CN110652985A - Preparation method and application of catalyst for hydrogenation of dimer acid - Google Patents
Preparation method and application of catalyst for hydrogenation of dimer acid Download PDFInfo
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- CN110652985A CN110652985A CN201910952017.XA CN201910952017A CN110652985A CN 110652985 A CN110652985 A CN 110652985A CN 201910952017 A CN201910952017 A CN 201910952017A CN 110652985 A CN110652985 A CN 110652985A
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- 239000002253 acid Substances 0.000 title claims abstract description 84
- 239000000539 dimer Substances 0.000 title claims abstract description 82
- 239000003054 catalyst Substances 0.000 title claims abstract description 80
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 185
- 238000006243 chemical reaction Methods 0.000 claims abstract description 135
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 85
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims abstract description 75
- 229910000838 Al alloy Inorganic materials 0.000 claims abstract description 55
- 239000007788 liquid Substances 0.000 claims abstract description 39
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 38
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000005406 washing Methods 0.000 claims abstract description 26
- 239000011148 porous material Substances 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 23
- 229910052751 metal Inorganic materials 0.000 claims abstract description 22
- 239000002184 metal Substances 0.000 claims abstract description 22
- 238000001914 filtration Methods 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 20
- 239000003513 alkali Substances 0.000 claims abstract description 16
- 239000002480 mineral oil Substances 0.000 claims abstract description 11
- 235000010446 mineral oil Nutrition 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 230000004913 activation Effects 0.000 claims abstract description 7
- 238000005520 cutting process Methods 0.000 claims abstract description 7
- 230000009467 reduction Effects 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 72
- 239000001257 hydrogen Substances 0.000 claims description 68
- 229910052739 hydrogen Inorganic materials 0.000 claims description 68
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 66
- 229910052757 nitrogen Inorganic materials 0.000 claims description 39
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000002245 particle Substances 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 18
- 239000010453 quartz Substances 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 12
- 238000002791 soaking Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 238000002844 melting Methods 0.000 claims description 11
- 230000008018 melting Effects 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 239000012442 inert solvent Substances 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 238000004090 dissolution Methods 0.000 claims description 8
- 230000003213 activating effect Effects 0.000 claims description 7
- 238000001994 activation Methods 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 238000003825 pressing Methods 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 230000001502 supplementing effect Effects 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 230000005284 excitation Effects 0.000 claims 1
- 230000008929 regeneration Effects 0.000 claims 1
- 238000011069 regeneration method Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 238000009903 catalytic hydrogenation reaction Methods 0.000 abstract description 2
- 229910045601 alloy Inorganic materials 0.000 description 12
- 239000000956 alloy Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 239000002994 raw material Substances 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- HCVSCPUDMOTGSX-UHFFFAOYSA-N 1-heptyl-2-pentylcyclohexane Chemical compound C(CCCCCC)C1C(CCCC1)CCCCC HCVSCPUDMOTGSX-UHFFFAOYSA-N 0.000 description 2
- ALMXBPKJWRADME-UHFFFAOYSA-N CCCCCCCC1CC=C(CC1CCCCC)C=C Chemical compound CCCCCCCC1CC=C(CC1CCCCC)C=C ALMXBPKJWRADME-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229940116226 behenic acid Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000017423 tissue regeneration Effects 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
- C07C2602/14—All rings being cycloaliphatic
- C07C2602/26—All rings being cycloaliphatic the ring system containing ten carbon atoms
- C07C2602/28—Hydrogenated naphthalenes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a preparation method and application of a catalyst for hydrogenation of dimer acid, wherein a metallic nickel block and an aluminum ingot are proportionally placed into a crucible and heated and melted; cooling to form nickel-aluminum alloy, and cutting into 0.1-1.5 cm3The nickel-aluminum alloy block or the nickel-aluminum molten metal liquid flows through a sieve with 20-40 meshes and is dropped into mineral oil to form aluminum alloy balls; dissolving nickel-aluminum alloy blocks or nickel-aluminum alloy balls by using alkali liquor, and then filtering, washing and drying to obtain honeycomb nickel blocks or nickel balls with uniform pore diameters; before the catalyst is used, reduction activation is carried out. The soaked activated catalyst, dimer acid and inert solventAdding the mixture into a reaction kettle for catalytic hydrogenation reaction. The catalyst obtained by the invention has the advantages of high specific surface area, high catalytic activity, uniform pore diameter and low cost. The catalyst of the invention is a special catalyst suitable for the hydrogenation reaction of dimer acid, and the conversion rate of dimer acid reaches 94-99%.
