CN110354877A - Adipic acid reduction prepares the catalyst and preparation method of 1,6-HD - Google Patents
Adipic acid reduction prepares the catalyst and preparation method of 1,6-HD Download PDFInfo
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- CN110354877A CN110354877A CN201910699999.6A CN201910699999A CN110354877A CN 110354877 A CN110354877 A CN 110354877A CN 201910699999 A CN201910699999 A CN 201910699999A CN 110354877 A CN110354877 A CN 110354877A
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- catalyst
- adipic acid
- hexylene glycol
- transition metal
- preparation
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- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000003054 catalyst Substances 0.000 title claims abstract description 55
- 239000001361 adipic acid Substances 0.000 title claims abstract description 30
- 235000011037 adipic acid Nutrition 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 230000009467 reduction Effects 0.000 title claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000243 solution Substances 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 21
- 239000011261 inert gas Substances 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 150000003624 transition metals Chemical class 0.000 claims abstract description 15
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 13
- 239000011259 mixed solution Substances 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000000694 effects Effects 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 7
- CUXQLKLUPGTTKL-UHFFFAOYSA-M microcosmic salt Chemical compound [NH4+].[Na+].OP([O-])([O-])=O CUXQLKLUPGTTKL-UHFFFAOYSA-M 0.000 claims abstract description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- 239000011574 phosphorus Substances 0.000 claims abstract description 5
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 3
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 3
- 229940051250 hexylene glycol Drugs 0.000 claims abstract 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N hexylene glycol Natural products CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims description 24
- 230000008569 process Effects 0.000 claims description 13
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 13
- -1 transition metal salt Chemical class 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 1
- 239000007789 gas Substances 0.000 claims 1
- 230000009466 transformation Effects 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 13
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 11
- 238000003756 stirring Methods 0.000 description 10
- 238000006722 reduction reaction Methods 0.000 description 9
- 229910019891 RuCl3 Inorganic materials 0.000 description 8
- 239000012279 sodium borohydride Substances 0.000 description 8
- 229910000033 sodium borohydride Inorganic materials 0.000 description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 7
- 239000003638 chemical reducing agent Substances 0.000 description 7
- 229910017604 nitric acid Inorganic materials 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 238000012545 processing Methods 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000013459 approach Methods 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002459 sustained effect Effects 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- UDSFAEKRVUSQDD-UHFFFAOYSA-N Dimethyl adipate Chemical compound COC(=O)CCCCC(=O)OC UDSFAEKRVUSQDD-UHFFFAOYSA-N 0.000 description 1
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 229910004619 Na2MoO4 Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910000808 amorphous metal alloy Inorganic materials 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000004621 biodegradable polymer Substances 0.000 description 1
- 229920002988 biodegradable polymer Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 125000002425 furfuryl group Chemical group C(C1=CC=CO1)* 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1856—Phosphorus; Compounds thereof with iron group metals or platinum group metals with platinum group metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of adipic acid reduction preparations 1, the catalyst of 6- hexylene glycol, it includes active component, transition metal, phosphorus and carrier, and the active component is Ru, and the transition metal is Co, Cu, at least one of Ni, Fe, Mo and Zn, the carrier is porous structure material, such as diatomite, active carbon.Configuration contains the soluble-salt of any of the above-described kind of transition metal and the mixed solution of microcosmic salt first, and inert gas is passed through into solution, is formed using inert gas bubble as the gas-liquid interface of template；Then certain density NaBH is slowly added dropwise into mixed solution4Solution is then rapidly added catalyst activity component；Carrier is added in mixed liquor after reaction, reaction a period of time, water washing to neutrality filters, and it is dry, obtain amorphous catalyst.The catalyst is at low cost, and the Transformation efficiency is up to 90 % of adipic acid, the yield of 1,6- hexylene glycol can reach 65%, achieve preferable technical effect, has preferable industrial prospect.
Description
Technical field:
The present invention relates to catalyst preparation technical fields, and in particular to a kind of preparation of inertia bubble template can be by oneself
The catalyst of diacid one-step synthesis method 1,6-HD.
