CN114247441B - Catalyst for preparing 1,2,4, 5-cyclohexane tetracarboxylic dianhydride by hydrogenation of pyromellitic anhydride and preparation method thereof - Google Patents
Catalyst for preparing 1,2,4, 5-cyclohexane tetracarboxylic dianhydride by hydrogenation of pyromellitic anhydride and preparation method thereof Download PDFInfo
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- CN114247441B CN114247441B CN202111398326.0A CN202111398326A CN114247441B CN 114247441 B CN114247441 B CN 114247441B CN 202111398326 A CN202111398326 A CN 202111398326A CN 114247441 B CN114247441 B CN 114247441B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 73
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 37
- LJMPOXUWPWEILS-UHFFFAOYSA-N 3a,4,4a,7a,8,8a-hexahydrofuro[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1C2C(=O)OC(=O)C2CC2C(=O)OC(=O)C21 LJMPOXUWPWEILS-UHFFFAOYSA-N 0.000 title claims abstract description 21
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 26
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical group [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002131 composite material Substances 0.000 claims abstract description 24
- 239000007864 aqueous solution Substances 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 10
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 9
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 8
- 239000011148 porous material Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 230000032683 aging Effects 0.000 claims description 6
- 239000012065 filter cake Substances 0.000 claims description 6
- 235000019353 potassium silicate Nutrition 0.000 claims description 6
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 230000032050 esterification Effects 0.000 claims description 5
- 238000005886 esterification reaction Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 238000006386 neutralization reaction Methods 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 238000004537 pulping Methods 0.000 claims description 4
- 238000003980 solgel method Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims 2
- 238000004090 dissolution Methods 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 10
- 238000005470 impregnation Methods 0.000 abstract description 9
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 229910000510 noble metal Inorganic materials 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 230000008929 regeneration Effects 0.000 abstract description 3
- 238000011069 regeneration method Methods 0.000 abstract description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 13
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellityc acid Natural products OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 10
- 238000011068 loading method Methods 0.000 description 9
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical class ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- ZPAKUZKMGJJMAA-UHFFFAOYSA-N Cyclohexane-1,2,4,5-tetracarboxylic acid Chemical compound OC(=O)C1CC(C(O)=O)C(C(O)=O)CC1C(O)=O ZPAKUZKMGJJMAA-UHFFFAOYSA-N 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium on carbon Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004642 Polyimide Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- -1 hydrogenated pyromellitic acid ester Chemical class 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 1
- RPNNPZHFJPXFQS-UHFFFAOYSA-N methane;rhodium Chemical compound C.[Rh] RPNNPZHFJPXFQS-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Classifications
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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
- 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
- B01J23/56—Platinum group metals
- B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B01J35/617—
-
- B01J35/618—
-
- B01J35/635—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/04—Ortho-condensed systems
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention discloses a catalyst for preparing 1,2,4, 5-cyclohexane tetracarboxylic dianhydride by hydrogenation of pyromellitic anhydride and a preparation method thereof, wherein the active component of the catalyst is Pt, the auxiliary agent is Ga, and the carrier is titanium silicon composite oxide, wherein the Pt content is 0.1-1.0wt%, ga: the mol ratio of Pt is 0.1-100, and the TiO in the titanium silicon composite oxide carrier 2 ：SiO 2 The molar ratio is 0.1-20, and the specific surface area is more than or equal to 500m 2 Per gram, pore volume is more than or equal to 0.6cm 3 And/g. The preparation method of the catalyst of the invention is that the active component can be introduced in the synthesis process of the titanium-silicon composite oxide, and the other active component is loaded on the carrier in an impregnation mode after the synthesis of the titanium-silicon composite oxide. The catalyst of the invention is resistant to strong acid, can be directly hydrogenated in aqueous solution, is not easy to deactivate, and has good performance after regeneration; the catalyst has low noble metal content, and the conversion rate of the reaction for preparing 1,2,4, 5-cyclohexane tetracarboxylic dianhydride by hydrogenation of pyromellitic anhydride is more than or equal to 99.5%, and the yield is more than or equal to 99.0%.
Description
Technical Field
The invention relates to the field of alicyclic dianhydride hydrogenation catalysts, in particular to a catalyst capable of resisting acid and having low noble metal loading and used for preparing 1,2,4, 5-cyclohexane tetracarboxylic dianhydride by directly hydrogenating pyromellitic anhydride and a preparation method thereof.