Description
Technical Field
The invention relates to a preparation method and application of a catalyst for hydrogenation of dimer acid, belonging to the technical field of chemical industry.
Background
The hydrogenated dimer acid is aliphatic saturated diacid with 36 carbon atoms, and is obtained by catalytically hydrogenating unsaturated dimer acid containing double bonds; because of the existence of two carboxyl reaction functional groups and no double bond in molecules, the thermal stability of the polymerization product is better, and the polymerization product is used for drug slow release and biological tissue repair and other special material industries.
In the prior art, hydrogenation reaction of dimer acid generates hydrogenated dimer acid, and catalysts such as platinum, palladium and the like are added in the reaction process, so that the cost is high; due to the high viscosity of the dimer acid, the catalyst is easy to wrap and has low activity, the service time of the catalyst is short, and the conversion rate of raw materials is limited; before the reaction is started, the loaded catalyst needs to be activated, and the activation process is often carried out under the condition of more than 200 ℃, and the activation condition is severer. In addition, the hydrogenation reaction of dimer acid is generally carried out in a tubular reactor, and the operations of stirring, temperature rise and pressurization are inconvenient.
Disclosure of Invention
In order to solve the defects, the invention provides a preparation method and application of a catalyst for hydrogenation of dimer acid, which improve the activity of the catalyst and the yield of products.
In order to achieve the purpose, the invention adopts the technical scheme that: a preparation method of a catalyst for hydrogenation of dimer acid is characterized by comprising the following steps:
1) putting a metallic nickel block and an aluminum ingot into a crucible in proportion, and heating and melting at 660-1460 ℃ to obtain a nickel-aluminum molten metal liquid; cooling to form nickel-aluminum alloy, and cutting into 0.1-1.5 cm3The nickel-aluminum alloy block or the nickel-aluminum molten metal liquid flows through a sieve with 20-40 meshes and is dropped into mineral oil to form nickel-aluminum alloy balls; dissolving nickel-aluminum alloy blocks or nickel-aluminum alloy balls by using 0.1-10.0 mol/L alkali liquor, wherein the ratio of the weight of the nickel-aluminum alloy to the volume of the alkali liquor is 1: 40-80, then filtering, washing and drying to obtain honeycomb nickel blocks or nickel balls with uniform pore sizes; the pore diameter of the honeycomb nickel block or nickel ball is equivalent to the molecular diameter of the dimer acid; the dimer acid is unsaturated dimer acid containing double bonds and has 1-2C ═ C bonds(ii) a The molar ratio of the metal nickel block to the aluminum ingot is 1: 1.8-3; because the content of aluminum is obviously higher than that of metallic nickel, more aluminum surrounds nickel, the volume proportion of holes in the formed honeycomb nickel block or nickel ball is improved, and the specific surface area of the catalyst is improved.
The nickel balls are spherical nickel, and the honeycomb nickel blocks and the nickel balls are anti-extrusion high-mechanical-strength catalysts.
2) The honeycomb nickel block or nickel ball is subjected to reduction activation before use: crushing the dried honeycomb nickel block into catalyst particles with the particle size of 30-40 meshes, placing the catalyst particles or nickel balls in a quartz tube, replacing air in the quartz tube by inert gas, introducing hydrogen flow, activating for 3-6 hours at the temperature of 90-150 ℃, and transferring to a reaction kettle in an inert gas atmosphere. Namely, the honeycomb nickel block obtained in the step 1) needs to be crushed into catalyst particles of 30-40 meshes to be placed in a quartz tube for activation, and the nickel balls (with the size of 20-40 meshes, preferably 30-40 meshes) obtained in the step 1) are directly placed in the quartz tube.
The catalyst prepared by the preparation method has the advantages of high specific surface area, high catalytic activity and uniform pore diameter. By setting the specific molar ratio of nickel to aluminum, the diameter of the reacted dimer acid is made to be equivalent to the pore size of the catalyst (to improve catalytic activity). The preparation method of the catalyst has low cost. When the catalyst is activated, the temperature is lower than that of the prior art, the requirement on the activation temperature is reduced, and the activity of the catalyst can still be ensured. The pore size distribution of the honeycomb nickel block or nickel ball is 2.0-30 nm, and the pore size distribution is mainly about 3.5 nm.