Background technique:
Glycol industrially has consequence, they are applied to various fine chemicals, the material of drug as raw material
Material and biodegradable polymer.1,6- hexylene glycol (HDO) is indispensable one of industrial chemicals, HDO can with organic acid,
Isocyanates, anhydride reaction can form different types of derivative, also can be used for synthesizing caprolactone/caprolactam and polymer,
Such as polyester, polyurethane and various adhesives, with mechanical strength, hydrolytic resistance, heat resistance, the chemical reagent resistance etc. for improving product
Performance.It is excellent as the materials environmental-protecting performance such as polyurethane made from raw material, polyester, coating using HDO, increasingly with mankind's environmental consciousness
Enhancing and relevant criterion are increasingly stringent, and promoting and applying environment-friendly material is inexorable trend；Therefore the world market of HDO is estimated
10.422 hundred million dollars of 2021 will be risen to from 7.278 hundred million in 2016 dollars, market demand with higher.
According to the difference of reactant, the synthetic route of HDO is broadly divided into following a few classes at present: one is with biomass carbon water
Compound is that raw material is by 5-HMF hydrogenation synthesis 1,6- hexylene glycol, and HDO can be obtained from two kinds of approach: DHMTHF intermediate
Open loop or the direct open loop of 5-HMF.In the case where the first approach, the selectivity of purpose product and the activity of catalyst need
It is further improved, it was reported that the open loop of DHMTHF is expected to be used for based on Rh-Re crystalline-state catalyst；With the tetrahydro of DHMTHF intermediate
Furfuryl group ring open loop is compared, and the direct open loop of HMF is based on catalyst Pd/SiO2+IrReOx/SiO2.But due to synthetic method craft
Route is too long, and production cost is excessively high, or there is the problems such as selectivity is not high, constrains their Progress in industrialization.The second is
Using chemical products adipic acid as raw material, HDO is also obtained from two kinds of approach, by one-step method (adipic acid direct-reduction preparation 1,6- oneself
Glycol) and two-step method (adipic acid and methanol esterification Dimethyl Adipate Catalyzed further hydrogenation synthesis 1,6-HD).With
Two-step method compares, and there is one-step method raw material simplicity to be easy to get, lower production costs, simplifies operation process, when reducing reaction
Between the advantages that.
With the research and discovery that deepens continuously to synthesis 1,6- hexylene glycol process, adipic acid directly synthesizes 1,6- hexylene glycol
Technical problem gradually captured, related ends also gradually are reported out.Jiang Jiawei et al. applies adipic acid one-step method
1,6- hexylene glycol is synthesized, the copper salt catalyst of crystalline silicate load, yield is about 87% or so.Murphy Vincent
J.；Dias Eric L. et al. synthesizes 1,6- hexylene glycol by Pt-W catalyst by adipic acid one-step method, and yield is about 83%.Specially
Sharp CN104549254A discloses a kind of catalyst prepared using Ru, Re, In and Ir as active component, and above method is although reality
The direct hydrogenation reduction by aliphatic dicarboxylic acid to aliphatic diol is showed.But above-mentioned catalyst is all that selection is expensive expensive
Metal is at high cost as raw material, and reusability is poor.For this purpose, the present invention compounds to obtain one by transition metal, phosphorus and ruthenium
The kind lower amorphous alloy catalyst of price, effectively can be reduced into 1,6- hexylene glycol, the conversion of adipic acid for adipic acid
Rate is up to 90%, and the yield of 1,6- hexylene glycol can reach 65%.
Summary of the invention:
It is an object of the invention to seek a kind of catalyst and preparation method thereof of adipic acid reduction preparation 1,6- hexylene glycol,
Which solve the catalyst that existing adipic acid restores preparation 1,6- hexylene glycol, the higher problems of preparation cost.
To achieve the goals above, the invention adopts the following technical scheme:
The catalyst of adipic acid reduction preparation 1,6- hexylene glycol, including active component, transition metal, phosphorus and carrier, it is described
Active component is Ru, and the transition metal is Co, Cu, Ni, Fe, at least one of Mo and Zn, and the carrier is porous structure
Material, such as diatomite, active carbon.
As its preferred embodiment, the transition metal is Zn, at least one of Cu and Co.
Scheme more preferably, the transition metal are Co.
As most preferred technical solution, the mass ratio of each metal is Ru:Co:P=1 in the catalyst in mass:
(3~50): (3~50).Wherein content is preferably 5wt% to Ru in the catalyst.
