CN103204764A - Heterogeneous catalyst and method for co-production of 1, 4-butanediol, gamma-butyrolactone and tetrahydrofuran - Google Patents
Heterogeneous catalyst and method for co-production of 1, 4-butanediol, gamma-butyrolactone and tetrahydrofuran Download PDFInfo
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- CN103204764A CN103204764A CN2012100283800A CN201210028380A CN103204764A CN 103204764 A CN103204764 A CN 103204764A CN 2012100283800 A CN2012100283800 A CN 2012100283800A CN 201210028380 A CN201210028380 A CN 201210028380A CN 103204764 A CN103204764 A CN 103204764A
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- Prior art keywords
- butyrolactone
- gamma
- tetrahydrofuran
- butyleneglycol
- reactive metal
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 title claims abstract description 110
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 title claims abstract description 76
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 27
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 title abstract description 17
- 238000004519 manufacturing process Methods 0.000 title abstract description 7
- 239000002638 heterogeneous catalyst Substances 0.000 title abstract 3
- 229910052751 metal Inorganic materials 0.000 claims abstract description 36
- 239000002184 metal Substances 0.000 claims abstract description 36
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 150000001299 aldehydes Chemical class 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims description 43
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 claims description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 9
- 239000011258 core-shell material Substances 0.000 claims description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- JTMCAHGCWBGWRV-UHFFFAOYSA-N 3-hydroxy-2-methylpropanal Chemical compound OCC(C)C=O JTMCAHGCWBGWRV-UHFFFAOYSA-N 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 7
- 229910052707 ruthenium Inorganic materials 0.000 claims description 7
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 6
- 229910052703 rhodium Inorganic materials 0.000 claims description 6
- 239000010948 rhodium Substances 0.000 claims description 6
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 6
- 239000011651 chromium Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims 2
- PIAOXUVIBAKVSP-UHFFFAOYSA-N γ-hydroxybutyraldehyde Chemical compound OCCCC=O PIAOXUVIBAKVSP-UHFFFAOYSA-N 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 239000012071 phase Substances 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- -1 polybutylene terephthalate Polymers 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 description 6
- AIDLAEPHWROGFI-UHFFFAOYSA-N 2-methylbenzene-1,3-dicarboxylic acid Chemical compound CC1=C(C(O)=O)C=CC=C1C(O)=O AIDLAEPHWROGFI-UHFFFAOYSA-N 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 230000009466 transformation Effects 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 229920001707 polybutylene terephthalate Polymers 0.000 description 3
- 229920000909 polytetrahydrofuran Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 241000935974 Paralichthys dentatus Species 0.000 description 2
- 229910000564 Raney nickel Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000000994 depressogenic effect Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000007037 hydroformylation reaction Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical group [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- ACWQBUSCFPJUPN-UHFFFAOYSA-N 2-methylbut-2-enal Chemical compound CC=C(C)C=O ACWQBUSCFPJUPN-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229920002334 Spandex Polymers 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910003120 Zn-Ce Inorganic materials 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 208000012826 adjustment disease Diseases 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000006210 cyclodehydration reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VSHTWPWTCXQLQN-UHFFFAOYSA-N n-butylaniline Chemical compound CCCCNC1=CC=CC=C1 VSHTWPWTCXQLQN-UHFFFAOYSA-N 0.000 description 1
- 230000000802 nitrating effect Effects 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229940069328 povidone Drugs 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 239000004759 spandex Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 238000003809 water extraction Methods 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
A heterogeneous catalyst and a process for the co-production of 1, 4-butanediol, gamma-butyrolactone and tetrahydrofuran, the process comprising: a heterogeneous catalyst having a first active metal and a second active metal is used to catalyze the hydrogenation of an aldehyde mixture comprising 4-hydroxybutyraldehyde to obtain 1, 4-butanediol, gamma-butyrolactone, and tetrahydrofuran.
Description
Technical field
The present invention relates to the preparation of 1,4-butyleneglycol and the method for its derivative of coproduction, especially, relate to having in the presence of the different-phase catalyst of at least two kinds of reactive metals and prepare 1, the method for 4-butyleneglycol and derivative thereof.
