CN114192160A - Ruthenium-nickel catalyst and preparation method and application thereof - Google Patents
Ruthenium-nickel catalyst and preparation method and application thereof Download PDFInfo
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- CN114192160A CN114192160A CN202111270195.8A CN202111270195A CN114192160A CN 114192160 A CN114192160 A CN 114192160A CN 202111270195 A CN202111270195 A CN 202111270195A CN 114192160 A CN114192160 A CN 114192160A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 91
- DEPMYWCZAIMWCR-UHFFFAOYSA-N nickel ruthenium Chemical compound [Ni].[Ru] DEPMYWCZAIMWCR-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000003756 stirring Methods 0.000 claims abstract description 39
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 37
- MHVJRKBZMUDEEV-UHFFFAOYSA-N (-)-ent-pimara-8(14),15-dien-19-oic acid Natural products C1CCC(C(O)=O)(C)C2C1(C)C1CCC(C=C)(C)C=C1CC2 MHVJRKBZMUDEEV-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000007864 aqueous solution Substances 0.000 claims abstract description 24
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims abstract description 24
- 238000005406 washing Methods 0.000 claims abstract description 23
- 238000001035 drying Methods 0.000 claims abstract description 20
- 239000011148 porous material Substances 0.000 claims abstract description 20
- 238000009826 distribution Methods 0.000 claims abstract description 8
- 230000015572 biosynthetic process Effects 0.000 claims abstract 2
- 238000003786 synthesis reaction Methods 0.000 claims abstract 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 31
- VENMWZIMYAYKOI-UHFFFAOYSA-N nickel(2+) propan-2-one dinitrate Chemical compound CC(=O)C.[N+](=O)([O-])[O-].[Ni+2].[N+](=O)([O-])[O-] VENMWZIMYAYKOI-UHFFFAOYSA-N 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 30
- MHVJRKBZMUDEEV-APQLOABGSA-N (+)-Pimaric acid Chemical compound [C@H]1([C@](CCC2)(C)C(O)=O)[C@@]2(C)[C@H]2CC[C@](C=C)(C)C=C2CC1 MHVJRKBZMUDEEV-APQLOABGSA-N 0.000 claims description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 241000779819 Syncarpia glomulifera Species 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000001739 pinus spp. Substances 0.000 claims description 14
- 229940036248 turpentine Drugs 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 12
- 238000005984 hydrogenation reaction Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 10
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 10
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 10
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000005909 Kieselgur Substances 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000004821 distillation Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 239000006228 supernatant Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 abstract description 16
- 229910052763 palladium Inorganic materials 0.000 abstract description 8
- -1 hydrogenated propylene pimaric acid Chemical compound 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 8
- 230000002194 synthesizing effect Effects 0.000 description 6
- 238000002156 mixing Methods 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000000643 oven drying Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000004831 Hot glue Substances 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Images
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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/892—Nickel and noble metals
-
- B01J35/615—
-
- B01J35/633—
-
- B01J35/635—
-
- B01J35/647—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/36—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by hydrogenation of carbon-to-carbon unsaturated bonds
Abstract
The existing synthesis technology of the hydrogenated propylene pimaric acid uses palladium or nickel catalyst, but the palladium catalyst is expensive, the nickel catalyst has high temperature and pressure, the color is difficult to meet the requirements, and the product is unqualified. The invention provides a ruthenium-nickel catalyst and a preparation method and application thereof, wherein the ruthenium-nickel catalyst is prepared by stirring, washing and drying a diatomite-loaded nickel catalyst and a ruthenium chloride aqueous solution, and the pore diameter distribution of the ruthenium-nickel catalyst is 6-15 nm; the specific surface area is 220-300 m2(ii)/g; the total pore volume is 0.4-0.6 cm3(ii) in terms of/g. The invention uses ruthenium-nickel bimetallic diatomite supported catalyst for the first time, has low cost compared with palladium catalyst, greatly enhanced activity compared with single nickel catalyst, simple preparation process and the obtained ruthenium-nickel catalystThe product of the hydrogenated propylene pimaric acid prepared by the agent has good quality and low production cost.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a ruthenium-nickel catalyst and a preparation method and application thereof.