The preparation method of above-mentioned adipic acid reduction preparation 1,6- hexylene glycol catalyst, specifically includes the following steps:
(1), the mixed solution for configuring transition metal salt and microcosmic salt, inert gas is passed through into solution, in solution surface shape
At using inert gas bubble as the gas-liquid interface of template；
(2), certain density NaBH is slowly added dropwise into mixed solution4Solution is then rapidly added catalyst activity group
Point, reaction a period of time；
(3), carrier is added in the mixed liquor after reaction, the reaction was continued a period of time, and water washing to neutrality filters, and it is dry,
Obtain amorphous catalyst, during the entire process of reaction always agitating solution and with certain rate be continually fed into inert gas dimension
Hold good gas-liquid interface.
The transition metal salt includes but is not limited to CoCl2·6H2O、CuCl2·6H2O、NiCl2·6H2O、FeCl2·
6H2O、Na2MoO4·2H2O、ZnCl2Deng the soluble-salt for containing above-mentioned transition metal.The microcosmic salt is Na2HPO4Or NaH2PO4。
The method of adipic acid reduction preparation 1,6- hexylene glycol, takes water as a solvent, under the catalytic action of above-mentioned catalyst,
6.5Mpa, under 120~350 DEG C of reaction condition, adipic acid reacts 5-12h with hydrogen, generates 1,6- hexylene glycol.It is catalyzed in the process
Agent: adipic acid: water=(0.05~0.1): 1:(2~15).
Compared with the prior art, the advantages of the present invention are as follows: (1) using transition metal and phosphorus as raw material, with noble metal Ru mono-
Production catalyst is played, the cost of manufacture of catalyst is reduced；(2) P elements are introduced, changes the crystalline structure of catalyst, is urged
Change effect preferably non-static catalyst, while first restoring transition metal salt and microcosmic salt, then reduction prepares Ru rapidly, passes through
The amorphous structure of catalyst is advanced optimized to the control of reaction process；(3) inert gas, shape are continually fed into preparation process
At using inert gas bubble as the gas-liquid interface of template, the reacting environment of gas-liquid interface is formed, the performance of catalyst is improved；(4)
NaBH4Hydrogen can be discharged during reaction, the formation for being conducive to gas-liquid interface is slowly added dropwise, and avoiding being added at one time causes
The occurrence of reunion；(5) the Transformation efficiency is up to 90 % of adipic acid, the yield of 1,6- hexylene glycol can reach 65%, achieve
Preferable technical effect has preferable industrial prospect.
Detailed description of the invention:
Fig. 1 is the Amorphous Ru CoP surface texture figure that embodiment 1 builds gas-liquid interface preparation in inertia bubble.
Specific embodiment:
The present invention will be further described with Figure of description combined with specific embodiments below.
Embodiment 1
(1) by NaH2PO4And CoCl2·6H2O is dissolved in 50mL water, wherein NaH2PO4For 320mg, CoCl2·6H2O is
270mg is subsequently passed nitrogen and stirs；
(2) by 20mL 0.2molL-1Reducing agent NaBH4It is slowly added into above-mentioned solution, is then rapidly added dropwise
1mL20mg·mL-1RuCl3·nH2O, reaction 1h or so, is then added the active carbon of hydrophilic modifying, continues reduction reaction
And the catalyst of tri- kinds of substances of Ru, Co and P is generated on the activated carbon, 2~12h is reacted, is dried overnight after water washing to neutrality, mistake
Filter, it is dry, obtain Amorphous Ru CoP/C catalyst.It agitating solution and is continually fed into whole process with certain rate always
Inert gas maintains good gas-liquid interface.The active carbon is at normal temperature, using 3% hydrogen peroxide and nitric acid mixed solution
The active carbon of processing for 24 hours.
Embodiment 2-6
In embodiment 2-6 catalyst preparation process in addition to transition metal salt (being shown in Table 1) is different from embodiment 1, other steps
It is identical as embodiment.
Embodiment 7
(1) by NaH2PO4、CoCl2·6H2O and RuCl3·nH2O is dissolved in 50mL water, wherein NaH2PO4For 320mg,
CoCl2·6H2O is 270mg, RuCl3·nH2O is 20mg, is subsequently passed nitrogen and stirs；
(2) by 20mL 0.2molL-1Reducing agent NaBH4It is slowly added to above-mentioned solution, reaction 1h or so dropwise, adds
Active carbon, the reaction was continued 2~12h, water washing is filtered to being dried overnight after neutral, dry, obtains crystalline state RuCoP catalyst.Institute
Stating active carbon is at normal temperature, using the active carbon of 3% hydrogen peroxide and the processing of nitric acid mixed solution for 24 hours.One in whole process
Straight agitating solution is simultaneously continually fed into the good gas-liquid interface of inert gas maintenance with certain rate.