Background technology
1,4-butyleneglycol (BDO) is a kind of important organic and fine chemical material, and it is widely used in fields such as medicine, chemical industry, weaving, papermaking, automobile and daily-use chemical industry.And more can produce tetrahydrofuran (THF) (tetrahydrofuran by butyleneglycol, abbreviation THF), polybutylene terephthalate (polybutylene terephthalate, abbreviation PBT), gamma-butyrolactone (gamma butyrolactone, abbreviation GBL), methyl-2-pyrrolidone (1-Methyl-2-pyrrolidone is called for short NMP) and urethane resin important specialization raw material (Specialty Chemicals) and solvents such as (PU resin).Tetrahydrofuran (THF) is the fine solvent of many materials, its can polyethylene dissolving, the vinylidene chloride resin, to butylaniline etc., can be used as the solvent of polymerization and esterification.The application that desolventizes, the THF main application is for producing polytetramethylene ether glycol (PTMEG), and PTMEG can make the PU spandex fiber with vulcabond.Gamma-butyrolactone is a kind of Organic Chemicals and medicine intermediate.In addition, GBL also can be used as the additive of lithium battery electrolytes.
Can make two kinds of aldehydes isomers by the hydroformylation reaction of vinylcarbinol on the general industry, as 4-acetaldol and 2-methyl-3 hydroxy propanal, again this twain-aldehyde compound mixture be carried out hydrogenation and make 1,4-butyleneglycol and 2-methyl isophthalic acid, ammediol.In the hydrogenation, supporting the catalyzer of nickel, rhodium or ruthenium, or Lei Shi nickel (Raney Nickel) usefulness is preferable.No. 1493154 English Patent and No. 5426250 United States Patent (USP) contain the aldehyde mixture hydrogenation of 4-acetaldol respectively as catalyzer with Lei Shi nickel and nickel metal, reaction times is 6 to 8 hours, primary product is 1,4-butyleneglycol, 2-methyl isophthalic acid, ammediol and propyl alcohol.No. 6127584 United States Patent (USP) is catalyzer with organo-metallic rhodium and ruthenium, and adds the hydrogenation that phosphorus compound contains the aldehyde mixture of 4-acetaldol, and product is 1,4-butyleneglycol, 2-methyl isophthalic acid, ammediol and isopropylcarbinol.
No. 4665205 United States Patent (USP) propose with sulfuric acid be catalyzer with 1,4-butyleneglycol cyclodehydration is the method for THF, transformation efficiency is near 99.9%, but sulfuric acid corrosion resistance is strong, increases the processing unit cost.It is the method for catalyzer that No. 481075 Japanese Patent proposes with the aluminum oxide, and this method needs earlier butyleneglycol to be vaporized, and then carries out gas-solid phase reaction under 250 ℃, and the shortcoming of reaction is that catalyst treatment efficient is on the low side, causes production cost to improve.Proposing respectively with solid heteropoly acid and zeolite at No. 2008/0161585 United States Patent (USP) and No. 101386610 Chinese patent is that catalyzer carries out the butyleneglycol dehydration in liquid phase reaction, has the problem that the catalyst treatment ability is on the low side and the life-span is short equally.
Gamma-butyrolactone is to carry out the dehydrogenation reaction manufacturing by 1,4-butyleneglycol, and the catalyzer that dehydrogenation reaction is used is the metal oxide of cupric, platinum, chromium, zinc, calcium isoreactivity composition, and spendable carrier is activated carbon, graphite etc.No. 3232874 Japanese Patent carries out 1,4-butyleneglycol dehydration reaction gamma-butyrolactone processed with the Cu-Cr-Ba complex metal oxides, and transformation efficiency is 96.1%, selection rate is 95.1%.No. 0584408 European patent proposes a kind of use Cu-Cr-Ba or Cu-Cr-Mn-Ba O composite metallic oxide catalyst, and in catalyzer, add Alkali-Metal Na or K, carry out gas-phase reaction in fixed bed reaction, transformation efficiency and selection rate can reach 91% and 94% respectively.No. 1562473 Chinese patent proposes with the Cu-Zn-Ce metal oxide that do not contain Cr as catalyzer, and transformation efficiency is higher than 98%, selection rate is 95%.
No. 6426437 United States Patent (USP) proposes coproduction 1; the flow process of 4-butyleneglycol and gamma-butyrolactone; with rhodium, ruthenium dual catalyst system, vinylcarbinol is carried out hydroformylation reaction in toluene solvant, the aldehyde mixture that contains the 4-acetaldol is proceeded homogeneous reaction under toluene solvant and hydrogen pressure; make 1; 4-butyleneglycol, gamma-butyrolactone and 2-methyl isophthalic acid, ammediol, then; with the water extraction product, and catalyzer stayed in toluene.Yet aforesaid method is soluble in toluene because of gamma-butyrolactone, needs to reclaim in addition the gamma-butyrolactone in the toluene solution, causes energy consumption to increase and catalyst loss.