Background
The acrylic pimaric acid is formed by acrylic acid modified rosin and is used as hot-melt pressure-sensitive adhesive, tackifying resin of the hot-melt adhesive and scaling powder in the electronic industry. The acrylic acid modified rosin has double bonds and other easily oxidized groups, so that the product has dark color (within a general Gardner color number of 5 #), and poor stability, and along with the transformation upgrading of products in the adhesive industry and the improvement of electronic welding requirements, the acrylic acid modified rosin puts higher requirements on the aspects of color, luster, stability and the like of the acrylic pimaric acid, and requires colorlessness and high stability. Compared with the acrylpimaric acid, the hydrogenated acrylpimaric acid has the characteristics of light color, high stability and better performance, and can meet the market requirements.
At present, few synthetic documents of the hydrogenated propylene pimaric acid exist, and palladium or nickel catalysts are mostly researched, but the palladium catalyst is expensive, the temperature and the pressure of the nickel catalyst are high, the color is difficult to meet the requirements, and the product is unqualified.
Therefore, how to provide a novel catalyst to simplify the preparation of the acrylpimaric acid, improve the product quality and reduce the production cost is a problem to be solved at present.
Disclosure of Invention
The invention aims to provide a ruthenium-nickel catalyst, a preparation method and application thereof, so that the hydrogenation reaction condition of the acrylpimaric acid is mild, side reactions are reduced, the product quality is improved, and the production cost is reduced.
The ruthenium-nickel catalyst is prepared by stirring, washing and drying a diatomite-loaded nickel catalyst and a ruthenium chloride aqueous solution, wherein the pore size distribution of the catalyst is 6-15 nm; the specific surface area is 220-300 m2(ii)/g; the total pore volume is 0.4-0.6 cm3/g。
The invention also provides a preparation method of the ruthenium-nickel catalyst, which comprises the following steps:
s1, preparing a nickel nitrate acetone solution: dissolving 20-100% by mass of nickel nitrate into acetone to obtain a nickel nitrate acetone solution;
s2, preparation of diatomaceous earth supported nickel catalyst: adding kieselguhr into the nickel nitrate acetone solution prepared in the step S1, stirring at normal temperature for 8-12 hours, distilling at 40 ℃ under reduced pressure for 1.5 hours, then drying at 70 ℃ in vacuum for 1-2 hours to obtain powdery solid, then carrying out heat treatment at 150-350 ℃ for 2-4 hours, and cooling to room temperature to obtain a kieselguhr-supported nickel catalyst;
s3, preparation of ruthenium-nickel catalyst: and (3) adding the ruthenium chloride aqueous solution into the diatomite-supported nickel catalyst prepared in the step S2, stirring for 1-2 h, removing a supernatant, washing with deionized water, washing with alcohol, and drying at 50 ℃ to obtain the ruthenium-nickel catalyst.
Further, the concentration of the nickel nitrate acetone solution in the S1 is 16.7-50%.
Further, the mass ratio of the diatomite to the nickel nitrate acetone solution in the S2 is as follows: 1: 3; the stirring speed is 100 r/min.
Further, the concentration of the ruthenium chloride aqueous solution in the S3 is 1-3 per mill, and the mass ratio of the ruthenium chloride aqueous solution to the diatomite-supported nickel catalyst is 1: 1; the stirring speed is 100 r/min.
