CN110354877B - Catalyst for preparing 1, 6-hexanediol by reducing adipic acid and preparation method - Google Patents
Catalyst for preparing 1, 6-hexanediol by reducing adipic acid and preparation method Download PDFInfo
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- CN110354877B CN110354877B CN201910699999.6A CN201910699999A CN110354877B CN 110354877 B CN110354877 B CN 110354877B CN 201910699999 A CN201910699999 A CN 201910699999A CN 110354877 B CN110354877 B CN 110354877B
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- adipic acid
- hexanediol
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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 54
- 239000003054 catalyst Substances 0.000 title claims abstract description 51
- 239000001361 adipic acid Substances 0.000 title claims abstract description 27
- 235000011037 adipic acid Nutrition 0.000 title claims abstract description 27
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims description 10
- 239000000243 solution Substances 0.000 claims abstract description 24
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 22
- 239000011261 inert gas Substances 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 239000011259 mixed solution Substances 0.000 claims abstract description 16
- 150000003624 transition metals Chemical class 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000007935 neutral effect Effects 0.000 claims abstract description 7
- 239000011574 phosphorus Substances 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 6
- 150000003017 phosphorus Chemical class 0.000 claims abstract description 6
- 229910052802 copper Inorganic materials 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
- 150000003839 salts Chemical class 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 230000008569 process Effects 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 12
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 9
- -1 transition metal salt Chemical class 0.000 claims description 9
- 230000003197 catalytic effect Effects 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical group [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 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 14
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 11
- 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
- 238000007142 ring opening reaction Methods 0.000 description 5
- 230000000052 comparative effect Effects 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
- 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
- 230000002194 synthesizing effect Effects 0.000 description 3
- UDSFAEKRVUSQDD-UHFFFAOYSA-N Dimethyl adipate Chemical compound COC(=O)CCCCC(=O)OC UDSFAEKRVUSQDD-UHFFFAOYSA-N 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- 229910021577 Iron(II) chloride Inorganic materials 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
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910000808 amorphous metal alloy Inorganic materials 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 229920002988 biodegradable polymer Polymers 0.000 description 1
- 239000004621 biodegradable polymer Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000013329 compounding 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
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 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
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910052738 indium Inorganic materials 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
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 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
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 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
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- 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
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- 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
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- 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
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- 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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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a catalyst for preparing 1, 6-hexanediol by reducing adipic acid, which comprises an active component, transition metal, phosphorus and a carrier, wherein the active component is Ru, the transition metal is at least one of Co, Cu, Ni, Fe, Mo and Zn, and the carrier is a porous structure material, such as diatomite, activated carbon and the like. Firstly, preparing a mixed solution containing soluble salt and phosphorus salt of any one of the transition metals, and introducing inert gas into the solution to form a gas-liquid interface taking bubbles of the inert gas as a template; then slowly dripping NaBH with certain concentration into the mixed solution4Solution, followed by rapid addition of the catalyst active component; and adding the mixed solution after the reaction into a carrier, reacting for a period of time, washing to be neutral, filtering, and drying to obtain the amorphous catalyst. The catalyst has low cost, the conversion rate of adipic acid is up to 90%, the yield of 1, 6-hexanediol can reach 65%, a good technical effect is obtained, and the catalyst has a good industrialization prospect.
Description
The technical field is as follows:
the invention relates to the technical field of catalyst preparation, in particular to a catalyst which is prepared by an inert bubble template method and can synthesize 1, 6-hexanediol from adipic acid by a one-step method.