For improving 1, the efficient of its derivative of 4-butyleneglycol coproduction, simplification manufacturing course, and improve the United States Patent (USP) shortcoming No. 6426437, still having needs a kind of coproduction 1 of exploitation, the method of 4-butyleneglycol, gamma-butyrolactone and tetrahydrofuran (THF), simplifying production process, to be beneficial to the separation of catalyzer, and promote the productive rate of gamma-butyrolactone and/or tetrahydrofuran (THF).
Summary of the invention
In view of this, the invention provides a kind of coproduction 1, the method for 4-butyleneglycol, gamma-butyrolactone and tetrahydrofuran (THF) comprises: make the aldehyde mixture that contains the 4-acetaldol carry out hydrogenation in the presence of different-phase catalyst.
The present invention also provides a kind of different-phase catalyst, comprising: inert support; And be carried on first reactive metal and second reactive metal on this inert support.
The present invention makes 1 by the aldehyde mixture that contains the 4-acetaldol under the hydrogen condition in the presence of different-phase catalyst, 4-butyleneglycol and derivative thereof.Especially, this different-phase catalyst is the core-shell type different-phase catalyst, and constitutes the core of this core-shell type different-phase catalyst by this first reactive metal and second reactive metal, is made of the housing of this core-shell type different-phase catalyst this inert support.
In specific embodiment, this first reactive metal is selected from ruthenium or rhodium; This second reactive metal chosen from Fe, palladium, platinum, copper or chromium.In addition, the material of there is no particular restriction this inert support, so long as not can with the aldehyde mixture reactor that contains the 4-acetaldol all can, this inert support is selected from SiO usually
2, Al
2O
3Or Zr
2O
3Again, the weight ratio of this first reactive metal and second reactive metal is 4: 1 to 1: 1.
Aforesaid aldehyde mixture also comprises 2-methyl-3 hydroxy propanal and propionic aldehyde, and this hydrogenation is to carry out in the presence of water.Wherein, 4-acetaldol in the aldehyde mixture can make 1,4-butyleneglycol and derivative gamma-butyrolactone and tetrahydrofuran (THF), can make the 2-methyl isophthalic acid by 2-methyl-3 hydroxy propanal in the aldehyde mixture, ammediol and derivative isopropylcarbinol thereof can make propyl alcohol by the propionic aldehyde in the aldehyde mixture.
Among the present invention, the addition of this different-phase catalyst accounts for 0.1 weight % to 5 weight % of reaction solution gross weight, is preferably 0.4 weight % to 2 weight %; Temperature of reaction is between 150 ℃ to 250 ℃, preferably between 180 ℃ to 220 ℃; Reaction pressure is between between the 200psig to 1500psig, preferably between between the 250psig to 500psig.
The present invention can be applicable to batch technology and continuous process, comprise continuous-stirring reactor (Continuous Stirred Tank Reactor, CSTR), fixed-bed reactor (Packed Bed Reactor), fluidized-bed reactor (Fluidized Bed Reactor) etc.
Method of the present invention, the different-phase catalyst of the application of the invention is produced 1,4-butyleneglycol, and promotes the productive rate of gamma-butyrolactone and/or tetrahydrofuran (THF), especially increases to 12 hours in the reaction times, can promote the productive rate of gamma-butyrolactone and/or tetrahydrofuran (THF) again.Moreover, under being 4: 1 to 1: 1 and temperature, the weight ratio of the first suitable reactive metal and second reactive metal also can promote the productive rate of gamma-butyrolactone.Again, use different-phase catalyst of the present invention can simplify production process, and have the segregative advantage of catalyzer.In addition, because method of the present invention can be carried out in water, only need reclaim gamma-butyrolactone at aqueous phase, and do not need to reclaim gamma-butyrolactone in organic phase and aqueous phase simultaneously as conventional art, therefore, except simplifying step, the present invention does not need to handle organic phase, has more avoided consume to dissolve in the catalyzer of organic phase.
Embodiment
Below, further specify characteristics of the present invention and effect by specific embodiment, but it is not to limit category of the present invention.