The invention also provides an application of the ruthenium-nickel catalyst, wherein the ruthenium-nickel catalyst is used for synthesizing the hydrogenated acrylic pimaric acid, and the specific method comprises the following steps:
adding acrylic rosin, turpentine and a ruthenium-nickel catalyst into a reactor according to the mass ratio of 1: 1-5: 0.001-0.005, stirring at room temperature for 0.5h, introducing nitrogen for replacement for 3 times, introducing hydrogen, increasing the pressure to 1-10 MPa, heating to 70-230 ℃, carrying out hydrogenation reaction for 1-5h, cooling to a proper temperature, filtering to remove the catalyst, and carrying out reduced pressure distillation to remove turpentine, thereby obtaining light-color high-stability hydrogenated acrylic pimaric acid.
Further, the hydrogenation reaction temperature is 120-200 ℃.
Further, the temperature is reduced to a proper temperature of 30-100 ℃.
The invention uses ruthenium-nickel bimetallic diatomite supported catalyst for the first time, compared with palladium catalystThe catalyst is low in cost, the activity of the catalyst is greatly enhanced compared with that of a single nickel catalyst, the preparation process is simple, the nickel catalyst loaded by diatomite is stirred and soaked in a ruthenium salt solution, then washing treatment is carried out, and the pores are distributed to be 6-15 nm; the specific surface area is 220-300 m2(ii)/g; the total pore volume is 0.4-0.6 cm3/g。
According to the invention, the self-made ruthenium-nickel catalyst is adopted for catalyzing the hydrogenation of the acrylpimaric acid for the first time, the reaction temperature is controlled to be 120-200 ℃, the pressure is controlled to be 1-10 MPa, the reaction condition is mild, the product quality is favorably improved, and the production cost is low.
Drawings
FIG. 1 is a scanning electron microscope (20 μm) of a ruthenium-nickel catalyst of the present invention;
FIG. 2 is a scanning electron microscope (10 μm) of a ruthenium-nickel catalyst of the present invention;
FIG. 3 is a scanning electron microscope (2 μm) of a ruthenium-nickel catalyst of the present invention;
FIG. 4 is a scanning electron microscope (1 μm) of a ruthenium-nickel catalyst of the present invention;
FIG. 5 is an infrared spectrum of a ruthenium-nickel catalyst of the present invention;
FIG. 6 is a diagram of a sample of the hydropropylenepimaric acid produced by the ruthenium-nickel catalyst of the present invention.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
A ruthenium-nickel catalyst is prepared by mixing, washing and drying a nickel catalyst loaded by diatomite and a ruthenium chloride aqueous solution, wherein the pore diameter distribution of the ruthenium-nickel catalyst is 11 nm-15 nm; specific surface area of 220m2(ii)/g; total pore volume 0.4cm3/g。
The preparation method of the ruthenium-nickel catalyst comprises the following steps:
s1, preparing a nickel nitrate acetone solution: dissolving 20% nickel nitrate into acetone to obtain 16.7% nickel nitrate acetone solution;
s2, preparation of diatomaceous earth supported nickel catalyst: adding diatomite into the nickel nitrate acetone solution prepared in the step S1, wherein the mass ratio of the diatomite to the nickel nitrate acetone solution is as follows: 1: 3; stirring at the normal temperature at the stirring speed of 100r/min for 12h, distilling at 40 ℃ under reduced pressure for 1.5h, drying at 70 ℃ under vacuum for 1h to obtain powdery solid, performing heat treatment at 150 ℃ for 4h, and cooling to room temperature to obtain a diatomite-loaded nickel catalyst;
s3, preparation of ruthenium-nickel catalyst: adding a ruthenium chloride aqueous solution with the concentration of 1 per mill into the diatomite-supported nickel catalyst prepared in the step S2, wherein the mass ratio of the ruthenium chloride aqueous solution to the diatomite-supported nickel catalyst is 1: 1; stirring for 2h at the stirring speed of 100r/min, discarding the supernatant, washing with deionized water, washing with alcohol, and drying at 50 deg.C to obtain the ruthenium-nickel catalyst.