The method comprises the following specific steps of dissolving nickel-aluminum alloy blocks or nickel-aluminum alloy balls by using 0.1-10.0 mol/L alkali liquor: putting the nickel-aluminum alloy block or the nickel-aluminum alloy ball into 0.1-10.0 mol/L sodium hydroxide or potassium hydroxide aqueous solution for soaking for 5-10 h to dissolve aluminum in the nickel-aluminum alloy, and obtaining a solid-liquid mixture;
aiming at the nickel-aluminum alloy block, the specific steps of filtering, washing and drying are as follows: filtering the solid-liquid mixture to obtain honeycomb nickel after aluminum dissolution, washing the honeycomb nickel after aluminum dissolution with ethanol or acetone for 1-5 times, and drying at 50-150 ℃ for 1-10 hours to obtain honeycomb nickel blocks with uniform pore diameters;
aiming at the nickel-aluminum alloy ball, the specific steps of filtering, washing and drying are as follows: and filtering the solid-liquid mixture to obtain nickel balls after aluminum dissolution, washing the nickel balls after aluminum dissolution with ethanol or acetone for 1-5 times, and drying at 50-150 ℃ for 1-10 hours to obtain the honeycomb nickel balls with uniform pore diameters.
Through content detection, the mass percent of nickel in the honeycomb nickel block is 91-95%. The nickel content percentage is obviously higher than that of the prior Raney Ni catalyst.
Preferably, step 1) is specifically: putting a metallic nickel block and an aluminum ingot into a crucible in proportion, heating and melting at 1000-1400 ℃ to obtain nickel-aluminum molten metal liquid, and cooling to room temperature to obtain uniformly distributed nickel-aluminum alloy; cutting the nickel-aluminum alloy into 0.1-1.0 cm3And dissolving the nickel-aluminum alloy block by using 1-5 mol/L alkali liquor, filtering, washing by using ethanol or acetone, and drying to obtain the honeycomb nickel block with uniform pore size.
In another technical scheme, the step 1) is specifically as follows: putting a metallic nickel block and an aluminum ingot into a crucible in proportion, heating and melting at 1100-1400 ℃ to obtain nickel-aluminum molten metal liquid, enabling the nickel-aluminum molten metal liquid to flow through a 30-40 mesh screen and drop into mineral oil (namely, the nickel-aluminum molten metal liquid flowing through the screen drops downwards into the mineral oil, the size of the dropped nickel-aluminum molten metal liquid is 30-40 meshes and is consistent with the size of a screen hole), enabling the alloy (namely, the nickel-aluminum molten metal liquid flowing through the screen hole) to shrink into nickel-aluminum alloy balls in the mineral oil due to surface tension, dissolving the nickel-aluminum alloy with 1-4 mol/L alkali liquor, filtering, washing with ethanol or acetone, and drying to obtain the honeycomb nickel balls with uniform apertures.
The invention also provides application of the catalyst for hydrogenating the dimer acid in hydrogenation catalytic reaction of the dimer acid, wherein the dimer acid has 1-2C-C bonds.
The application specifically comprises the following steps:
adding the activated catalyst for hydrogenation of the dimer acid into a reaction kettle, adding a mixture of the dimer acid and an inert solvent into the reaction kettle, wherein the volume ratio of the dimer acid to the inert solvent is 1: 2-8, the mass percentage of the catalyst in a dimer acid hydrogenation reaction system (the reaction system consists of the catalyst, the dimer acid, hydrogen and the inert solvent) is 0.2-5%, introducing nitrogen into the reaction kettle to replace air in the reaction kettle (namely nitrogen replacement), introducing hydrogen into the reaction kettle to replace nitrogen in the reaction kettle (namely hydrogen replacement), and then introducing hydrogen into the reaction kettle to enable the hydrogen pressure of the reaction kettle to reach 1.5-3.5 MPa (keeping a certain hydrogen pressure to ensure the completion of the hydrogenation reaction and the pressure of the reaction system to be smaller, so as to improve the safety of a reaction device); heating to 120-220 ℃ for hydrogenation reaction, supplementing hydrogen for continuous reaction when the hydrogen pressure in the reaction kettle is reduced to 1.0MPa or below, repeating the operation until the hydrogen pressure in the reaction kettle is stable, and finishing the reaction; the time of single kettle secondary hydrogenation reaction is generally 2-6 h;
and opening a valve at the bottom of the reaction kettle, and performing filter pressing on the discharged material by using nitrogen, wherein the catalyst for hydrogenation of the dimer acid is left in the reaction kettle for the hydrogenation reaction of the next kettle. Through detection, when the catalyst for hydrogenating dimer acid is continuously used for hydrogenation reaction for 20 hours, 30 hours, 40 hours and 50 hours, the catalytic activity is respectively 98%, 96%, 95% and 92% of the initial catalytic activity.