Embodiment 8
(1) by NaH2PO4And CoCl2·6H2O is dissolved in 50mL water, wherein NaH2PO4For 100.7mg, CoCl2·6H2O is
81mg is subsequently passed nitrogen and stirs；
(2) by 20mL 0.2molL-1Reducing agent NaBH4It is slowly added to above-mentioned solution dropwise, is then rapidly added 1mL
20mg·mL-1RuCl3·nH2O, reaction 1h or so, adds under room temperature, at 3% hydrogen peroxide and nitric acid mixed solution
The active carbon of reason for 24 hours reacts 2-12h, is dried overnight after water washing to neutrality, filters, dry, obtains amorphous state
RuCo0.2P0.2/ C catalyst.In whole process always agitating solution and with certain rate be continually fed into inert gas maintain it is good
Good gas-liquid interface.
Embodiment 8
(1) by NaH2PO4And CoCl2·6H2O is dissolved in 50mL water, wherein NaH2PO4For 151mg, CoCl2·6H2O is
121.5mg is subsequently passed nitrogen and stirs；
(2) by 20mL0.2molL-1Reducing agent NaBH4It is slowly added to above-mentioned solution dropwise；Then it is rapidly added 1mL
20mg·mL-1RuCl3·nH2O, reaction 1h or so, adds under room temperature, at 3% hydrogen peroxide and nitric acid mixed solution
The active carbon of reason for 24 hours reacts 2-12h, is dried overnight after water washing to neutrality, filters, dry, obtains amorphous state
RuCo0.3P0.3/ C catalyst.In whole process always agitating solution and with certain rate be continually fed into inert gas maintain it is good
Good gas-liquid interface.
Comparative example 1
By 1mL 20mgmL-1RuCl3·nH2O is dissolved in 50mL water, is subsequently passed nitrogen and stirs, by 20mL
0.2mol·L-1Reducing agent NaBH4It is slowly added in above-mentioned solution dropwise, reaction 1h or so is added under room temperature, using 3% mistake
The active carbon of hydrogen oxide and the processing of nitric acid mixed solution for 24 hours, sustained response for a period of time, are dried overnight after water washing to neutrality,
Obtain crystalline state Ru catalyst.It agitating solution and inert gas is continually fed into certain rate remains good always in whole process
Gas-liquid interface.
Comparative example 2
By RuCl3·3H2O and CoCl2·6H2O is dissolved in 50mL water, wherein NaH2PO4For 320mg, CoCl2·6H2O is
270mg is subsequently passed nitrogen and stirs, by 20mL 0.2molL-1Reducing agent NaBH4It is slowly added to be added dropwise above-mentioned molten
Liquid, reaction 1h or so, adds under room temperature, using the active carbon of 3% hydrogen peroxide and the processing of nitric acid mixed solution for 24 hours, reaction 2
~12h, water washing obtain crystalline state RuCo catalyst to being dried overnight after neutral.Agitating solution and with one always in whole process
Fixed rate is continually fed into inert gas and maintains good gas-liquid interface.
Comparative example 3
By NaH2PO4It is dissolved in 50mL water, wherein NaH2PO4For 320mg, it is subsequently passed nitrogen and stirs；It will
20mL0.2mol·L-1Reducing agent NaBH4It is slowly added in above-mentioned solution dropwise；Then it is rapidly added 1mL 20mgmL- 1RuCl3·nH2O, reaction 1h or so, adds under room temperature, using the work of 3% hydrogen peroxide and the processing of nitric acid mixed solution for 24 hours
Property charcoal, sustained response 2-12h, water washing is filtered to being dried overnight after neutral, dry, obtains Amorphous Ru P catalyst.Entirely
It agitating solution and inert gas is continually fed into certain rate maintains good gas-liquid interface always in the process.