The background art comprises the following steps:
diols are industrially important as raw materials for various fine chemicals, materials for pharmaceuticals and biodegradable polymers. 1, 6-Hexanediol (HDO) is one of indispensable chemical raw materials, and HDO can react with organic acid, isocyanate and anhydride to form different types of derivatives, and can also be used for synthesizing caprolactone/caprolactam and polymers, such as polyester, polyurethane and various adhesives, so as to improve the mechanical strength, hydrolysis resistance, heat resistance, chemical reagent resistance and other properties of products. Materials such as polyurethane, polyester and paint prepared by taking HDO as a raw material have excellent environmental protection performance, and the popularization and application of environment-friendly materials are inevitable trends along with the increasing awareness of human environmental protection and the stricter relevant standards; the global market for HDO is therefore expected to grow from $ 7.278 billion in 2016 to $ 10.422 billion in 2021, with higher market demand.
The current routes for HDO synthesis are mainly divided into the following categories, according to the reactants: one is to synthesize 1, 6-hexanediol by hydrogenation of 5-HMF, which is a raw material of biomass carbohydrate, and HDO can be obtained from two ways: ring opening of DHMTHF intermediate or direct ring opening of 5-HMF. In the case of the first route, the selectivity of the desired product and the activity of the catalyst need to be further improved, and crystalline catalysts based on Rh-Re have been reported to be promising for the ring opening of DHMTHF; direct ring opening of HMF is based on the catalyst Pd/SiO as compared to tetrahydrofurfuryl ring opening of DHMTHF intermediates2+IrReOx/SiO2. However, the synthesis method has the problems of too long process route, too high production cost, low selectivity and the like, and the industrial progress of the synthesis method is restricted. The other is that the chemical product adipic acid is used as a raw material, HDO is also obtained from two ways, namely a one-step method (the adipic acid is directly reduced to prepare 1, 6-hexanediol) and a two-step method (adipic acid and methanol are esterified to synthesize dimethyl adipate, and then the dimethyl adipate is further hydrogenated to synthesize the 1, 6-hexanediol). Compared with the two-step method, the one-step method has the advantages of simple and easily obtained raw materials, lower production cost, simplified reaction operation flow, reduced reaction time and the like.
With the continuous and intensive research and exploration on the process of synthesizing 1, 6-hexanediol, the technical problem of directly synthesizing 1, 6-hexanediol from adipic acid is gradually overcome, and related results are gradually reported. Jiangjiawei et al used adipic acid to synthesize 1, 6-hexanediol by one-step method, and the yield of the copper salt catalyst loaded by crystalline silicate was about 87%. Murphy Vincent j.; dias Eric L. et al synthesized 1, 6-hexanediol from adipic acid in a one-step process over a Pt-W catalyst at a yield of about 83%. Patent CN104549254A discloses a catalyst prepared with Ru, Re, In and Ir as active components, although the above method achieves direct hydrogenation reduction from aliphatic dicarboxylic acids to aliphatic diols. However, the catalysts are all prepared from expensive noble metals, so that the cost is high and the reusability is poor. Therefore, the amorphous alloy catalyst with low price is obtained by compounding the transition metal, the phosphorus and the ruthenium, the adipic acid can be effectively reduced into the 1, 6-hexanediol, the conversion rate of the adipic acid is up to 90%, and the yield of the 1, 6-hexanediol can reach 65%.
The invention content is as follows:
the invention aims to find a catalyst for preparing 1, 6-hexanediol by reducing adipic acid and a preparation method thereof, which solve the problem of higher preparation cost of the existing catalyst for preparing 1, 6-hexanediol by reducing adipic acid.
In order to achieve the purpose, the invention adopts the following technical scheme:
the catalyst for preparing the 1, 6-hexanediol by reducing the adipic acid comprises an active component, transition metal, phosphorus and a carrier, wherein the active component is Ru, the transition metal is at least one of Co, Cu, Ni, Fe, Mo and Zn, and the carrier is a porous structure material such as diatomite, activated carbon and the like.
Preferably, the transition metal is at least one of Zn, Cu and Co.
More preferably, the transition metal is Co.
As the most preferable technical means, the mass ratio of each metal in the catalyst is Ru: co: p is 1: (3-50): (3-50). Wherein the Ru content in the catalyst is preferably 5 wt.%.