Preferably, the inert solvent is cyclohexane, which does not react with hydrogen, and the addition of the inert solvent can reduce the viscosity of dimer acid and improve the reaction efficiency. The inert solvent may also be benzene, toluene, xylene, etc.
When the activity of the catalyst for hydrogenation of dimer acid is obviously reduced, the catalyst needs to be washed, regenerated and activated to realize recycling. Preferably, the number of nitrogen substitution and hydrogen substitution is 2 to 4. In the hydrogenation reaction process, the reaction kettle is always stirred, the diffusion mass transfer of hydrogen in a high-viscosity reaction system is enhanced, the defects of dimer acid polymerization and aggregation agglomeration are overcome, and the reaction efficiency is improved.
Compared with the prior art, the invention has the beneficial effects that: the catalyst obtained by the invention has high specific surface area, uniform pore diameter and high catalytic activity. By setting the specific molar ratio of nickel to aluminum, the diameter of the reaction molecule dimer acid is equivalent to the pore size of the catalyst (so as to improve the catalytic activity), and the cost is low. The catalyst is a special catalyst suitable for dimer acid hydrogenation reaction, and the conversion rate of the dimer acid catalytic hydrogenation reaction reaches 94-99%.
Detailed Description
The present invention is further illustrated by the following specific examples.
Example 1
1) Preparation of the catalyst: putting a metallic nickel block and an aluminum ingot into a crucible according to the mol ratio of 1:3, heating and melting at 1350 ℃ to obtain nickel-aluminum molten metal liquid, and cooling to room temperature to obtain uniformly distributed nickel-aluminum alloy; cutting the nickel-aluminum alloy into 0.5cm3The nickel-aluminum alloy block is put into 5mol/L sodium hydroxide or potassium hydroxide aqueous solution for soaking for 5 hours to dissolve aluminum in the nickel-aluminum alloy (the ratio of the weight g of the alloy to the volume ml of alkali liquor is 1:80, and stirring is carried out in the soaking process), so as to obtain a solid-liquid mixture; filtering the solid-liquid mixture to obtain honeycomb nickel with aluminum dissolved, washing the honeycomb nickel with ethanol for 3 times, washing with acetone for 1 time, and drying at 50 ℃ for 1h to obtain honeycomb nickel blocks with uniform pore diameters; crushing the dried honeycomb nickel block into catalyst particles with the particle size of 30-40 meshes, placing the catalyst particles in a quartz tube, replacing air in the quartz tube by nitrogen (namely, replacing the air by the nitrogen), introducing hydrogen flow, activating at the temperature of 100 ℃ for 4 hours, and transferring the activated catalyst particles into a reaction kettle; the mass percentage of nickel in the honeycomb nickel block is 91.1%.
2) Hydrogenation reaction of dimer acid: adding the activated blocky honeycomb nickel catalyst into a reaction kettle under the protection of inert gas, adding a mixture of dimer acid and cyclohexane into the reaction kettle, wherein the volume ratio of the dimer acid to the cyclohexane is 1:2, the dimer acid hydrogenation catalyst accounts for 1.0 percent of the total mass of a reaction system, introducing nitrogen into the reaction kettle to replace air in the reaction kettle (nitrogen replacement is carried out for 3 times), then introducing hydrogen into the reaction kettle to replace the nitrogen in the reaction kettle (hydrogen replacement is carried out for 3 times), then introducing hydrogen into the reaction kettle to ensure that the hydrogen pressure of the reaction kettle reaches 2.0MPa, and opening and stirring; heating to 160 ℃ for hydrogenation reaction, supplementing hydrogen to continue the reaction until the hydrogen pressure in the reaction kettle is reduced to below 1.0MPa, and ending the reaction (the hydrogen pressure is not reduced any more) when the hydrogen pressure in the reaction kettle is stable (the hydrogen pressure is not reduced), wherein the hydrogen consumption time of the hydrogenation reaction is 2.5 h); and opening a valve at the bottom of the reaction kettle, and performing filter pressing on the discharged material by using nitrogen, wherein the catalyst for hydrogenation of the dimer acid is remained in the reaction kettle. The product was tested and the conversion of dimer acid was 95.6%.
Materials (cyclohexane and dimer acid) can be added to continue a new hydrogenation reaction. Filtering while the solution is hot and cooling to room temperature. The reaction process is as follows:
raw materials: 2-nonanoic acid-3- (2-heptanoic acid) vinyl-4-heptyl-5-pentyl-cyclohexene.
The product is as follows: 1, 2-dinonylnonanoic acid 3-heptyl-4 pentyl-cyclohexane.