Background
The 1,2,4, 5-cyclohexane tetracarboxylic dianhydride is used as a dianhydride monomer for synthesizing colorless transparent polyimide, and the polyimide synthesized by using the dianhydride monomer and diamine monomer not only has good transparency, but also has high breakdown strength, higher heat resistance, high glass transition temperature, low moisture absorption rate, low dielectric constant and dielectric loss, and good adhesion with metal and other base materials, and has wide application prospect in the high and new technical fields of electronics, optics, aerospace and the like.
Chinese patent CN 104926649B discloses a method for preparing hydrogenated pyromellitic acid ester by catalytic hydrogenation of pyromellitic acid ester and then preparing 1,2,4, 5-cyclohexane tetracarboxylic dianhydride by hydrolysis, and specifically discloses a method for preparing Pd-C or Ru-C with a loading amount of up to 5wt% by catalytic hydrogenation, wherein the loading amount of noble metal used by the catalyst is large, so that the production process cost is high, and the process does not have economy.
Chinese patent CN 108069978B discloses a synthesis method of 1,2,4, 5-cyclohexane tetracarboxylic dianhydride, which requires esterification and hydrogenation of pyromellitic acid, and has long process route and complicated operation procedure, and the catalyst is Ru-Pd/Al 2 O 3 The total loading of noble metal is more than 1wt%, the noble metal is used high, and the production cost is high.
Chinese patent CN 103992330B discloses a method for preparing electronic-grade hydrogenated pyromellitic dianhydride, wherein the catalyst used in hydrogenation is Pd-C or Ru-C or Pt-C with active component loading up to 5wt%, and the catalyst accounts for more than 7% of the pyromellitic dianhydride, which results in higher operation cost and extremely adverse production cost.
In the preparation of 1,2,4, 5-cyclohexane tetracarboxylic dianhydride, the technical key is that a hydrogenation catalyst is prepared, one route for synthesizing 1,2,4, 5-cyclohexane tetracarboxylic dianhydride is through catalytic hydrogenation of pyromellitic acid to obtain hydrogenated pyromellitic acid, and the hydrogenation medium is easy to inactivate a conventional rhodium carbon and palladium carbon catalyst because the pyromellitic acid is acidic, and the other route is through esterification of pyromellitic acid (dianhydride) into an ester substance, and then hydrogenation is carried out after the ester substance is converted into an acidic substance, but the process route is long and complicated, and the production efficiency is low.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provide a catalyst for preparing 1,2,4, 5-cyclohexane tetracarboxylic dianhydride by hydrogenation of pyromellitic anhydride, which has low active component loading, high catalytic activity, long service life and difficult deactivationThe catalyst adopts titanium-silicon composite oxide as a carrier, and the catalyst Pt-Ga/TiO prepared by the carrier 2 -SiO 2 The active component has low loading, is used for preparing 1,2,4, 5-cyclohexane tetracarboxylic dianhydride by hydrogenation of pyromellitic anhydride, has high catalytic activity, long service life and difficult inactivation, and can be directly hydrogenated without esterification, thereby having simple process route.
The invention is realized by the following technical scheme.
The invention relates to a catalyst for preparing 1,2,4, 5-cyclohexane tetracarboxylic dianhydride by hydrogenation of pyromellitic anhydride, which consists of active components Pt, an auxiliary agent Ga and a titanium silicon composite oxide carrier, wherein the Pt content is 0.1-1.0wt%, the molar ratio of Ga to Pt is 0.1-100, and TiO in the titanium silicon composite oxide carrier 2 ：SiO 2 The molar ratio is 0.1-20, and the specific surface area is more than or equal to 500m 2 Per gram, pore volume is more than or equal to 0.6cm 3 /g。
The preparation method of the catalyst comprises two methods, wherein one method is to introduce active components in the synthesis process of the titanium-silicon composite oxide to prepare the catalyst, and the other method is to load the active components on a carrier in an impregnation mode after the titanium-silicon composite oxide carrier is synthesized.
