CN111036194A - Preparation method of catalyst for hydrogenation of phthalate - Google Patents
Preparation method of catalyst for hydrogenation of phthalate Download PDFInfo
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- CN111036194A CN111036194A CN201811189800.7A CN201811189800A CN111036194A CN 111036194 A CN111036194 A CN 111036194A CN 201811189800 A CN201811189800 A CN 201811189800A CN 111036194 A CN111036194 A CN 111036194A
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- catalyst
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- heat treatment
- hydrogenation
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- 239000003054 catalyst Substances 0.000 title claims abstract description 45
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 18
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 29
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 239000001301 oxygen Substances 0.000 claims abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 11
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 45
- 239000007864 aqueous solution Substances 0.000 claims description 29
- 238000001704 evaporation Methods 0.000 claims description 14
- 238000005470 impregnation Methods 0.000 claims description 14
- 239000002202 Polyethylene glycol Substances 0.000 claims description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 13
- 229920001223 polyethylene glycol Polymers 0.000 claims description 13
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 10
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 10
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 10
- 238000001556 precipitation Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- 230000008021 deposition Effects 0.000 claims description 7
- 229910052763 palladium Inorganic materials 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 230000002829 reductive effect Effects 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000002671 adjuvant Substances 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 2
- 229910052681 coesite Inorganic materials 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- 229910052906 cristobalite Inorganic materials 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 2
- 239000012279 sodium borohydride Substances 0.000 claims description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 2
- 229910052682 stishovite Inorganic materials 0.000 claims description 2
- 229910052905 tridymite Inorganic materials 0.000 claims description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- 238000009388 chemical precipitation Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 239000002245 particle Substances 0.000 description 31
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 18
- 238000002791 soaking Methods 0.000 description 17
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 12
- 238000011068 loading method Methods 0.000 description 11
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 11
- 239000000843 powder Substances 0.000 description 10
- 229910001961 silver nitrate Inorganic materials 0.000 description 9
- 238000000151 deposition Methods 0.000 description 6
- 125000005498 phthalate group Chemical class 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 4
- 229910052814 silicon oxide Inorganic materials 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910000420 cerium oxide Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 239000012018 catalyst precursor Substances 0.000 description 2
- 238000005234 chemical deposition Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- HORIEOQXBKUKGQ-UHFFFAOYSA-N bis(7-methyloctyl) cyclohexane-1,2-dicarboxylate Chemical compound CC(C)CCCCCCOC(=O)C1CCCCC1C(=O)OCCCCCCC(C)C HORIEOQXBKUKGQ-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- QYMFNZIUDRQRSA-UHFFFAOYSA-N dimethyl butanedioate;dimethyl hexanedioate;dimethyl pentanedioate Chemical compound COC(=O)CCC(=O)OC.COC(=O)CCCC(=O)OC.COC(=O)CCCCC(=O)OC QYMFNZIUDRQRSA-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 239000008029 phthalate plasticizer Substances 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/50—Silver
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/52—Gold
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/303—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by hydrogenation of unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the technical field of catalysis, and particularly relates to a preparation method of a catalyst for hydrogenation of phthalate. The method comprises the following steps: a) carrying an active component on a carrier to obtain A; b) carrying the auxiliary agent on the A to obtain B; c) carrying out heat treatment on the B in an inert atmosphere to obtain C; d) and carrying out heat treatment on the C in an oxygen-containing atmosphere to obtain the catalyst. Compared with the prior art, the catalyst for hydrogenation of phthalate prepared by the method has high catalytic performance and low loss rate of active components.
Description
Technical Field
The invention belongs to the technical field of catalysis, and particularly relates to a preparation method of a catalyst for hydrogenation of phthalate.
Background
Phthalates (PAEs) are currently the most widely used plasticizers in the polyvinyl chloride industry. As PAEs are eco-toxic and are not chemically bonded to the main structure of the plastic, PAEs are continuously released from the plastic during use. Therefore, in plastic products in foreign countries, especially in the field where the plastic products are frequently in contact with human bodies during use, the use of PAEs is very severely limited. With the increasing emphasis on green, environmental protection and health in China, the development of environment-friendly plasticizers, which are substitutes of PAEs, has become a necessary trend in the development of plastic technology.
US4754064 discloses a catalyst for preparing 1, 2-cyclohexanedicarboxylic acid dibasic ester and a preparation method thereof. Soaking the active components in macroporous carrier, air drying, oven drying, calcining, and adding into the solution2Reducing and activating at 300 deg.C and normal pressure.