Example 2
1) Preparation of the catalyst: putting a metallic nickel block and an aluminum ingot into a crucible according to the mol ratio of 1:2, heating and melting at 1350 ℃ to obtain nickel-aluminum molten metal liquid, and spraying the molten alloy liquid into a container containing mineral oil through a 40-mesh screen to obtain nickel-aluminum alloy balls with the granularity of 30-40 meshes. Soaking the alloy ball block in 4mol/L sodium hydroxide or potassium hydroxide aqueous solution for 8h to dissolve aluminum in the nickel-aluminum alloy (the ratio of the weight g of the alloy to the volume ml of the alkali liquor is 1:80, stirring in the soaking process) to obtain a solid-liquid mixture; filtering the solid-liquid mixture to obtain a honeycomb nickel ball with aluminum dissolved, washing the honeycomb nickel ball with ethanol for 3 times, washing with acetone for 1 time, and drying at 50 ℃ for 1h to obtain the honeycomb nickel ball with uniform pore diameter; placing spherical catalyst particles (namely honeycomb nickel balls) in a quartz tube, replacing air in a reactor by nitrogen (namely nitrogen replacement is used for removing air), introducing high-purity hydrogen flow, activating at the temperature of 100 ℃ for 4 hours, and transferring to a reaction kettle; the mass percentage of nickel in the honeycomb nickel ball is 94.5%.
2) Hydrogenation reaction of dimer acid: adding the activated spherical catalyst particles into a reaction kettle, adding a mixture of dimer acid and cyclohexane into the reaction kettle, wherein the volume ratio of the dimer acid to the cyclohexane is 1:4, the catalyst for hydrogenation of the dimer acid is 1.2 percent of the total mass of the reaction system, introducing nitrogen into the reaction kettle to replace air in the reaction kettle (replacing the nitrogen for 3 times), then introducing hydrogen into the reaction kettle to replace the nitrogen in the reaction kettle (replacing the hydrogen for 3 times), then introducing hydrogen into the reaction kettle to ensure that the hydrogen pressure of the reaction kettle reaches 2.0MPa, and opening and stirring; heating to 160 ℃ for hydrogenation reaction, supplementing hydrogen to continue the reaction until the hydrogen pressure in the reaction kettle is reduced to below 1.0MPa, and ending the reaction (the time of the hydrogenation reaction is 2.3 hours); and opening a valve at the bottom of the reaction kettle, and performing filter pressing on the discharged material by using nitrogen, wherein the catalyst for hydrogenation of the dimer acid is remained in the reaction kettle. The product was tested and the conversion of dimer acid was 98.1%.
The reaction process is as follows:
raw materials: 2-nonanoic acid-3- (2-heptanoic acid) vinyl-4-heptyl-5-pentyl-cyclohexene.
The product is as follows: 1, 2-dinonylnonanoic acid 3-heptyl-4 pentyl-cyclohexane.
Example 3
1) Preparation of the catalyst: putting a metallic nickel block and an aluminum ingot into a crucible according to the mol ratio of 1:2, heating and melting at 1350 ℃ to obtain nickel-aluminum molten metal liquid, and spraying the molten alloy liquid into a container containing mineral oil through a 40-mesh screen to obtain nickel-aluminum alloy balls with the granularity of 30-40 meshes. Soaking the alloy ball block in 4mol/L sodium hydroxide or potassium hydroxide aqueous solution for 8h to dissolve aluminum in the nickel-aluminum alloy (the ratio of the weight g of the alloy to the volume ml of the alkali liquor is 1:80, stirring in the soaking process) to obtain a solid-liquid mixture; filtering the solid-liquid mixture to obtain a honeycomb nickel ball with aluminum dissolved, washing the honeycomb nickel ball with ethanol for 3 times, washing with acetone for 1 time, and drying at 50 ℃ for 1h to obtain the honeycomb nickel ball with uniform pore diameter; placing spherical catalyst particles (namely honeycomb nickel balls) in a quartz tube, replacing air in a reactor by nitrogen (namely nitrogen replacement is used for removing air), introducing high-purity hydrogen flow, activating at the temperature of 100 ℃ for 4 hours, and transferring to a reaction kettle; the mass percentage of nickel in the honeycomb nickel ball is 94.5%.