Transformation efficiency and the productive rate put down in writing in this specification sheets calculate according to following equation:
Transformation efficiency=[aldehyde compound addition-reaction back aldehyde compound residual content] (mol)/aldehyde compound addition (mol)]
Productive rate=product growing amount (mol)/[aldehyde compound addition-reaction back aldehyde compound residual content] (mol)
The mensuration of catalyst metal content: catalyzer by aqueous nitric acid (1wt%) boil nitrated after, respectively with the standardized solution of 0.1wt%Ru standard substance (Fluke), 0.1wt%Fe standard substance (Aldrich), the about 0.1wt% concentration of 0.1wt%Pd standard substance (Fluke) preparing metal concentration, demarcate each metal inspection amount line of Atomic Absorption Spectroscopy AAS, measure the catalyst metal content after nitrated.
Embodiment 1
(1) Preparation of Catalyst
0.236 gram ruthenium chloride and 0.078g iron nitrate are dissolved in 15 ml deionized water, after adding 1.28g macromolecule stabilizer Povidone, then, add 0.52 milliliter of formaldehyde of reductive agent, under alkaline environment, stir, make its dissolving, clean with acetone subsequently, take out black colloidal solution and dry.After drying is finished, itself and 5.735 ml deionized water, 1.695 milliliters of ammoniacal liquor, 33.215 milliliters of ethanol are mixed to dissolving each other, add 2.675g template tetraethyl-oxygen siloxanes (TEOS) again, stirred 24 hours, take out black colloidal solution and dry.Then air atmosphere, 400 ℃ of following calcination 3 hours, then, calcined 3 hours to 5 hours under argon gas and hydrogen gas mixture atmosphere, the weight ratio that namely gets required inert support and be silicon-dioxide and Ru/Fe is 4: 1 catalyzer.Catalyzer identifies that with atomic absorption spectrum the catalyst metal content weight ratio is 4: 1 through nitric acid nitrating.
(2) carry out hydrogenation
Be that 4: 1 catalyzer places hydrogenation reactor with the weight ratio of reaction solution and Ru/Fe, reaction solution consists of the 4-acetaldol of 15.1wt%, 2-methyl-3 hydroxy propanal of 3.6wt%, the propionic aldehyde (50 milliliters) of 1.3wt%, wherein, water-content is 80wt%), catalyst concn is 0.4wt%.The control temperature of reaction is 200 ℃, builds with hydrogen and is depressed into 400psig.In the sampling of 3 hours reaction times, sample is with the gas chromatograph analysis, and it the results are shown in table one.
Comparative example 1
50 milliliters of reaction solutions and Raney's nickel catalyst are placed hydrogenation reactor, reaction solution consists of the 4-acetaldol of 15.1wt%, 2-methyl-3 hydroxy propanal of 3.6wt%, the propionic aldehyde of 1.3wt%, the control temperature of reaction is 200 ℃, builds with hydrogen and is depressed into 400psig.In the sampling of 3 hours reaction times, sample is with the gas chromatograph analysis, and it the results are shown in table one.
Table one
* derivative " 2-methyl isophthalic acid, ammediol " and " methyl methacrylaldehyde " productive rate of " other " described in table one and follow-up tabulation expression 2-methyl-3 hydroxy propanal are summed up.
According to table one experimental result as can be known, compared to comparative example 1, promoted the productive rate of gamma-butyrolactone.In addition, compared to No. 6426437 United States Patent (USP), the present invention can produce tetrahydrofuran (THF), and simplifies step, avoids consuming catalyzer.
Embodiment 2
Repeat the Preparation of Catalyst of embodiment 1.Do the hydrogenation test with the catalyzer of embodiment 1, adjusting temperature of reaction is 220 ℃.By table two experimental result as can be known, along with temperature of reaction improves, gamma-butyrolactone and tetrahydrofuran (THF) productive rate significantly increase more thereupon.
Table two
Embodiment 3
Repeat the Preparation of Catalyst of embodiment 1.Do the hydrogenation test with the catalyzer of embodiment 1.The adjustment reaction pressure is 300psig.By table three experimental result as can be known, reduce reaction pressure and be conducive to improve the gamma-butyrolactone productive rate
Table three
Embodiment 4
Repeat the Preparation of Catalyst of embodiment 1, adjust weight ratio that ruthenium chloride and iron nitrate consumption obtain Ru/Fe and be 2: 1 catalyzer.Carry out the hydrogenation test of embodiment 1 with this catalyzer.It the results are shown in table four.
Table four
Embodiment 5
Repeat the Preparation of Catalyst of embodiment 1, iron nitrate is replaced with Palladous nitrate, the weight ratio of preparation Ru/Pd is 4: 1 catalyzer, carries out the hydrogenation test of embodiment 1 with this catalyzer under 500psig, and it the results are shown in table five.
