium nitrate solution 600ml deionized water dissolving.The preparation of base metal M solution is, gets 1.2g cupric nitrate, 1.4g zinc nitrate, 4.9ml concentration and is 50% manganese nitrate solution or 1.8g aluminum nitrate and use the 120ml deionized water dissolving respectively.
225g (about 100ml) 26～40 purpose gacs with 600ml palladium nitrate solution dipping, are fully stirred, left standstill then 4 hours, 80 ℃ in loft drier dry 12 hours, make 2%Pd/C; Get 25g2%Pd/C,, fully stir, left standstill 4 hours with containing the 120ml solution impregnation of Cu, again 80 ℃ in loft drier dry 12 hours, make catalyzer 2%Pd0.6%Cu/C; Use the same method and make catalyzer: 2%Pd0.6%Zn/C and 2%Pd1.5%Mn/C.Under 300～500 ℃ temperature condition, catalyzer is carried out roasting then, the preceding carrier (nitrate) of each element is decomposed, thereby make each element form with oxide compound on absorbent charcoal carrier exist with nitrogen protection.
5ml (about 2.5g) the catalyzer 5ml fixed-bed micro-reactor of packing into is reduced.Reaction raw materials is a gamma-butyrolactone, and concrete reductive condition is that at first the temperature rise rate with 1 ℃/min is raised to 280 ℃, reduces 12 hours in the presence of hydrogen; The flow of reduction hydrogen is 500ml/min, and pressure is normal pressure.Catalyzer after the reduction is that 250 ℃, pressure are that 6.0MPa, LHSV are 0.36h in temperature
-1, GHSV is 6000h
-1Condition under GBL is carried out hydrogenation, in detail reaction result is listed in the table 1.
Table 1 Pd and a kind of base metal combination catalyst reaction result
Selectivity %
Catalyzer is formed transformation efficiency/%
THF BDO BuOH BuAC Others
2％Pd/C 29.3 6.9 0 4.0 87.6 1.6
2％Pd·0.6％Cu/C 16.6 46.8 0 4.6 47.2 1.5
2％Pd·0.6％Zn/C 16.8 85.6 3.3 1.8 7.7 1.65
2％Pd·1.5％Mn/C 24.8 48.7 0 4.1 43.9 3.3
Embodiment 2
Prepare a kind of precious metal and two kinds of base metals and load on catalyzer on the absorbent charcoal carrier: 2%Pd0.3～1.5%M simultaneously
10.3～1.5%M
2/ C, wherein M
1And M
2Represent a kind of in the base metal elements such as Cu, Zn, Mn and Al respectively.
Prepare 2%Pd/C with method with embodiment 1.Get 1.2g cupric nitrate and 1.4g zinc nitrate 120ml deionized water dissolving, get 25g 2%Pd/C and use dipping method to make catalyzer: 2%Pd0.6%Cu0.6%Zn/C with embodiment 1; Get 1.2g cupric nitrate and 4.9ml concentration and be 50% manganese nitrate solution and prepare catalyzer: 2%Pd0.6%Cu1.5%Mn/C with the method for the above-mentioned catalyzer of preparation; With catalyzer being handled with the heat treating method of embodiment 1.With catalyst reduction condition catalyzer is activated with embodiment 1.Under the reaction conditions with embodiment 1 catalyzer is estimated, detailed reaction result is listed in the table 2.
The catalyst reaction result of table 2 Pd and two kinds of base metal combinations
Transformation efficiency selectivity/%
Catalyzer is formed
/％ THF BDO BuOH BuAC Others
2％Pd·0.6％Cu·0.6％Zn/C 26.68 1.9 0 1.9 15.3 1.0
2％Pd·0.6％Cu·1.5％Mn/C 36.9 52.2 0 2.7 41.4 3.6
Embodiment 3
Prepare a kind of precious metal and three kinds of base metals and load on catalyzer on the absorbent charcoal carrier: 2%Pd0.3～1.5%M simultaneously
10.3～1.5%M
20.3～1.5%M
3/ C, wherein M
1, M
2And M
3Represent a kind of in the base metal elements such as Cu, Zn, Mn and Al respectively.