2) Hydrogenation reaction of dimer acid: adding the activated spherical catalyst particles into a reaction kettle, adding a mixture of dimer acid and cyclohexane into the reaction kettle, wherein the volume ratio of the dimer acid to the cyclohexane is 1:4, the catalyst for hydrogenation of the dimer acid is 1.2 percent of the total mass of the reaction system, introducing nitrogen into the reaction kettle to replace air in the reaction kettle (replacing the nitrogen for 3 times), then introducing hydrogen into the reaction kettle to replace the nitrogen in the reaction kettle (replacing the hydrogen for 3 times), then introducing hydrogen into the reaction kettle to ensure that the hydrogen pressure of the reaction kettle reaches 2.0MPa, and opening and stirring; heating to 160 ℃ for hydrogenation reaction, supplementing hydrogen to continue the reaction until the hydrogen pressure in the reaction kettle is reduced to below 1.0MPa, and ending the reaction (the time for the hydrogenation reaction is 2.2 hours); and opening a valve at the bottom of the reaction kettle, and performing filter pressing on the discharged material by using nitrogen, wherein the catalyst for hydrogenation of the dimer acid is remained in the reaction kettle. The product was tested and found to have a dimer acid conversion of 97.9%. The reaction raw material is (1-octanoic acid-2-octyl-3-nonanoic acid-undecene) shown in the formula I. The hydrogenation reaction product is 10, 11-dioctyl-1, 20-docosanoic acid.
Example 4
1) Preparation of the catalyst: putting a metallic nickel block and an aluminum ingot into a crucible according to the mol ratio of 1:2, heating and melting at 1350 ℃ to obtain nickel-aluminum molten metal liquid, and spraying the molten alloy liquid into a container containing mineral oil through a 40-mesh screen to obtain nickel-aluminum alloy balls with the granularity of 30-40 meshes. Soaking the alloy ball block in 4mol/L sodium hydroxide or potassium hydroxide aqueous solution for 8h to dissolve aluminum in the nickel-aluminum alloy (the ratio of the weight g of the alloy to the volume ml of the alkali liquor is 1:80, stirring in the soaking process) to obtain a solid-liquid mixture; filtering the solid-liquid mixture to obtain a honeycomb nickel ball with aluminum dissolved, washing the honeycomb nickel ball with ethanol for 3 times, washing with acetone for 1 time, and drying at 50 ℃ for 1h to obtain the honeycomb nickel ball with uniform pore diameter; placing spherical catalyst particles (namely honeycomb nickel balls) in a quartz tube, replacing air in a reactor by nitrogen (namely nitrogen replacement is used for removing air), introducing high-purity hydrogen flow, activating at the temperature of 100 ℃ for 4 hours, and transferring to a reaction kettle; the mass percentage of nickel in the honeycomb nickel ball is 94.5%.
2) Hydrogenation reaction of dimer acid: adding the activated spherical catalyst into a reaction kettle, adding a mixture of dimer acid and cyclohexane into the reaction kettle, wherein the volume ratio of dimer acid to cyclohexane is 1:2, the catalyst for hydrogenating dimer acid is continuously used for 5 times, the catalyst is 1.2 percent of the total mass of a reaction system, introducing nitrogen into the reaction kettle to replace air in the reaction kettle (replacing nitrogen for 3 times), then introducing hydrogen into the reaction kettle to replace nitrogen in the reaction kettle (replacing hydrogen for 3 times), then introducing hydrogen into the reaction kettle to ensure that the hydrogen pressure of the reaction kettle reaches 2.0MPa, and opening and stirring; heating to 160 ℃ for hydrogenation reaction, supplementing hydrogen to continue the reaction until the hydrogen pressure in the reaction kettle is reduced to below 1.0MPa, and ending the reaction (the hydrogen pressure is not reduced) when the hydrogen pressure in the reaction kettle is stable (namely the hydrogen pressure is not reduced), wherein the hydrogen pressure is 3.0h for the hydrogenation reaction; and opening a valve at the bottom of the reaction kettle, and performing filter pressing on the discharged material by using nitrogen, wherein the catalyst for hydrogenation of the dimer acid is remained in the reaction kettle. The product was tested and the conversion of dimer acid was 96.3%.
The raw material used in the reaction is a formula II (2, 3-dioctanoate-7-butyl-8-hexenyl-1, 5-dicyclohexyl diene), and the product after hydrogenation is 2-hexyl-3-butyl-6, 7-dioctanoate-bicyclohexane.