The invention provides a preparation method of a catalyst for preparing 1,2,4, 5-cyclohexane tetracarboxylic dianhydride by hydrogenation of pyromellitic anhydride, which comprises the following steps:
1) Preparation of SiO 2 An aqueous solution of water glass with a content of 5-25 wt% is used as a base solution, which is called A solution;
2) Preparation of TiO 2 An aqueous solution of titanyl sulfate with the content of 10-18 wt% and chloroplatinic acid and gallium chloride are added, which is called solution B;
3) Slowly adding the solution B into the solution A under the condition of stirring, carrying out neutralization reaction, and controlling the pH value of the reaction end point to be 5-10 after the sol-gel process;
4) Adding ammonia water solution into the solution to adjust the pH value to 6-9, aging at the temperature of 40-120 ℃, separating solid from liquid, and pulping and washing with deionized water; drying and roasting the filter cake to obtain an oxidized catalyst sample;
5) The catalyst in oxidation state is pure hydrogen at 500-550 ℃ and the space velocity is 500h -1 ～1500h -1 Reducing for 3-7 h to obtain the reduced catalyst.
The preparation method of the catalyst for preparing 1,2,4, 5-cyclohexane tetracarboxylic dianhydride by hydrogenation of pyromellitic anhydride provided by the invention comprises the following steps:
1) Configuration of SiO 2 An aqueous solution of water glass with a content of 5-25 wt% is used as a base solution;
2) Configuring TiO 2 An aqueous solution of titanyl sulfate in an amount of 10 to 18 wt%;
3) Adding the solution B into the solution A at a certain speed under the condition of stirring, carrying out neutralization reaction, and controlling the pH value of the reaction end point to be 5-10 after the sol-gel process;
4) Adding ammonia water solution into the solution to adjust the pH value to 6-9, aging at 40-120 ℃, separating solid from liquid, and pulping and washing with deionized water;
5) Drying and roasting the filter cake to obtain a titanium-silicon composite oxide carrier sample; preparing a proper amount of chloroplatinic acid and gallium chloride into an aqueous solution, immersing the aqueous solution into a titanium-silicon composite oxide carrier, and drying and roasting the titanium-silicon composite oxide carrier to obtain an oxidized catalyst sample.
6) The sample is purified hydrogen gas at 500-550 ℃ and the space velocity is 500h -1 ～1500h -1 Reducing for 3-7 h to obtain the reduced catalyst.
The catalyst can be used for directly hydrogenating the reaction raw material pyromellitic anhydride after being dissolved in water, or for firstly esterifying and then hydrogenating the pyromellitic anhydride. The catalyst can be used for hydrogenation in a continuous fixed bed reactor, the hydrogenation condition is that the temperature is 60-120 ℃, the pressure is 4-10 MPa, and the space velocity is 1-10 h -1 Or can be used for kettle reactor hydrogenation, the hydrogenation condition is that the temperature is 60-120 ℃, the pressure is 1-10 MPa, and the catalyst is: pyromellitic anhydride as a reaction material=0.1 to 0.5 (mass ratio). The hydrogenation product is decompressed and dried to obtain 1,2,4, 5-cyclohexane tetracarboxylic acid, and the 1,2,4, 5-cyclohexane tetracarboxylic acid is dehydrated by acetic anhydride to obtain 1,2,4, 5-cyclohexane tetracarboxylic dianhydride. The adding amount of acetic anhydride is 3-8 times of the mass of 1,2,4, 5-cyclohexane tetracarboxylic acid, and the dehydration temperature is 60 DEG C～120℃。
The invention has the following advantages:
the catalyst adopts the titanium-silicon composite oxide as a carrier, and the carrier material has a surface structure with high specific surface and large pore volume, is not easy to change the surface structure in an acidic medium, and has good thermal stability and hydrothermal stability. The catalyst preparation method disclosed by the invention adds active components in the carrier synthesis process, or introduces auxiliary agents in the impregnation process, so that the active components are highly dispersed on the carrier, and the catalyst Pt-Ga/TiO prepared by the carrier 2 -SiO 2 The active component has low loading, is used for preparing 1,2,4, 5-cyclohexane tetracarboxylic dianhydride by hydrogenation of pyromellitic anhydride, has high catalytic activity, long service life and difficult inactivation, and can be directly hydrogenated without esterification, thereby having simple process route.
The specific embodiment is as follows:
the following examples are given to illustrate the technical principle, implementation method and effect of the present invention, but the method and core idea of the present invention are not limited thereto.
Example 1
Catalyst A: the active component Pt and the auxiliary agent Ga in the catalyst A are introduced in the synthesis process of the titanium-silicon composite oxide, and Pt:0.9w%, ga:1.6w%.