Chinese patent CN106984310A discloses a preparation method and application of a catalyst for hydrogenation of phthalate plasticizer. Treating the carrier with an aqueous alkaline substance solution; soaking the treated carrier in a mixed aqueous solution of ruthenium and an auxiliary agent overnight, drying, grinding, washing with deionized water, drying, and grinding to obtain a catalyst precursor; the catalyst precursor is activated in a normal pressure hydrogen atmosphere.
The phthalate hydrogenation catalysts reported at present are mostly aimed at liquid-phase batch hydrogenation reactions, and the reaction temperature and pressure are low. As is well known, the fixed bed continuous reaction process has obvious advantages compared with the batch process, such as simple process, continuous production, high product stability, easy on-line detection, product quality control and the like. However, the reaction temperature is high, and the raw materials continuously pass through the catalyst bed layer, which easily causes sintering and loss of the noble metal active component, and is a technical problem to be solved in the field.
Disclosure of Invention
The invention aims to provide a preparation method of a catalyst for phthalate hydrogenation, which improves the catalytic performance of the catalyst and greatly reduces the loss rate of active components.
The invention is mainly characterized in that the roasting is carried out in inert atmosphere in the presence of an auxiliary agent, and then a heat treatment mode of roasting in oxygen-containing atmosphere is adopted, so that the firmness degree of the active components on the carrier is improved.
The invention relates to a preparation method of a catalyst for hydrogenation of phthalate, which is realized by the following technical scheme: a) carrying an active component on a carrier to obtain A; b) carrying the auxiliary agent on the A to obtain B; c) carrying out heat treatment on the B in an inert atmosphere to obtain C; d) and carrying out heat treatment on the C in an oxygen-containing atmosphere to obtain the catalyst.
Generally, in step a), the active component comprises at least one of Ru, Pd, Ag, Au, Ni, Rh.
a) In the step (b), the carrier contains Al2O3、SiO2、ZrO2、TiO2、CeO2And a molecular sieve.
a) In the step (b), the supporting comprises one of an impregnation method, a chemical deposition precipitation method and a reduction deposition precipitation method.
The reduction deposition precipitation method adopts one of hydrazine hydrate solution and sodium borohydride solution.
b) In the step, the adjuvant comprises one of polyethylene glycol, citric acid, and ethylene glycol.
In the step b), the loading is to dip A in an aqueous solution of an auxiliary agent, and evaporate water to dryness under disturbance conditions.
The loading times are 1-5 times, and the dipping temperature is 50-80 ℃.
c) In the step (b), the heat treatment is carried out under an inert atmosphere2And treating for 1-5 h at 350-1000 ℃ in one atmosphere of Ar and He.
d) In the step, the heat treatment in the oxygen-containing atmosphere is carried out for 1-5 hours at 500-800 ℃ in the air or oxygen atmosphere.
Compared with the prior art, the catalyst for hydrogenation of phthalate prepared by the method has high catalytic performance and low loss rate of active components.
Detailed Description
The following examples are provided only for further explanation of the contents and effects of the present invention and are not intended to limit the present invention.
Example 1
Granulating aluminum oxide powder into 20-40-mesh particles, preparing a ruthenium trichloride aqueous solution by adopting an isometric impregnation method, measuring the mass of ruthenium chloride according to the loading amount of ruthenium on the final catalyst being 1%, dropwise adding the ruthenium trichloride aqueous solution onto the aluminum oxide particles, and then evaporating to dryness in a rotary evaporator at 90 ℃ to obtain A. Preparing 60% polyethylene glycol aqueous solution with volume fraction of 2 times of volume of A, soaking A in the aqueous solution at 50 deg.C for 3h, and evaporating to dryness at 90 deg.C in rotary evaporator to obtain B. Placing B in N2Then treating the C at 500 ℃ for 5h in an oxygen atmosphere to obtain a catalyst Cat.1.