The ruthenium-nickel catalyst is used for synthesizing the hydrogenated acrylic pimaric acid, and the specific method comprises the following steps:
adding acrylic rosin, turpentine and a ruthenium-nickel catalyst into a reactor according to the mass ratio of 1:1:0.001, stirring for 0.5h at room temperature, introducing nitrogen for replacement for 3 times, introducing hydrogen, increasing the pressure to 1MPa, heating to 70 ℃, performing hydrogenation reaction for 5h, cooling to 50 ℃, filtering to remove the catalyst, and performing reduced pressure distillation to remove turpentine to obtain light-color high-stability hydrogenated acrylic pimaric acid.
The technical indexes of the hydrogenated acrylic pimaric acid prepared in the embodiment are as follows: color (hansencolor): 150; softening point (. degree. C.): 130, 130; acid value (mg KOH/g): 228.
example 2
A ruthenium-nickel catalyst is prepared by stirring, washing and drying a nickel catalyst loaded by diatomite and a ruthenium chloride aqueous solution, wherein the pores are distributed at 9-13 nm; specific surface area 240m2(ii)/g; total pore volume 0.45cm3/g。
The preparation method of the ruthenium-nickel catalyst comprises the following steps:
s1, preparing a nickel nitrate acetone solution: dissolving 100% by mass of nickel nitrate into acetone to obtain a 50% nickel nitrate acetone solution;
s2, preparation of diatomaceous earth supported nickel catalyst: adding diatomite into the nickel nitrate acetone solution prepared in the step S1, wherein the mass ratio of the diatomite to the nickel nitrate acetone solution is as follows: 1: 3; stirring at the normal temperature at the stirring speed of 100r/min for 8 hours, distilling at 40 ℃ under reduced pressure for 1.5 hours, then drying at 70 ℃ in vacuum for 2 hours to obtain powdery solid, then carrying out heat treatment at 350 ℃ for 2 hours, and cooling to room temperature to obtain a diatomite-loaded nickel catalyst;
s3, preparation of ruthenium-nickel catalyst: adding a ruthenium chloride aqueous solution with the concentration of 3 per mill into the diatomite-supported nickel catalyst prepared in the step S2, wherein the mass ratio of the ruthenium chloride aqueous solution to the diatomite-supported nickel catalyst is 1: 1; stirring for 1h at the stirring speed of 100r/min, discarding the supernatant, washing with deionized water, washing with alcohol, and drying at 50 deg.C to obtain the ruthenium-nickel catalyst.
The ruthenium-nickel catalyst is used for synthesizing the hydrogenated acrylic pimaric acid, and the specific method comprises the following steps:
adding acrylic rosin, turpentine and a ruthenium-nickel catalyst into a reactor according to the mass ratio of 1:5:0.002, stirring for 0.5h at room temperature, introducing nitrogen for replacement for 3 times, introducing hydrogen, boosting the pressure to 10MPa, heating to 230 ℃, performing hydrogenation reaction for 1h, cooling to 60 ℃, filtering to remove the catalyst, and performing reduced pressure distillation to remove turpentine to obtain light-color high-stability hydrogenated acrylic pimaric acid.
The technical indexes of the hydrogenated acrylic pimaric acid prepared in the embodiment are as follows: color (hansencolor): 150; softening point (. degree. C.): 132; acid value (mg KOH/g): 230.