100g of water glass was dissolved in 0.9kg of deionized water and used as a base solution, referred to as solution A. 100g of titanyl sulfate was dissolved in 0.9kg of deionized water, and 3g of chloroplatinic acid and 5g of gallium chloride, referred to as solution B, were added. Slowly adding the solution B into the solution A under the condition of stirring at 50 ℃ and 200rpm, controlling the pH value of the titration end point to be 7,80 ℃ and aging for 3 hours, and washing with deionized water to be neutral. And drying the obtained filter cake and roasting at 550 ℃ to obtain an oxidized catalyst sample. The sample was reduced at 550℃under pure hydrogen for 5h to give reduced catalyst A.
Example 2
Catalyst B: after the active component Pt and the auxiliary agent Ga in the catalyst B are synthesized on the titanium-silicon composite oxide, the active component Pt and the auxiliary agent Ga are introduced by an impregnation method, and Pt:0.9w%, ga:1.6w%.
100g of water glass was dissolved in 0.9kg of deionized water and used as a base solution, referred to as solution A. 100g of titanyl sulfate was dissolved in 0.9kg of deionized water and designated as solution B. Slowly adding the solution B into the solution A under the condition of stirring at 50 ℃ and 200rpm, controlling the pH value of the titration end point to be 7,80 ℃ and aging for 3 hours, and washing with deionized water to be neutral. And drying the obtained filter cake and roasting at 550 ℃ to obtain a titanium-silicon composite oxide sample.
3g of chloroplatinic acid and 5g of gallium chloride are dissolved in 1mol/L hydrochloric acid aqueous solution to prepare impregnating solution, active components are loaded on the titanium-silicon composite oxide by an equal volume impregnation method, and the catalyst sample in an oxidation state is obtained after drying and roasting at 550 ℃. The sample was reduced at 550℃under pure hydrogen for 5h to give catalyst B in the reduced state.
Comparative example 1
Catalyst C: the catalyst C is active component Pt and additive Ga which are loaded on the commercial active carbon by an impregnation method, and the Pt is as follows: 0.9w%, ga:1.6w%.
3g of chloroplatinic acid and 5g of gallium chloride are dissolved in 1mol/L hydrochloric acid aqueous solution to prepare impregnating solution, active components are loaded on active carbon by an isovolumetric impregnation method, and an oxidized catalyst sample is obtained after drying and roasting at 550 ℃. The sample was reduced at 550℃under pure hydrogen for 5h to give catalyst C in the reduced state.
Comparative example 2
Catalyst D: the catalyst D is prepared by loading active components Pt and an auxiliary agent Ga on commercial alumina by an impregnation method, wherein the Pt is as follows: 0.9w%, ga:1.6w%.
3g of chloroplatinic acid and 5g of gallium chloride are dissolved in 1mol/L hydrochloric acid aqueous solution to prepare impregnating solution, active components are loaded on active carbon by an isovolumetric impregnation method, and an oxidized catalyst sample is obtained after drying and roasting at 550 ℃. The sample was reduced at 550℃under pure hydrogen for 5h to give reduced catalyst D.
Catalysts A, B, C and D are used for the reaction of preparing 1,2,4, 5-cyclohexane tetracarboxylic dianhydride by hydrogenating pyromellitic dianhydride under the same conditions, and are used for hydrogenation in a continuous fixed bed reactor, wherein the hydrogenation conditions are that the feed is an aqueous solution of pyromellitic dianhydride, and the pyromellitic dianhydride is obtained by the steps of: water=1:8 (massRatio), temperature 90 ℃, pressure 6MPa and airspeed 5h -1 The results of the continuous fixed bed reactor hydrogenation are shown in Table 1.
TABLE 1
As can be seen from the results of hydrogenation in the continuous fixed bed reactor of Table 1, the prepared catalysts A and B have better reactivity and stability than the catalysts C and D prepared by using conventional activated carbon or alumina as a carrier.
The catalyst can also be used for hydrogenation in a kettle reactor, wherein the hydrogenation condition is that the kettle is an aqueous solution of pyromellitic dianhydride, and the pyromellitic dianhydride is: water=1:8 (mass ratio), temperature 90 ℃, pressure 6MPa, catalyst: pyromellitic anhydride as a reaction raw material=0.1 (mass ratio). The catalyst reacts in an autoclave for 4 hours, after the reaction is finished, the catalyst and the product are subjected to solid-liquid separation, the catalyst is dried in the air for regeneration and then is used for the next reaction, and the hydrogenation result of the kettle reactor is shown in table 2.