Example 5
1) Preparation of the catalyst: putting a metallic nickel block and an aluminum ingot into a crucible according to the mol ratio of 1:3, heating and melting at 1350 ℃ to obtain nickel-aluminum molten metal liquid, and cooling to room temperature to obtain uniformly distributed nickel-aluminum alloy; cutting the nickel-aluminum alloy into 0.5cm3The nickel-aluminum alloy block is put into 5mol/L sodium hydroxide or potassium hydroxide aqueous solution for soaking for 5 hours to dissolve aluminum in the nickel-aluminum alloy (the ratio of the weight g of the alloy to the volume ml of the alkali liquor is 1:80, stirring is carried out in the soaking process), and solid and liquid are obtainedMixing; filtering the solid-liquid mixture to obtain honeycomb nickel with aluminum dissolved, washing the honeycomb nickel with ethanol for 3 times, washing with acetone for 1 time, and drying at 50 ℃ for 1h to obtain honeycomb nickel blocks with uniform pore diameters; crushing the dried honeycomb nickel block into catalyst particles with the particle size of 30-40 meshes, placing the catalyst particles in a quartz tube, replacing air in the quartz tube by nitrogen (namely, replacing the air by the nitrogen), introducing hydrogen flow, activating at the temperature of 100 ℃ for 4 hours, and transferring the activated catalyst particles into a reaction kettle; the mass percentage of nickel in the honeycomb nickel block is 91.1%.
2) Hydrogenation reaction of dimer acid: adding the activated blocky honeycomb nickel catalyst into a reaction kettle under the protection of inert gas, adding a mixture of dimer acid and cyclohexane into the reaction kettle, wherein the volume ratio of the dimer acid to the cyclohexane is 1:2, the catalyst for hydrogenating the dimer acid is continuously used for 3 times, the catalyst for hydrogenating the dimer acid is 1.0 percent of the total mass of a reaction system, introducing nitrogen into the reaction kettle to replace air in the reaction kettle (replacing the nitrogen for 3 times), then introducing hydrogen into the reaction kettle to replace the nitrogen in the reaction kettle (replacing the hydrogen for 3 times), then introducing hydrogen into the reaction kettle to ensure that the hydrogen pressure of the reaction kettle reaches 2.0MPa, and opening and stirring; heating to 160 ℃ for hydrogenation reaction, supplementing hydrogen to continue the reaction until the hydrogen pressure in the reaction kettle is reduced to below 1.0MPa, and ending the reaction (the hydrogen pressure is not reduced any more) when the hydrogen pressure in the reaction kettle is stable (the hydrogen pressure is not reduced at this time), wherein the hydrogen pressure is 2.7 h; and opening a valve at the bottom of the reaction kettle, and performing filter pressing on the discharged material by using nitrogen, wherein the catalyst for hydrogenation of the dimer acid is remained in the reaction kettle. The product was tested and the conversion of dimer acid was 96.9%.
The raw material used in the reaction is a formula II (2, 3-dioctanoate-7-butyl-8-hexenyl-1, 5-dicyclohexyl diene), and the product after hydrogenation is 2-hexyl-3-butyl-6, 7-dioctanoate-bicyclohexane.
The above-described embodiments of the present invention do not limit the scope of the present invention. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the scope of the claims of the present invention.
Claims (9)
1. A preparation method of a catalyst for hydrogenation of dimer acid is characterized by comprising the following steps:
1) putting a metallic nickel block and an aluminum ingot into a crucible in proportion, and heating and melting at 660-1460 ℃ to obtain a nickel-aluminum molten metal liquid; cooling to form nickel-aluminum alloy, and cutting into 0.1-1.5 cm3The nickel-aluminum alloy block or the nickel-aluminum molten metal liquid flows through a sieve with 20-40 meshes and is dropped into mineral oil to form nickel-aluminum alloy balls; dissolving nickel-aluminum alloy blocks or nickel-aluminum alloy balls by using 0.1-10.0 mol/L alkali liquor, wherein the ratio of the weight of the nickel-aluminum alloy to the volume of the alkali liquor is 1: 40-80, then filtering, washing and drying to obtain honeycomb nickel blocks or nickel balls with uniform pore sizes; the pore diameter of the honeycomb nickel block or nickel ball is equivalent to the molecular diameter of the dimer acid; the dimer acid has 1-2C = C bonds; the molar ratio of the metal nickel block to the aluminum ingot is 1: 1.8-3;
2) the honeycomb nickel block or nickel ball is subjected to reduction activation before use: crushing the dried honeycomb nickel block into catalyst particles with the particle size of 30-40 meshes, placing the catalyst particles or nickel balls in a quartz tube, replacing air in the quartz tube by inert gas, introducing hydrogen flow, activating for 3-6 h at the temperature of 90-150 ℃, and transferring into a reaction kettle in the atmosphere of inert gas.