The preparation method of the catalyst for preparing the 1, 6-hexanediol by reducing the adipic acid comprises the following steps:
(1) preparing a mixed solution of transition metal salt and phosphorus salt, introducing inert gas into the solution, and forming a gas-liquid interface taking inert gas bubbles as a template on the surface of the solution;
(2) slowly dripping NaBH with certain concentration into the mixed solution4The solution is added with the active components of the catalyst quickly and reacted for a period of time;
(3) adding the reacted mixed solution into a carrier, continuously reacting for a period of time, washing to be neutral, filtering and drying to obtain the amorphous catalyst, stirring the solution all the time in the whole reaction process, and continuously introducing inert gas at a certain speed to maintain a good gas-liquid interface.
The transition metal salt includes, but is not limited to CoCl2·6H2O、CuCl2·6H2O、NiCl2·6H2O、FeCl2·6H2O、Na2MoO4·2H2O、ZnCl2And soluble salts containing the above transition metals. The phosphorus salt is Na2HPO4Or NaH2PO4。
A method for preparing 1, 6-hexanediol by reducing adipic acid comprises the steps of reacting adipic acid with hydrogen for 5-12 hours under the catalytic action of a catalyst under the conditions of 6.5Mpa and 120-350 ℃ by taking water as a solvent to generate the 1, 6-hexanediol. The catalyst in the process: adipic acid: water (0.05-0.1): 1: (2-15).
Compared with the prior art, the invention has the advantages that: (1) transition metal and phosphorus are used as raw materials, and the transition metal and the phosphorus are used together with noble metal Ru to prepare the catalyst, so that the preparation cost of the catalyst is reduced; (2) introducing phosphorus element, changing the crystal structure of the catalyst to obtain a non-static catalyst with better catalytic effect, reducing the transition metal salt and the phosphorus salt at the same time, then quickly reducing to prepare Ru, and further optimizing the amorphous structure of the catalyst by controlling the reaction process; (3) in the preparation process, inert gas is continuously introduced to form a gas-liquid interface taking inert gas bubbles as a template, so that a reaction site of the gas-liquid interface is formed, and the performance of the catalyst is improved; (4) NaBH4In the process of reactionHydrogen is released in the process, and the slow dripping is favorable for forming a gas-liquid interface, so that the agglomeration condition caused by one-time addition is avoided; (5) the conversion rate of adipic acid is up to 90%, the yield of 1, 6-hexanediol can reach 65%, a good technical effect is obtained, and the method has a good industrial prospect.
Description of the drawings:
FIG. 1 is a diagram of the surface structure of amorphous RuCoP prepared at the gas-liquid interface created by inert gas bubbles in example 1.
The specific implementation mode is as follows:
the invention is further described with reference to the following detailed description and the accompanying drawings.
Example 1
(1) Reacting NaH with2PO4And CoCl2·6H2O dissolved in 50mL of water, in which NaH2PO4320mg of CoCl2·6H2O is 270mg, followed by introduction of nitrogen and stirring;
(2) 20mL of 0.2 mol. L-1Reducing agent NaBH4Slowly added dropwise to the above solution, followed by rapid addition of 1mL of 20 mg. multidot.mL-1RuCl3·nH2And O, reacting for about 1h, adding hydrophilic modified activated carbon, continuing to perform reduction reaction and generate catalysts of Ru, Co and P on the activated carbon, reacting for 2-12h, washing to be neutral, drying overnight, filtering, and drying to obtain the amorphous RuCoP/C catalyst. The solution is stirred all the time in the whole process and inert gas is continuously introduced at a certain speed to maintain a good gas-liquid interface. The activated carbon is treated for 24 hours by adopting a mixed solution of 3 percent hydrogen peroxide and nitric acid at normal temperature.
Examples 2 to 6
Examples 2-6 the catalyst preparation process was carried out in the same manner as in example 1 except that the transition metal salt (see Table 1) was different from that of example 1.