As can be seen from the hydrogenation result of the kettle reactor in Table 2, the prepared catalysts A and B have better reactivity and stability than the catalysts C and D prepared by using conventional activated carbon or alumina as the carrier by using the titanium-silicon composite oxide as the carrier, and after regeneration, the performance of the catalysts A and B is basically the same as the initial performance, and the performance of the catalysts C and D is obviously reduced compared with the initial performance.
Claims (4)
1. The catalyst for preparing 1,2,4, 5-cyclohexane tetracarboxylic dianhydride by hydrogenation of pyromellitic anhydride is characterized by comprising an active component Pt, an auxiliary agent Ga and a titanium silicon composite oxide carrier, wherein the Pt content is 0.1-1.0wt%, and the Ga: the molar ratio of Pt is 0.1-100, and TiO in the titanium silicon composite oxide carrier 2 ：SiO 2 The molar ratio is 0.1-20, and the specific surface area is more than or equal to 500m 2 Per gram, pore volume is more than or equal to 0.6cm 3 /g; the preparation method of the catalyst comprises the following steps:
1) Preparation of SiO 2 The water solution of water glass with the content of 5wt% -25% by weight is used as base solution, and is called solution A;
2) Preparation of TiO 2 An aqueous solution of titanyl sulfate with the content of 10-wt wt% to 18wt% is called as solution B;
3) Slowly adding the solution B into the solution A under the condition of stirring, carrying out a neutralization reaction, and controlling the pH value of a reaction end point to be 5-10 after a sol-gel process;
4) Adding ammonia water solution into the solution to adjust the pH value to 6-9, aging at the temperature of 40-120 ℃, separating solid from liquid, and pulping and washing with deionized water; drying and roasting the filter cake to obtain a titanium-silicon composite oxide carrier;
5) Preparing chloroplatinic acid and gallium chloride into aqueous solution, dipping the aqueous solution into the titanium-silicon composite oxide carrier, and drying and roasting the aqueous solution to obtain an oxidized catalyst sample;
6) The catalyst in oxidation state is pure hydrogen at 500-550 ℃ and the space velocity is 500h -1 ~1500h -1 And reducing for 3-7 h to obtain the reduced catalyst.
2. A method for preparing the catalyst for preparing 1,2,4, 5-cyclohexane tetracarboxylic dianhydride by hydrogenation of pyromellitic anhydride according to claim 1, which is characterized by comprising the following steps:
1) Preparation of SiO 2 The water solution of water glass with the content of 5wt% -25% by weight is used as base solution, and is called solution A;
2) Preparation of TiO 2 An aqueous solution of titanyl sulfate with the content of 10-wt wt% to 18wt% is called as solution B;
3) Slowly adding the solution B into the solution A under the condition of stirring, carrying out a neutralization reaction, and controlling the pH value of a reaction end point to be 5-10 after a sol-gel process;
4) Adding ammonia water solution into the solution to adjust the pH value to 6-9, aging at the temperature of 40-120 ℃, separating solid from liquid, and pulping and washing with deionized water; drying and roasting the filter cake to obtain a titanium-silicon composite oxide carrier;
5) Preparing chloroplatinic acid and gallium chloride into aqueous solution, dipping the aqueous solution into the titanium-silicon composite oxide carrier, and drying and roasting the aqueous solution to obtain an oxidized catalyst sample;
6) The catalyst in oxidation state is pure hydrogen at 500-550 ℃ and the space velocity is 500h -1 ~1500h -1 And reducing for 3-7 h to obtain the reduced catalyst.
3. Use of the catalyst of claim 1 in the hydrogenation of pyromellitic anhydride to produce 1,2,4, 5-cyclohexane tetracarboxylic dianhydride.
4. The use according to claim 3, wherein the catalyst is used for direct hydrogenation of pyromellitic anhydride as a reaction raw material after dissolution in water, or for esterification and hydrogenation of pyromellitic anhydride; the hydrogenation mode is continuous fixed bed reactor hydrogenation or kettle reactor hydrogenation.
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| CN112473709A (en) * | 2019-09-11 | 2021-03-12 | 王宏涛 | Catalyst for synthesizing succinic acid by aqueous phase catalytic hydrogenation and application thereof |
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| CN112473709A (en) * | 2019-09-11 | 2021-03-12 | 王宏涛 | Catalyst for synthesizing succinic acid by aqueous phase catalytic hydrogenation and application thereof |
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