example 3
A ruthenium-nickel catalyst is prepared by mixing, washing and drying a nickel catalyst loaded by diatomite and a ruthenium chloride aqueous solution, wherein the pore diameter distribution of the ruthenium-nickel catalyst is 10 nm-15 nm; specific surface area of 250m2(ii)/g; total pore volume 0.5cm3/g。
The preparation method of the ruthenium-nickel catalyst comprises the following steps:
s1, preparing a nickel nitrate acetone solution: dissolving 40% nickel nitrate into acetone to obtain a nickel nitrate acetone solution with the concentration of 28.6%;
s2, preparation of diatomaceous earth supported nickel catalyst: adding diatomite into the nickel nitrate acetone solution prepared in the step S1, wherein the mass ratio of the diatomite to the nickel nitrate acetone solution is as follows: 1: 3; stirring at the normal temperature at the stirring speed of 100r/min for 9 hours, distilling at 40 ℃ under reduced pressure for 1.5 hours, then drying at 70 ℃ under vacuum for 1.5 hours to obtain powdery solid, then carrying out heat treatment at 200 ℃ for 3.5 hours, and cooling to room temperature to obtain the diatomite-loaded nickel catalyst;
s3, preparation of ruthenium-nickel catalyst: adding a ruthenium chloride aqueous solution with the concentration of 2 per mill into the diatomite-supported nickel catalyst prepared in the step S2, wherein the mass ratio of the ruthenium chloride aqueous solution to the diatomite-supported nickel catalyst is 1: 1; stirring for 1.5h at a stirring speed of 100r/min, discarding the supernatant, washing with deionized water, washing with alcohol, and oven drying at 50 deg.C to obtain the ruthenium-nickel catalyst.
The ruthenium-nickel catalyst is used for synthesizing the hydrogenated acrylic pimaric acid, and the specific method comprises the following steps:
adding acrylic rosin, turpentine and a ruthenium-nickel catalyst into a reactor according to the mass ratio of 1:2:0.003, stirring for 0.5h at room temperature, introducing nitrogen for replacement for 3 times, introducing hydrogen, boosting the pressure to 3MPa, heating to 120 ℃, performing hydrogenation reaction for 4h, cooling to 80 ℃, filtering to remove the catalyst, and performing reduced pressure distillation to remove turpentine to obtain light-color high-stability hydrogenated acrylic pimaric acid.
The technical indexes of the hydrogenated acrylic pimaric acid prepared in the embodiment are as follows: color (hansencolor): 125; softening point (. degree. C.): 133; acid value (mg KOH/g): 240.
example 4
A ruthenium-nickel catalyst is prepared by mixing, washing and drying a nickel catalyst loaded by diatomite and a ruthenium chloride aqueous solution, wherein the pore diameter distribution of the ruthenium-nickel catalyst is 8 nm-12 nm; specific surface area 260m2(ii)/g; total pore volume 0.55cm3/g。
The preparation method of the ruthenium-nickel catalyst comprises the following steps:
s1, preparing a nickel nitrate acetone solution: dissolving 80% by mass of nickel nitrate into acetone to obtain a 44.4% nickel nitrate acetone solution;
s2, preparation of diatomaceous earth supported nickel catalyst: adding diatomite into the nickel nitrate acetone solution prepared in the step S1, wherein the mass ratio of the diatomite to the nickel nitrate acetone solution is as follows: 1: 3; stirring at the normal temperature at the stirring speed of 100r/min for 10 hours, distilling at 40 ℃ under reduced pressure for 1.5 hours, then drying at 70 ℃ in vacuum for 2 hours to obtain powdery solid, then carrying out heat treatment at 300 ℃ for 2 hours, and cooling to room temperature to obtain a diatomite-loaded nickel catalyst;
s3, preparation of ruthenium-nickel catalyst: adding a ruthenium chloride aqueous solution with the concentration of 2.5 per mill into the diatomite-supported nickel catalyst prepared in the step S2, wherein the mass ratio of the ruthenium chloride aqueous solution to the diatomite-supported nickel catalyst is 1: 1; stirring for 2h at the stirring speed of 100r/min, discarding the supernatant, washing with deionized water, washing with alcohol, and drying at 50 deg.C to obtain the ruthenium-nickel catalyst.
The ruthenium-nickel catalyst is used for synthesizing the hydrogenated acrylic pimaric acid, and the specific method comprises the following steps:
adding acrylic rosin, turpentine and a ruthenium-nickel catalyst into a reactor according to the mass ratio of 1:3:0.004, stirring for 0.5h at room temperature, introducing nitrogen for replacement for 3 times, introducing hydrogen, boosting the pressure to 8MPa, heating to 200 ℃, performing hydrogenation reaction for 3h, cooling to 90 ℃, filtering to remove the catalyst, and performing reduced pressure distillation to remove turpentine to obtain light-color high-stability hydrogenated acrylic pimaric acid.