Example 2
Granulating aluminum oxide powder into particles of 20-40 meshes, preparing a palladium chloride aqueous solution by adopting an isometric impregnation method, measuring the mass of palladium chloride according to the final loading amount of palladium on the catalyst of 0.5%, dropwise adding the palladium chloride aqueous solution on the aluminum oxide particles, and then evaporating to dryness in a rotary evaporator at 90 ℃ to obtain A. Preparing 60% volume fraction polyethylene glycol aqueous solution, the volume of the aqueous solution is 2 times of the volume of A, soaking A in the aqueous solution at 60 ℃ for 3h, and evaporating to dryness at 90 ℃ in a rotary evaporator to complete primary soaking; then, another impregnation with polyethylene glycol was carried out to obtain B. Placing B in N2Then treating the C at the temperature of 600 ℃ for 4h in an oxygen atmosphere to obtain a catalyst Cat.2.
Example 3
Granulating silicon oxide powder into particles of 20-40 meshes, preparing a platinum nitrate aqueous solution, wherein the mass of the platinum nitrate is measured according to the platinum loading amount on the final catalyst being 0.2%, and the volume of the solution is silicon oxideAdding silicon oxide particles into a platinum nitrate solution, wherein the volume of the silicon oxide particles is 2 times that of the particles; and (2) dropwise adding 1mol/L sodium hydroxide solution serving as a precipitator into the solution by adopting a chemical deposition precipitation method, continuously stirring, maintaining for 10min when the pH value of the solution reaches 7.5, washing the silicon oxide particles for 3 times by using deionized water, and drying for 4h at 100 ℃ to obtain A. Preparing a saturated citric acid solution, adding water with the volume 4 times that of the solution for dilution, taking the solution with the volume 2 times that of the solution A, soaking the solution A in the solution at 60 ℃ for 3 hours, and evaporating the solution to dryness at 90 ℃ in a rotary evaporator to finish 1-time soaking; then, citric acid impregnation was performed again to obtain B. Placing B in N2At 500 ℃ for 4h to obtain C, and then treating the C in air at 700 ℃ for 2h to obtain a catalyst Cat.3.
Example 4
Granulating titanium oxide powder into particles of 20-40 meshes, preparing a chloroauric acid solution, metering the mass of the chloroauric acid according to the load of gold on the final catalyst being 0.1%, wherein the volume of the solution is 2 times of that of the titanium oxide particles, and adding the titanium oxide particles into the chloroauric acid solution; by adopting a reduction deposition precipitation method, 40 percent hydrazine hydrate solution is dropwise added into the solution as a reducing agent and is stirred vigorously continuously, the adding amount is 1.5 times of the amount of the hydrazine hydrate solution required by reducing all chloroauric acid, then titanium oxide particles are washed for 3 times by deionized water and dried for 4 hours at 100 ℃, and A is obtained. Preparing 50% of glycol aqueous solution with the volume fraction of 2 times of the volume of A, soaking A in the solution at 80 ℃ for 3h, and evaporating to dryness at 90 ℃ in a rotary evaporator to complete primary soaking; then, the citric acid was impregnated 4 times to obtain B. And (3) treating the B in Ar gas at 800 ℃ for 2h to obtain C, and then treating the C in air at 800 ℃ for 2h to obtain a catalyst Cat.4.
Example 5
Granulating zirconia powder into particles of 20-40 meshes, preparing a silver nitrate solution, measuring the mass of silver nitrate according to the final silver loading amount on the catalyst to be 0.1%, wherein the volume of the solution is 2 times of that of the zirconia particles, and adding the zirconia particles into the silver nitrate solution; by adopting a reduction deposition precipitation method, 30 percent hydrazine hydrate solution is dropwise added into the solution as a reducing agent and is stirred vigorously, the adding amount is 1.5 times of the amount of the hydrazine hydrate solution required by reducing all silver nitrate, then the zirconium oxide particles are washed for 3 times by deionized water and dried for 4 hours at 100 ℃, and A is obtained. Preparing 50% volume fraction polyethylene glycol aqueous solution, the volume of the solution is 2 times of the volume of A, soaking A in the aqueous solution at 80 ℃ for 3h, and evaporating to dryness at 90 ℃ in a rotary evaporator to complete primary soaking; then, 4 times of impregnation with polyethylene glycol was performed to obtain B. And (3) treating the B in He gas at 1000 ℃ for 1h to obtain C, and then treating the C in air at 800 ℃ for 1h to obtain a catalyst Cat.5.