Embodiment 6
Repeat the step of embodiment 5, improving the reaction times is 12 hours, and its reaction result is listed in table five.
Table five
By table five result as can be known, second reactive metal is adjusted into Pd can improves the tetrahydrofuran (THF) productive rate, prolong its productive rate of reaction times and more can further improve to 22.4%.
Claims (18)
1. coproduction 1, the method for 4-butyleneglycol, gamma-butyrolactone and tetrahydrofuran (THF) comprises:
Make the aldehyde mixture that contains the 4-acetaldol carry out hydrogenation in the presence of different-phase catalyst, wherein, this different-phase catalyst comprises inert support and is carried on first reactive metal and second reactive metal on this inert support.
2. coproduction 1 according to claim 1, the method of 4-butyleneglycol, gamma-butyrolactone and tetrahydrofuran (THF), it is characterized in that, this different-phase catalyst is the core-shell type different-phase catalyst, and constitute the core of this core-shell type different-phase catalyst by this first reactive metal and second reactive metal, constituted the housing of this core-shell type different-phase catalyst by this inert support.
3. coproduction 1 according to claim 1, the method for 4-butyleneglycol, gamma-butyrolactone and tetrahydrofuran (THF) is characterized in that, this first reactive metal is selected from ruthenium or rhodium.
4. coproduction 1 according to claim 1, the method for 4-butyleneglycol, gamma-butyrolactone and tetrahydrofuran (THF) is characterized in that, this second reactive metal chosen from Fe, palladium, platinum, copper or chromium.
5. coproduction 1 according to claim 1, the method for 4-butyleneglycol, gamma-butyrolactone and tetrahydrofuran (THF) is characterized in that, this inert support is selected from SiO
2, Al
2O
3Or Zr
2O
3
6. coproduction 1 according to claim 1, the method for 4-butyleneglycol, gamma-butyrolactone and tetrahydrofuran (THF) is characterized in that, carries out this hydrogenation at 150 ℃ to 250 ℃.
7. coproduction 1 according to claim 6, the method for 4-butyleneglycol, gamma-butyrolactone and tetrahydrofuran (THF) is characterized in that, carries out this hydrogenation at 180 ℃ to 220 ℃.
8. coproduction 1 according to claim 1, the method for 4-butyleneglycol, gamma-butyrolactone and tetrahydrofuran (THF) is characterized in that, carries out this hydrogenation at the pressure of 200psig to 1500psig.
9. coproduction 1 according to claim 8, the method for 4-butyleneglycol, gamma-butyrolactone and tetrahydrofuran (THF) is characterized in that, carries out this hydrogenation at the pressure of 250psig to 500psig.
10. coproduction 1 according to claim 1, the method for 4-butyleneglycol, gamma-butyrolactone and tetrahydrofuran (THF) is characterized in that, the weight ratio of this first reactive metal and second reactive metal is 4: 1 to 1: 1.
11. coproduction 1 according to claim 1, the method for 4-butyleneglycol, gamma-butyrolactone and tetrahydrofuran (THF) is characterized in that, this aldehyde mixture also comprises 2-methyl-3 hydroxy propanal and propionic aldehyde.
12. coproduction 1 according to claim 1, the method for 4-butyleneglycol, gamma-butyrolactone and tetrahydrofuran (THF) is characterized in that, this hydrogenation is to carry out in the presence of water.
13. a different-phase catalyst comprises:
Inert support; And
Be carried on first reactive metal and second reactive metal on this inert support.
14. different-phase catalyst according to claim 13, it is characterized in that, this different-phase catalyst is the core-shell type different-phase catalyst, and constitutes the core of this core-shell type different-phase catalyst by this first reactive metal and second reactive metal, is made of the housing of this core-shell type different-phase catalyst this inert support.
15. different-phase catalyst according to claim 13 is characterized in that, this first reactive metal is selected from ruthenium or rhodium.
16. different-phase catalyst according to claim 13 is characterized in that, this second reactive metal chosen from Fe, palladium, platinum, copper or chromium.
17. different-phase catalyst according to claim 13 is characterized in that, this inert support is selected from SiO
2, Al
2O
3Or Zr
2O
3
18. different-phase catalyst according to claim 13 is characterized in that, the weight ratio of this first reactive metal and second reactive metal is 4: 1 to 1: 1.