Example 7
(1) Reacting NaH with2PO4、CoCl2·6H2O and RuCl3·nH2O dissolved in 50mL of water, in which NaH2PO4320mg of CoCl2·6H2O270 mg, RuCl3·nH220mg of O, then introducing nitrogen and stirring;
(2) 20mL of 0.2 mol. L-1Reducing agent NaBH4And (3) slowly adding the solution dropwise, reacting for about 1h, adding active carbon, continuously reacting for 2-12h, washing to neutrality by water, drying overnight, filtering, and drying to obtain the crystalline RuCoP catalyst. The activated carbon is treated for 24 hours by adopting a mixed solution of 3 percent hydrogen peroxide and nitric acid at normal temperature. The solution is stirred all the time in the whole process and inert gas is continuously introduced at a certain speed to maintain a good gas-liquid interface.
Example 8
(1) Reacting NaH2PO4And CoCl2·6H2O dissolved in 50mL of water, in which NaH2PO4100.7mg of CoCl2·6H2O was 81mg, followed by introduction of nitrogen and stirring;
(2) 20mL of 0.2 mol. L-1Reducing agent NaBH4The solution was slowly added dropwise, followed by rapid addition of 1mL of 20 mg. multidot.mL-1RuCl3·nH2O, reacting for about 1h, adding activated carbon which is treated by 3 percent hydrogen peroxide and nitric acid mixed solution for 24h at normal temperature, reacting for 2-12h, washing to be neutral, drying overnight, filtering and drying to obtain amorphous RuCo0.2P0.2a/C catalyst. The solution is stirred all the time in the whole process and inert gas is continuously introduced at a certain speed to maintain a good gas-liquid interface.
Example 8
(1) Reacting NaH with2PO4And CoCl2·6H2O dissolved in 50mL of water, in which NaH2PO4151mg of CoCl2·6H2When the O content is 121.5mg, introducing nitrogen and stirring;
(2) 20 mL0.2mol.L-1Reducing agent NaBH4Slowly adding the solution dropwise; then 1mL of 20 mg. multidot.mL was added rapidly-1RuCl3·nH2O, reacting for about 1h, adding activated carbon which is treated by 3 percent hydrogen peroxide and nitric acid mixed solution for 24h at normal temperature, reacting for 2-12h, washing with water to be neutral, and dryingDrying overnight, filtering, drying to obtain amorphous RuCo0.3P0.3a/C catalyst. The solution is stirred all the time in the whole process and inert gas is continuously introduced at a certain speed to maintain a good gas-liquid interface.
Comparative example 1
1mL of 20 mg/mL-1RuCl3·nH2O was dissolved in 50mL of water, followed by introduction of nitrogen and stirring, and 20mL of 0.2 mol. L-1Reducing agent NaBH4And (3) slowly adding the solution dropwise into the solution, reacting for about 1h, adding activated carbon treated by a mixed solution of 3% hydrogen peroxide and nitric acid for 24h at normal temperature, reacting for a period of time, washing to neutrality by water, and drying overnight to obtain the crystalline Ru catalyst. The solution is stirred all the time in the whole process and inert gas is continuously introduced at a certain speed to maintain a good gas-liquid interface.
Comparative example 2
Adding RuCl3·3H2O and CoCl2·6H2O dissolved in 50mL of water, in which NaH2PO4320mg of CoCl2·6H2O270 mg, followed by introduction of nitrogen and stirring, 20mL of 0.2 mol. L-1Reducing agent NaBH4And (3) slowly adding the solution dropwise, reacting for about 1h, adding activated carbon treated by a mixed solution of 3% hydrogen peroxide and nitric acid at normal temperature for 24h, reacting for 2-12h, washing to neutrality by water, and drying overnight to obtain the crystalline RuCo catalyst. The solution is stirred all the time in the whole process and inert gas is continuously introduced at a certain speed to maintain a good gas-liquid interface.