2. The preparation method of the catalyst for hydrogenation of dimer acid according to claim 1, wherein the specific steps of dissolving the nickel-aluminum alloy block or the nickel-aluminum alloy ball with 0.1-10.0 mol/L alkali solution are as follows: putting the nickel-aluminum alloy block or the nickel-aluminum alloy ball into 0.1-10.0 mol/L sodium hydroxide or potassium hydroxide aqueous solution for soaking for 5-10 h to dissolve aluminum in the nickel-aluminum alloy, and obtaining a solid-liquid mixture;
aiming at the nickel-aluminum alloy block, the specific steps of filtering, washing and drying are as follows: filtering the solid-liquid mixture to obtain a honeycomb nickel block after aluminum dissolution, washing the honeycomb nickel block after aluminum dissolution with ethanol or acetone for 1-5 times, and drying at 50-150 ℃ for 1-10 hours to obtain a honeycomb nickel block with uniform pore diameter;
aiming at the nickel-aluminum alloy ball, the specific steps of filtering, washing and drying are as follows: and filtering the solid-liquid mixture to obtain nickel balls after aluminum dissolution, washing the nickel balls after aluminum dissolution with ethanol or acetone for 1-5 times, and drying at 50-150 ℃ for 1-10 hours to obtain the honeycomb nickel balls with uniform pore diameters.
3. The method for preparing the catalyst for hydrogenation of dimer acid according to claim 2, wherein the mass percentage of nickel in the honeycomb nickel block and the nickel ball is 91-95%.
4. The method for preparing a catalyst for hydrogenation of dimer acid according to claim 2, wherein the step 1) is specifically as follows: putting a metallic nickel block and an aluminum ingot into a crucible in proportion, heating and melting at 1000-1400 ℃ to obtain nickel-aluminum molten metal liquid, and cooling to room temperature to obtain uniformly distributed nickel-aluminum alloy; cutting the nickel-aluminum alloy into 0.1-1.0 cm3Dissolving the nickel-aluminum alloy block by using 1-5 mol/L alkali liquor, and then filtering, washing and drying to obtain a honeycomb nickel block with uniform pore diameter;
or, the step 1) is specifically: putting a metallic nickel block and an aluminum ingot into a crucible in proportion, heating and melting at 1100-1400 ℃ to obtain nickel-aluminum molten metal liquid, enabling the nickel-aluminum molten metal liquid to flow through a 30-40 mesh screen and drop into mineral oil, enabling the nickel-aluminum molten metal liquid to shrink into nickel-aluminum alloy balls in the mineral oil due to surface tension, dissolving the nickel-aluminum alloy with 1-4 mol/L alkali liquor, then filtering, washing with ethanol or acetone, and drying to obtain the honeycomb nickel balls with uniform pore diameters.
5. Use of a catalyst for hydrogenation of dimer acid according to any of claims 1-4 in the catalytic reaction of hydrogenation of dimer acid, wherein said dimer acid has 1-2C = C bonds.
6. Use according to claim 5, characterized in that it comprises the following steps:
adding the activated catalyst for hydrogenating the dimer acid into a reaction kettle, adding a mixture of the dimer acid and an inert solvent into the reaction kettle, wherein the volume ratio of the dimer acid to the inert solvent is 1: 2-8, the mass percentage of the catalyst for hydrogenating the dimer acid in a reaction system is 0.5-2%, introducing nitrogen into the reaction kettle to replace air in the reaction kettle, introducing hydrogen into the reaction kettle to replace the nitrogen in the reaction kettle, and then introducing hydrogen into the reaction kettle to enable the hydrogen pressure of the reaction kettle to reach 1.5-3.5 MPa; heating to 120-220 ℃ for hydrogenation reaction, supplementing hydrogen for continuous reaction when the hydrogen pressure in the reaction kettle is reduced to 1.0MPa or below, repeating the operation until the hydrogen pressure in the reaction kettle is stable, and finishing the reaction;
and opening a valve at the bottom of the reaction kettle, and performing filter pressing on the discharged material by using nitrogen, wherein the catalyst for hydrogenation of the dimer acid is left in the reaction kettle for the hydrogenation reaction of the next kettle.
7. Use according to claim 6, characterized in that the inert solvent is cyclohexane, benzene, toluene or xylene, preferably cyclohexane.
8. The use according to claim 6, wherein when the activity of the catalyst for hydrogenation of dimer acid is reduced, the catalyst is subjected to washing, regeneration and activation treatment.
9. The use according to claim 6, wherein the number of nitrogen replacements and hydrogen replacements is 2 to 4; in the hydrogenation reaction process, excitation stirring is always carried out in the reaction kettle.
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