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| TW101101671A TWI471296B (en) | 2012-01-17 | 2012-01-17 | A heterogeneous catalyst and a method of producing 1,4-butanediol, γ-butyrolactone and tetrahydrofuran |
| TW101101671 | 2012-01-17 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103861616A (en) * | 2014-02-24 | 2014-06-18 | 万华化学集团股份有限公司 | Catalyst, preparation method thereof and method for performing cooperative production on 1,4-butanediol, gamma-butyrolactone and tetrahydrofuran in presence of catalyst |
| WO2023080071A1 (en) * | 2021-11-02 | 2023-05-11 | 株式会社レゾナック | Method for producing 4-hydroxybutyl aldehyde, method for producing gamma butyrolactone, method for producing n-methyl-2-pyrrolidone, and compound |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0584408A2 (en) * | 1992-08-25 | 1994-03-02 | Tonen Chemical Corporation | Process for the preparation of gamma-butyrolactone |
| US5426250A (en) * | 1993-01-11 | 1995-06-20 | Darien Chemical Corporation | Process for preparing 1,4-butanediol |
| CN1177310A (en) * | 1995-03-03 | 1998-03-25 | 纳幕尔杜邦公司 | Improved Ru, Re/carbon catalyst fro hydrogenation in aqueous solution |
| US6426437B1 (en) * | 2000-12-13 | 2002-07-30 | Arco Chemical Technology, L.P. | Hydroformylation process |
| CN1736604A (en) * | 2005-07-27 | 2006-02-22 | 北京化工大学 | Egg shell type metal catalyst, its preparing process and application method |
| CN102019431A (en) * | 2010-09-30 | 2011-04-20 | 大连理工大学 | Metallic nano cluster/silicon dioxide hollow nuclear shell structured nanoparticles and preparation method thereof |
| CN102070501A (en) * | 2009-11-25 | 2011-05-25 | Sk能源株式会社 | Method for preparing n-methylpyrrolidone from 1,4-butanediol |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110250122A1 (en) * | 2008-11-07 | 2011-10-13 | The Regents Of The University Of California | Core-Shell Nanocatalyst For High Temperature Reactions |
-
2012
- 2012-01-17 TW TW101101671A patent/TWI471296B/en not_active IP Right Cessation
- 2012-01-30 CN CN201210028380.0A patent/CN103204764B/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0584408A2 (en) * | 1992-08-25 | 1994-03-02 | Tonen Chemical Corporation | Process for the preparation of gamma-butyrolactone |
| US5426250A (en) * | 1993-01-11 | 1995-06-20 | Darien Chemical Corporation | Process for preparing 1,4-butanediol |
| CN1177310A (en) * | 1995-03-03 | 1998-03-25 | 纳幕尔杜邦公司 | Improved Ru, Re/carbon catalyst fro hydrogenation in aqueous solution |
| US6426437B1 (en) * | 2000-12-13 | 2002-07-30 | Arco Chemical Technology, L.P. | Hydroformylation process |
| CN1736604A (en) * | 2005-07-27 | 2006-02-22 | 北京化工大学 | Egg shell type metal catalyst, its preparing process and application method |
| CN102070501A (en) * | 2009-11-25 | 2011-05-25 | Sk能源株式会社 | Method for preparing n-methylpyrrolidone from 1,4-butanediol |
| CN102019431A (en) * | 2010-09-30 | 2011-04-20 | 大连理工大学 | Metallic nano cluster/silicon dioxide hollow nuclear shell structured nanoparticles and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103861616A (en) * | 2014-02-24 | 2014-06-18 | 万华化学集团股份有限公司 | Catalyst, preparation method thereof and method for performing cooperative production on 1,4-butanediol, gamma-butyrolactone and tetrahydrofuran in presence of catalyst |
| CN103861616B (en) * | 2014-02-24 | 2016-03-09 | 万华化学集团股份有限公司 | A kind of catalyst, its preparation method and adopt this catalyst coproduction to prepare the method for BDO, gamma-butyrolacton and oxolane |
| WO2023080071A1 (en) * | 2021-11-02 | 2023-05-11 | 株式会社レゾナック | Method for producing 4-hydroxybutyl aldehyde, method for producing gamma butyrolactone, method for producing n-methyl-2-pyrrolidone, and compound |
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|---|---|
| CN103204764B (en) | 2015-09-02 |
| TW201331169A (en) | 2013-08-01 |
| TWI471296B (en) | 2015-02-01 |
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