Method with embodiment 1 prepares 2%Pd/C.Get 1.2g cupric nitrate, 1.4g zinc nitrate and 4.9ml concentration and be 50% manganese nitrate solution, be dissolved into the 120ml mixing solutions, use with the method for embodiment 1 25g 2%Pd/C is flooded preparation 2%Pd0.6%Cu0.6%Zn1.5%Mn/C; Get 1.2g cupric nitrate, 1.8g aluminum nitrate and 4.9ml concentration and be 50% manganese nitrate solution, be dissolved into the 120ml mixing solutions, use the method preparation with embodiment 1: 2%Pd0.6%Cu0.3%Al1.5%Mn/C.Method with embodiment 1 is heat-treated catalyzer.With similarly to Example 1 reductive condition catalyzer is activated.React under the condition identical with embodiment 1, detailed reaction result is listed in the table 3.
The catalyst reaction result of table 3 Pd and three kinds of base metal combinations
Transformation efficiency selectivity/%
Catalyzer is formed
/％ THF BDO BuOH BuAC Others
2％Pd·0.6％Cu·0.6％Zn·1.5％Mn/C 89.7 81.1 0.5 14.0 3.2 1.2
2％Pd·0.6％Cu·0.3％Al·1.5％Mn/C 69.7 77.7 0.2 1.6 19.0 1.4
Embodiment 4
Prepare a kind of precious metal and four kinds of base metals and load to catalyzer on the absorbent charcoal carrier: 2%Pd0.6%Cu0.6%Zn1.5%Mn0.3%Al/C simultaneously
Method with embodiment 1 prepares 2%Pd/C.With 1.2g cupric nitrate, 1.4g zinc nitrate, 4.9ml concentration is 50% manganese nitrate solution and 1.75g aluminum nitrate 115ml deionized water dissolving, obtains about 120ml base metal nitrate mixed solution.The above-mentioned 25g 2%Pd/C that makes of method dipping with embodiment 1 makes catalyzer: 2%Pd0.6%Cu0.6%Zn1.5%Mn0.3%Al/C.Method with embodiment 1 is heat-treated catalyzer.With similarly to Example 1 reductive condition catalyzer is activated.At 230～270 ℃ of temperature, pressure 2～8.0MPa, LHSV 0.24～12hr
-1, GHSV 1200～12000h
-r1Condition under to the gamma-butyrolactone shortening, experimental result is listed in the table 4.
The catalyst reaction result of table 4 Pd and four kinds of base metal combinations
Reaction conditions selectivity (%)
Transformation efficiency
Temperature, pressure LHSV GHSV
THF BDO BuOH BuAC Others
/℃ /Mpa /h
-1 /h
-1 /％
230 6.0 0.24 6000 62.0 79.8 2.0 11.5 2.2 4.5
250 6.0 0.24 6000 74.8 81.2 0.5 5.8 8.5 4.0
270 6.0 0.24 6000 94.9 71.4 0.1 24.6 1.1 2.8
250 2.0 0.24 6000 67.2 47.8 0.4 4.8 20.6 26.4
250 6.0 0.24 6000 83.0 73.2 1.9 4.6 5.4 14.9
250 8.0 0.24 6000 88.0 79.8 6.1 3.2 1.2 9.7
250 6.0 0.24 6000 99.3 85.1 0 14.5 0 0.4
250 6.0 2.40 6000 26.8 36.1 55.0 0.4 0 8.5
250 6.0 12.0 6000 9.80 16.3 78.3 0.4 0 5.0
250 6.0 0.24 1200 76.6 68.8 0 1.8 22.1 7.3
250 6.0 0.24 6000 91.5 81.5 0 5.7 3.2 9.6
250 6.0 0.24 12000 78.3 84.7 2.1 9 1.4 2.8
Embodiment 5
The toxilic acid aqueous solution with 25% is that raw material carries out catalytic hydrogenation reaction, reaction conditions and result's row and table 5.