Comparative example 3
Reacting NaH with2PO4Dissolved in 50mL of water, in which NaH2PO4320mg, followed by nitrogen and stirring; 20 mL0.2mol.L-1Reducing agent NaBH4Slowly adding the mixture into the solution drop by drop; then 1mL of 20 mg. multidot.mL was added rapidly- 1RuCl3·nH2O, reacting for about 1h, adding activated carbon which is treated by a mixed solution of 3 percent hydrogen peroxide and nitric acid for 24h at normal temperature, continuously reacting for 2-12h, washing to be neutral, drying overnight, filtering, and drying to obtain amorphous RuP catalystAnd (3) preparing. The solution is stirred all the time in the whole process and inert gas is continuously introduced at a certain speed to maintain a good gas-liquid interface.
The catalysts prepared in examples 1 to 8 and comparative examples 1 to 3 were evaluated by the following methods:
a batch reactor was charged with 0.2g of adipic acid solids, 70mL of deionized water and 0.1g of the above catalyst and sealed. Firstly introducing N2The residual air in the reactor is discharged and repeatedly operated for three times, and then H is introduced2Purging was carried out three times. Then through H2The reactor was pressurized to about 6.5MPa and once the system reached a set temperature of 240 ℃, the stirring was started. This point was set to start (t ═ 0) and the stirring system was started at a stirring rate of 400rpm, and the reaction was allowed to proceed for 8 h. After the reaction, the reaction mixture was cooled, decompressed, and the catalyst was filtered, and the reaction mixture was analyzed by gas chromatography, and the specific results are shown in table 1.
TABLE 1
Claims (5)
1. The application of the catalyst in preparing 1, 6-hexanediol by catalyzing reduction of adipic acid is characterized in that the catalyst comprises an active component, transition metal, phosphorus and a carrier, wherein the active component is Ru, the transition metal is at least one of Co, Cu, Ni, Fe, Mo and Zn, and the carrier is a porous structure material;
the preparation method of the catalyst for preparing the 1, 6-hexanediol by reducing the adipic acid comprises the following steps:
(1) preparing a mixed solution of transition metal salt and phosphorus salt, and introducing inert gas into the solution to form a gas-liquid interface taking inert gas bubbles as a template;
(2) slowly dripping NaBH with certain concentration into the mixed solution4The solution is added with the active component of the catalyst quickly and reacted for a period of time;
(3) adding the reacted mixed solution into a carrier, reacting for a period of time, washing with water to be neutral, filtering, and drying to obtain an amorphous catalyst, stirring the solution all the time in the whole reaction process, and continuously introducing inert gas at a certain speed to maintain a good gas-liquid interface;
according to the method for preparing 1, 6-hexanediol by reducing adipic acid, water is used as a solvent, adipic acid and hydrogen react for 5-12h under the catalytic action of a catalyst under the reaction conditions of 6.5MPa and 120-350 ℃ to generate 1, 6-hexanediol, and the catalyst in the process: adipic acid: water = (0.05-0.1): 1: (2-15).
2. Use according to claim 1, wherein the transition metal is at least one of Zn, Cu and Co.
3. Use according to claim 1, wherein the transition metal is Co.
4. Use according to claim 3, wherein the mass ratio of Ru: co: p = 1: (10-50): (10-50).
5. The use according to claim 1, wherein the transition metal salt comprises a soluble salt of the transition metal and the phosphorus salt is Na2HPO4 Or 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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| 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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| "Boosting the hydrogen evolution performance of ruthenium clusters through synergistic coupling with cobalt phosphide";Junyuan Xu et al.;《Energy &Environmental Science》;20180411;第11卷;摘要和实验部分 * |
| "气-液界面制备贵金属合金催化剂及电催化应用研究";马元元;《中国优秀博硕士学位论文全文数据库（硕士）工程科技Ⅰ辑》;20170315(第03期);第23-25页 * |
| Junyuan Xu et al.."Boosting the hydrogen evolution performance of ruthenium clusters through synergistic coupling with cobalt phosphide".《Energy &Environmental Science》.2018,第11卷摘要和实验部分. * |
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