Example 6
Granulating cerium oxide powder into particles of 20-40 meshes, preparing a silver nitrate solution, measuring the mass of silver nitrate according to the final silver loading amount on the catalyst to be 0.1%, wherein the volume of the solution is 2 times of that of zirconium oxide particles, and adding the cerium oxide particles into the silver nitrate solution; by adopting a reduction deposition precipitation method, 30 percent hydrazine hydrate solution is dropwise added into the solution as a reducing agent and is stirred vigorously, the adding amount is 1.5 times of the amount of the hydrazine hydrate solution required by reducing all silver nitrate, and then cerium oxide particles are dried for 4 hours at 100 ℃ after being washed for 3 times by deionized water to obtain A. Preparing 50% volume fraction polyethylene glycol aqueous solution, the volume of the solution is 2 times of the volume of A, soaking A in the aqueous solution at 80 ℃ for 3h, and evaporating to dryness at 90 ℃ in a rotary evaporator to complete primary soaking; then, 3 times of impregnation with polyethylene glycol was performed to obtain B. And (3) treating the B in He gas at 1000 ℃ for 1h to obtain C, and then treating the C in air at 800 ℃ for 1h to obtain a catalyst Cat.6.
Example 7
Granulating aluminum oxide powder into 20-40 mesh particles, and preparing a mixed solution (n) of ruthenium chloride and palladium nitrateRu/nPt= 1/1), measured as the total precious metal loading on the final catalyst is 0.1% solute mass, solution volume is 2 times alumina particle volume, alumina particles are added to silver nitrate solution; by adopting a reduction deposition precipitation method, 60 percent hydrazine hydrate solution as a reducing agent is dropwise added into the solution and is stirred vigorously continuously, the adding amount is 1.5 times of the amount of the hydrazine hydrate solution required by reducing all noble metal salts, and then alumina particles are removedAfter washing with ionized water for 3 times, drying at 100 ℃ for 4h to obtain A. Preparing 50% volume fraction polyethylene glycol aqueous solution, the volume of the solution is 2 times of the volume of A, soaking A in the aqueous solution at 80 ℃ for 3h, and evaporating to dryness at 90 ℃ in a rotary evaporator to complete primary soaking; then, 3 times of impregnation with polyethylene glycol was performed to obtain B. And (3) treating the B in N2 gas at 700 ℃ for 3h to obtain C, and then treating the C in air at 600 ℃ for 2h to obtain a catalyst Cat.7.
Comparative example 1
Granulating aluminum oxide powder into particles of 20-40 meshes, preparing a palladium chloride aqueous solution by adopting an isometric impregnation method, measuring the mass of palladium chloride according to the final loading amount of palladium on the catalyst of 0.5%, dropwise adding the palladium chloride aqueous solution on the aluminum oxide particles, and then evaporating to dryness in a rotary evaporator at 90 ℃ to obtain A. Then treating the A in an oxygen atmosphere at 600 ℃ for 4h to obtain a catalyst Cat.2-1.
Comparative example 2
Granulating aluminum oxide powder into particles of 20-40 meshes, preparing a palladium chloride aqueous solution by adopting an isometric impregnation method, measuring the mass of palladium chloride according to the final loading amount of palladium on the catalyst of 0.5%, dropwise adding the palladium chloride aqueous solution on the aluminum oxide particles, and then evaporating to dryness in a rotary evaporator at 90 ℃ to obtain A. Placing A in N2Treating at 450 deg.c for 4 hr to obtain catalyst Cat.2-2.
Comparative example 3
Granulating aluminum oxide powder into particles of 20-40 meshes, preparing a palladium chloride aqueous solution by adopting an isometric impregnation method, measuring the mass of palladium chloride according to the final loading amount of palladium on the catalyst of 0.5%, dropwise adding the palladium chloride aqueous solution on the aluminum oxide particles, and then evaporating to dryness in a rotary evaporator at 90 ℃ to obtain A. Preparing 60% volume fraction polyethylene glycol aqueous solution, the volume of the aqueous solution is 2 times of the volume of A, soaking A in the aqueous solution at 60 ℃ for 3h, and evaporating to dryness at 90 ℃ in a rotary evaporator to complete primary soaking; then, another impregnation with polyethylene glycol was carried out to obtain B. Placing B in N2Treating at 450 deg.c for 4 hr to obtain catalyst Cat.2-3.