The technical indexes of the hydrogenated acrylic pimaric acid prepared in the embodiment are as follows: color (hansencolor): 125; softening point (. degree. C.): 135 of the total weight of the raw materials; acid value (mg KOH/g): 235.
example 5
A ruthenium-nickel catalyst is prepared by mixing, washing and drying a nickel catalyst loaded by diatomite and a ruthenium chloride aqueous solution, wherein the pore diameter distribution of the ruthenium-nickel catalyst is 6 nm-10 nm; specific surface area 300m2(ii)/g; total pore volume 0.6cm3/g。
The preparation method of the ruthenium-nickel catalyst comprises the following steps:
s1, preparing a nickel nitrate acetone solution: dissolving 60% by mass of nickel nitrate into acetone to obtain a 37.5% nickel nitrate acetone solution;
s2, preparation of diatomaceous earth supported nickel catalyst: adding diatomite into the nickel nitrate acetone solution prepared in the step S1, wherein the mass ratio of the diatomite to the nickel nitrate acetone solution is as follows: 1: 3; stirring at the normal temperature at the stirring speed of 100r/min for 11h, distilling at 40 ℃ under reduced pressure for 1.5h, drying at 70 ℃ under vacuum for 1.5h to obtain powdery solid, performing heat treatment at 250 ℃ for 2.5h, and cooling to room temperature to obtain a diatomite-loaded nickel catalyst;
s3, preparation of ruthenium-nickel catalyst: adding a ruthenium chloride aqueous solution with the concentration of 1.5 per mill into the diatomite-supported nickel catalyst prepared in the step S2, wherein the mass ratio of the ruthenium chloride aqueous solution to the diatomite-supported nickel catalyst is 1: 1; stirring for 1.5h at a stirring speed of 100r/min, discarding the supernatant, washing with deionized water, washing with alcohol, and oven drying at 50 deg.C to obtain the ruthenium-nickel catalyst.
The ruthenium-nickel catalyst is used for synthesizing the hydrogenated acrylic pimaric acid, and the specific method comprises the following steps:
adding acrylic rosin, turpentine and a ruthenium-nickel catalyst into a reactor according to the mass ratio of 1:4:0.005, stirring for 0.5h at room temperature, introducing nitrogen for replacement for 3 times, introducing hydrogen, boosting the pressure to 5MPa, heating to 160 ℃, performing hydrogenation reaction for 2.5h, cooling to 60 ℃, filtering to remove the catalyst, and performing reduced pressure distillation to remove turpentine to obtain light-color high-stability hydrogenated acrylic pimaric acid.
The technical indexes of the hydrogenated acrylic pimaric acid prepared in the embodiment are as follows: color (hansencolor): 100, respectively; softening point (. degree. C.): 135 of the total weight of the raw materials; acid value (mg KOH/g): 230.