The embodiment 1-8 and comparative example 1-3 catalyst prepared is evaluated using following methods:
0.2g adipic acid solid, 70mL deionized water and above-mentioned 0.1g catalyst, sealing are added in batch reactor
In the reactor.First it is passed through N2Residual air discharge in reactor is operated three times repeatedly, then is passed through H2Purging is three times.Then
Pass through H2Reactor is forced into 6.5MPa or so, once system reaches 240 DEG C of set temperature, opens stirring.The point is set
Start stirring system for beginning (t=0) and with the stirring rate of 400rpm, reacts 8h.After reaction, cooling pressure release filtering
Catalyst, reaction solution are analyzed with gas-chromatography, and concrete outcome is as shown in table 1.
Table 1
Claims (7)
1. adipic acid reduction preparation 1,6- hexylene glycol catalyst, which is characterized in that including active component, transition metal, phosphorus and
Carrier, the active component are Ru, and the transition metal is Co, Cu, Ni, Fe, at least one of Mo and Zn, and the carrier is
Porous structure material, such as diatomite, active carbon.
2. the catalyst of adipic acid reduction preparation 1,6- hexylene glycol according to claim 1, which is characterized in that the transition
Metal is Zn, at least one of Cu and Co.
3. the catalyst of adipic acid reduction preparation 1,6- hexylene glycol according to claim 1, which is characterized in that the transition
Metal is Co.
4. the catalyst of adipic acid reduction preparation 1,6- hexylene glycol according to claim 1, which is characterized in that in mass
The mass ratio of each metal is Ru:Co:P=1:(10~50 in the catalyst): (10~50).
5. the catalyst of adipic acid reduction preparation 1,6- hexylene glycol according to claim 1-4, which is characterized in that
The method of adipic acid reduction preparation 1,6- hexylene glycol, takes water as a solvent, under the catalytic action of the catalyst, in 6.5Mpa,
Under 120~350 DEG C of reaction condition, adipic acid reacts 5-12h with hydrogen, generates 1,6- hexylene glycol.Catalyst in the process: oneself two
Acid: water=(0.05~0.1): 1:(2~15).
6. a kind of preparation method of described in any item adipic acid reduction preparation 1, the 6- hexylene glycol catalyst of claim 1-4,
It is characterized in that, specifically includes the following steps:
(1), the mixed solution for configuring transition metal salt and microcosmic salt is passed through inert gas into solution, is formed with inert gas gas
Bubble is the gas-liquid interface of template；
(2), certain density NaBH is slowly added dropwise into mixed solution4Solution is then rapidly added catalyst activity component, instead
It should a period of time；
(3), carrier being added in the mixed liquor after reaction, reaction a period of time, water washing to neutrality filters, and it is dry, obtain amorphous
State catalyst, during the entire process of reaction always agitating solution and with certain rate be continually fed into inert gas maintain it is good
Gas-liquid interface.
7. the preparation method of adipic acid reduction preparation 1,6- hexylene glycol catalyst according to claim 6, which is characterized in that
The transition metal salt includes the soluble-salt of the transition metal, and the microcosmic salt is Na2HPO4Or NaH2PO4。
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| CN104549254A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Catalyst for preparing 1,6-hexanediol through direct reduction of adipic acid |
| CN105561993A (en) * | 2016-02-23 | 2016-05-11 | 上海华谊（集团）公司 | Catalyst for producing ethyl alcohol and co-producing ethyl acetate through acetic acid hydrogenation and preparation method |
| CN105597752A (en) * | 2015-12-22 | 2016-05-25 | 中国科学院广州能源研究所 | Supported carbon material catalyst for preparing C5 and C6 alkane through sugar alcohol selective hydrodeoxygenation and preparation method for catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104549254A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Catalyst for preparing 1,6-hexanediol through direct reduction of adipic acid |
| CN105597752A (en) * | 2015-12-22 | 2016-05-25 | 中国科学院广州能源研究所 | Supported carbon material catalyst for preparing C5 and C6 alkane through sugar alcohol selective hydrodeoxygenation and preparation method for catalyst |
| CN105561993A (en) * | 2016-02-23 | 2016-05-11 | 上海华谊（集团）公司 | Catalyst for producing ethyl alcohol and co-producing ethyl acetate through acetic acid hydrogenation and preparation method |
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| JUNYUAN XU ET AL.: ""Boosting the hydrogen evolution performance of ruthenium clusters through synergistic coupling with cobalt phosphide"", 《ENERGY &ENVIRONMENTAL SCIENCE》 * |
| 马元元: ""气-液界面制备贵金属合金催化剂及电催化应用研究"", 《中国优秀博硕士学位论文全文数据库（硕士）工程科技Ⅰ辑》 * |
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