Used catalyzer is identical with embodiment 4.
The toxilic acid hydrogenation in aqueous solution reaction result of table 5 pair 25%
Reaction conditions transforms selectivity (%)
Pressure and temp LHSV GHSV leads
THF BDO GBL BuOH BuAC Others
/MPa /℃ /h
-1 /h
-1 /％
6.0 250 0.24 6000 100 72.8 0 9.7 11.5 5.1 0.9
6.0 230 0.24 6000 100 68.3 0 18.9 5.8 6.8 0.2
From the data of table 1～5 as can be seen, the inventive method is the feedstock production tetrahydrofuran (THF) with toxilic acid, succsinic acid or gamma-butyrolactone, can obtain effect preferably under lower pressure.
Claims (9)
1. the preparation method of a tetrahydrofuran (THF), comprise: in the presence of hydrogenation catalyst, make a kind of hydrogenatable precursor that is selected from toxilic acid, succsinic acid and the gamma-butyrolactone or wherein more than one mixture contact with hydrogen, separate and also to collect tetrahydrofuran (THF), hydrogenation catalyst wherein is made up of one or more the base metal that is selected from a kind of precious metal in palladium, platinum, ruthenium, the rhenium and is selected from copper, zinc, manganese, aluminium, iron and the nickel that is carried on the inorganic carrier.
2. according to the described preparation method of claim 1, it is characterized in that described carrier is selected from gac, aluminum oxide and titanium oxide.
3. according to the described preparation method of claim 1, it is characterized in that the charge capacity of precious metal on catalyzer is 0.1～10%, non-noble metal charge capacity is 0.1～30%.
4. according to the described preparation method of claim 1, it is characterized in that the charge capacity of precious metal is 1～6%, non-noble metal charge capacity is 3～10%.
5. according to the described preparation method of claim 1, it is characterized in that, described catalyzer immersion process for preparing, that is: with solution that contains a kind of precious metal chemical complex and the solution that contains one or more non-noble metal compounds, be divided into one or more impregnation steps, the incipient impregnation inorganic carrier, after each step dipping, the gained catalyzer all is dried, drying temperature between 30～200 ℃, the roasting under 150～800 ℃ of conditions of dried catalyzer.
6. according to the described preparation method of claim 1, it is characterized in that, in 150～500 ℃ temperature range, reduce before described catalyzer uses with the mixed gas of pure hydrogen or hydrogen and rare gas element.
7. according to the described preparation method of claim 1, it is characterized in that, wiring solution-forming when toxilic acid, succsinic acid use, strength of solution is 20～40%.
8. according to the described preparation method of claim 1, it is characterized in that hydrogen gas space velocity is 200～20000hr
-1, the liquid hourly space velocity of hydrogenatable precursor is 0.1～20hr
-1, 150～300 ℃ of temperature of reaction, reaction pressure are 1～15MPa.
9. according to claim 1 or 8 described preparation methods, it is characterized in that hydrogen gas space velocity is 800～15000hr
-1, the liquid hourly space velocity of hydrogenatable precursor is 0.2～15hr
-1, 200～280 ℃ of temperature of reaction, reaction pressure are 2～10MPa.
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| CN104888802A (en) * | 2015-05-21 | 2015-09-09 | 中国科学院青岛生物能源与过程研究所 | Catalyst for preparing butyric acid and preparation method and application of catalyst |
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| CN111905755B (en) * | 2020-07-16 | 2022-07-05 | 浙江恒逸石化研究院有限公司 | Catalyst for hydrogenation of 2,2,4, 4-tetramethyl-1, 3-cyclobutanedione and preparation method and application thereof |
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| CN119504662A (en) * | 2024-11-20 | 2025-02-25 | 聚碳氧联新材料科技(无锡)有限公司 | A kind of tetrahydrofuran and preparation method thereof |
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