palladium, nickel catalysts and the ruthenium-nickel catalyst of the invention were used for the preparation of pimaric acid hydride with the following differences (1000 kg of pimaric acid hydride prepared):
in conclusion, the ruthenium-nickel catalyst obtained by the invention has the pore diameter distribution of 6-15 nm; the specific surface area is 220-300 m2(ii)/g; the total pore volume is 0.4-0.6 cm3(ii) in terms of/g. The catalytic activity of the catalyst is greatly superior to that of a single nickel catalyst (the single nickel catalyst cannot be used for producing the hydrogenated propylene pimaric acid product), and the price of the catalyst is higher than that of a palladium catalystThe cost is low, the preparation method is simple and feasible, and the hydrogenated acrylic pimaric acid product prepared by the ruthenium-nickel catalyst has excellent quality and low production cost.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements, etc. made by those skilled in the art within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (8)
1. A ruthenium-nickel catalyst is prepared by stirring, washing and drying a diatomite-loaded nickel catalyst and a ruthenium chloride aqueous solution, wherein the pore diameter distribution of the catalyst is 6-15 nm; the specific surface area is 220-300 m2(ii)/g; the total pore volume is 0.4-0.6 cm3/g。
2. The method for preparing a ruthenium-nickel catalyst according to claim 1, comprising the steps of:
s1, preparing a nickel nitrate acetone solution: dissolving 20-100% by mass of nickel nitrate into acetone to obtain a nickel nitrate acetone solution;
s2, preparation of diatomaceous earth supported nickel catalyst: adding kieselguhr into the nickel nitrate acetone solution prepared in the step S1, stirring at normal temperature for 8-12 hours, distilling at 40 ℃ under reduced pressure for 1.5 hours, then drying at 70 ℃ in vacuum for 1-2 hours to obtain powdery solid, then carrying out heat treatment at 150-350 ℃ for 2-4 hours, and cooling to room temperature to obtain a kieselguhr-supported nickel catalyst;
s3, preparation of ruthenium-nickel catalyst: and (3) adding the ruthenium chloride aqueous solution into the diatomite-supported nickel catalyst prepared in the step S2, stirring for 1-2 h, removing a supernatant, washing with deionized water, washing with alcohol, and drying at 50 ℃ to obtain the ruthenium-nickel catalyst.
3. The method of preparing a ruthenium-nickel catalyst according to claim 2, wherein the concentration of the nickel nitrate in the nickel nitrate acetone solution in S1 is 16.7 to 50%.
4. The method for preparing the ruthenium-nickel catalyst according to claim 2, wherein the mass ratio of the diatomite to the nickel nitrate acetone solution in the S2 is as follows: 1: 3; the stirring speed is 100 r/min.
5. The method for preparing the ruthenium-nickel catalyst according to claim 2, wherein the concentration of the aqueous solution of ruthenium chloride in the S3 is 1-3 per thousand, and the mass ratio of the aqueous solution of ruthenium chloride to the diatomite-supported nickel catalyst is 1: 1; the stirring speed is 100 r/min.
6. The use of the ruthenium-nickel catalyst according to any one of claims 1 to 5 for the synthesis of hydroacrylpimaric acid by the following specific method:
adding acrylic rosin, turpentine and a ruthenium-nickel catalyst into a reactor according to the mass ratio of 1: 1-5: 0.001-0.005, stirring at room temperature for 0.5h, introducing nitrogen for replacement for 3 times, introducing hydrogen, increasing the pressure to 1-10 MPa, heating to 70-230 ℃, carrying out hydrogenation reaction for 1-5h, cooling to a proper temperature, filtering to remove the catalyst, and carrying out reduced pressure distillation to remove turpentine, thereby obtaining light-color high-stability hydrogenated acrylic pimaric acid.
7. The use of the ruthenium-nickel catalyst according to claim 6, wherein the hydrogenation reaction temperature is 120 to 200 ℃.
8. The use of the ruthenium-nickel catalyst according to claim 6, wherein the temperature reduction to a suitable temperature is 30 to 100 ℃.
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| CN105879874A (en) * | 2016-05-16 | 2016-08-24 | 连中博 | High-dispersion loaded nickel catalyst and preparation method thereof |
| CN108559403A (en) * | 2018-01-09 | 2018-09-21 | 广西鼎弘树脂有限公司 | A kind of an ultra shallow color high stability acrylic acid rosin and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105879874A (en) * | 2016-05-16 | 2016-08-24 | 连中博 | High-dispersion loaded nickel catalyst and preparation method thereof |
| CN108559403A (en) * | 2018-01-09 | 2018-09-21 | 广西鼎弘树脂有限公司 | A kind of an ultra shallow color high stability acrylic acid rosin and preparation method thereof |
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