Example 8
The above examples 1 to 7 and comparative examples 1 to 3 were mixedThe catalyst is flaked and formed into a cylinder with the diameter of 3 multiplied by 3mm, and the catalyst is respectively used for the hydrogenation reaction of diisononyl phthalate. A fixed bed reactor (. phi.35 mm) was charged with 50mL of catalyst, first at 5vol.% H2/N2Reducing at 250 deg.C for 4 hr, regulating the temperature to 180 deg.C, hydrogenating, and switching gas to H2Adjusting the hydrogenation reaction pressure to be 8MPa, starting a diisononyl phthalate liquid-phase infusion pump, adjusting the hydrogen-ester ratio to be 50, starting timing sampling after reacting for 30min, and respectively taking samples at 100, 200 and 300h time points after timing for analysis, wherein the results are shown in the following table 1.
Table 1 catalyst test results
As can be seen from the data in Table 1, in the hydrogenation reaction of diisononyl phthalate, the hydrogenation catalyst prepared by the method has the advantages that the size of metal crystal grains is obviously reduced, and the hydrogenation catalyst has higher selective hydrogenation activity and higher selectivity of diisononyl cyclohexane-1, 2-dicarboxylate compared with the catalyst prepared by the prior art. And the loss rate of the noble metal can be obviously reduced, so that the service life of the catalyst is prolonged.
Claims (10)
1. The preparation method of the catalyst for hydrogenation of phthalate is characterized by comprising the following steps: a) carrying an active component on a carrier to obtain A; b) carrying the auxiliary agent on the A to obtain B; c) carrying out heat treatment on the B in an inert atmosphere to obtain C; d) and carrying out heat treatment on the C in an oxygen-containing atmosphere to obtain the catalyst.
2. The method according to claim 1, wherein the active component in step a) comprises at least one of Ru, Pd, Pt, Ag, Au, Ni, Rh.
3. The method according to claim 1, wherein the carrier in the step a) contains Al2O3、SiO2、ZrO2、TiO2、CeO2And a molecular sieve.
4. The method of claim 1, wherein the supporting in step a) comprises one of impregnation, chemical precipitation, and reductive precipitation.
5. The method according to claim 4, wherein the reductive deposition precipitation method uses one of a hydrazine hydrate solution and a sodium borohydride solution.
6. The method of claim 1, wherein the adjuvant in step b) comprises one of polyethylene glycol, citric acid, and ethylene glycol.
7. The method according to claim 1, wherein the supporting in step b) is carried out by immersing A in an aqueous solution of an adjuvant and evaporating water under turbulent conditions.
8. The method according to claim 7, wherein the supporting is performed 1 to 5 times, and the impregnation temperature is 50 to 80 ℃.
9. The method according to claim 1, wherein the heat treatment under inert atmosphere in step c) is performed under N2And treating for 1-5 h at 350-1000 ℃ in one atmosphere of Ar and He.
10. The method according to claim 1, wherein the heat treatment in the oxygen-containing atmosphere in step d) is performed at 500 to 800 ℃ for 1 to 5 hours in an air or oxygen atmosphere.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19927978A1 (en) * | 1999-06-18 | 2000-12-21 | Basf Ag | New esters of cyclohexane-1,3- and -1,4-dicarboxylic acid, useful as toxicologically acceptable plasticizers, e.g. for PVC, obtained by hydrogenation of corresponding isophthalate and terephthalate esters |
| CN104549333A (en) * | 2013-10-23 | 2015-04-29 | 中国石油化工股份有限公司 | Preparation method for residual oil hydrogenation and demetalization catalyst |
| CN104549328A (en) * | 2013-10-22 | 2015-04-29 | 中国石油化工股份有限公司 | Method for preparing residual oil hydro-demetallization catalyst |
| CN104689814A (en) * | 2015-02-15 | 2015-06-10 | 中国海洋石油总公司 | Method for preparing phthalate hydrogenation catalyst |
-
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19927978A1 (en) * | 1999-06-18 | 2000-12-21 | Basf Ag | New esters of cyclohexane-1,3- and -1,4-dicarboxylic acid, useful as toxicologically acceptable plasticizers, e.g. for PVC, obtained by hydrogenation of corresponding isophthalate and terephthalate esters |
| CN104549328A (en) * | 2013-10-22 | 2015-04-29 | 中国石油化工股份有限公司 | Method for preparing residual oil hydro-demetallization catalyst |
| CN104549333A (en) * | 2013-10-23 | 2015-04-29 | 中国石油化工股份有限公司 | Preparation method for residual oil hydrogenation and demetalization catalyst |
| CN104689814A (en) * | 2015-02-15 | 2015-06-10 | 中国海洋石油总公司 | Method for preparing phthalate hydrogenation catalyst |
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