CN110078617A - A method of cyclohexane cyclohexanedimethanodibasic ester is prepared with phthalic acid ester catalytic hydrogenation - Google Patents
A method of cyclohexane cyclohexanedimethanodibasic ester is prepared with phthalic acid ester catalytic hydrogenation Download PDFInfo
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- CN110078617A CN110078617A CN201910396856.8A CN201910396856A CN110078617A CN 110078617 A CN110078617 A CN 110078617A CN 201910396856 A CN201910396856 A CN 201910396856A CN 110078617 A CN110078617 A CN 110078617A
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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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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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
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/303—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by hydrogenation of unsaturated carbon-to-carbon bonds
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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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
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- C07C2601/14—The ring being saturated
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Abstract
The invention belongs to technical field of catalytic hydrogenation, and in particular to a kind of method that phthalic acid ester catalytic hydrogenation prepares cyclohexane cyclohexanedimethanodibasic ester, using continuous fixed-bed catalytic hydrogenation technique, and at 110~160 DEG C of temperature, 3~7MPa of pressure, 0.2~0.4h of air speed‑1Under the conditions of hydrogen is added to phthalic acid ester, obtain cyclohexane cyclohexanedimethanodibasic ester, yield 99.83%.Used catalyst activity component is Ni, and content is 10~15w%, and auxiliary agent is iron, and content is 0.5~3w%, and surplus is carrier gama-alumina.
Description
Technical field
The invention belongs to catalytic hydrogenation fields, and in particular to one kind prepares hexamethylene diformazan by raw material of phthalic acid ester
The method of acid esters.
Background technique
Polyvinyl chloride (PVC) is a kind of widely used thermoplastic resin, but since its processing is more difficult, is being processed
When plasticizer need to be added.Currently, widely used plasticizer is mainly phthalic ester plasticizer, including phthalic acid
Dioctyl ester (DOP), diisononyl phthalate (DINP) etc., but as people are to the continuous depth of this kind of plasticizer toxicity research
Enter, safety and come out to environmental hazard is increasingly prominent, thus the use of phthalic ester plasticizer is in global model
It is all limited by very large in enclosing, the demand of environmentally friendly plasticizer also increases increasingly, therefore is badly in need of developing new one
The novel environment-friendly plasticizer in generation.And the hydrogenated products performance of diisononyl phthalate is more excellent than the former, is expected to replace adjacent
Phthalic acid dinonyl.
Chinese patent CN108940305A discloses the preparation method of hydrogenation catalyst and cyclohexane cyclohexanedimethanodibasic dibasic ester.With
One or more of metal rhodium, ruthenium and palladium are active component, and Cu and/or Ag are auxiliary element, active carbon and/or oxidation
Aluminium is carrier, prepares hydrogenation catalyst, and the content of the active element is 0.1~8w%, preferably 0.3~6w%, described to help
The content of agent element is 0.1~4w%, preferably 0.2~2w%.Using fixed bed reactors, air speed is 0.5~3h-1, temperature
It is 80~160 DEG C, 0.5~7MPa of reaction pressure.Conversion ratio is 99.7%, selectively only up to be to 98.2%.What is used is expensive
Metal is at high cost, and has 1.8% by-product to generate.
Chinese patent CN103240101A discloses a kind of preparation method of catalyst for hydrogenation of phthalic acid dicarboxylic ester,
The catalyst uses aluminium oxide-silicon oxide mixture carrier, and active component is noble metal Ru or/and Pd, in carrier formative stage
It is added to transition metal Ni auxiliary agent.Reaction-ure conversion-age and selectivity all reach 99% or more.But its is that noble metal is urged
Agent, higher cost.
The purpose of the present invention is producing environment-friendlyplasticizer plasticizer cyclohexane cyclohexanedimethanodibasic ester, and the catalyst activity component used is
Base metal considerably reduces production cost, and reaction effect is good, and conversion ratio, selectivity are high.
Summary of the invention
The purpose of the present invention is to provide a kind of methods for producing cyclohexane cyclohexanedimethanodibasic ester, are made with metallic nickel substitution noble metal
For the active component of phthalic acid ester hydrogenation catalyst, production cost is reduced.Auxiliary agent iron is additionally incorporated, disperses nickel preferably
In carrier surface, and phthalic acid ester preferably can be adsorbed on carrier surface by iron, improve the utilization rate of catalyst, to mention
The conversion ratio and selectivity of high reactant.
The method that the present invention prepares cyclohexane cyclohexanedimethanodibasic ester by raw material of phthalic acid ester is, in the work of nickel-base catalyst
Under, using continuous fixed-bed catalytic hydrogenation technique, cyclohexane cyclohexanedimethanodibasic ester is prepared；
Wherein, the active component of catalyst is Ni, and content is 10~15%, auxiliary agent Fe, and content is 0.5~3%,
Remaining is carrier gama-alumina, use continuous fixed bed hydrogenation technique actual conditions for, at 110~160 DEG C of temperature, pressure 3~
7MPa, 0.2~0.4h of air speed-1, catalyst amount 20ml.Phthalic acid ester hydrogenation reaction is carried out, hexamethylene two is then obtained
Formic acid esters.
The preparation method of the catalyst carries out as steps described below:
(1) methylcellulose, citric acid, sesbania powder and the boehmite of calculation amount are weighed, after mixing extrusion, 70
~80 DEG C dry, and 3~6h is roasted at 600~800 DEG C of Muffle furnace, obtains gamma-aluminium oxide carrier.
Wherein, methylcellulose and sesbania powder are the 1% of carrier quality, and methylcellulose is adhesive, make to intend thin water
Aluminium stone is more preferably mediated；Sesbania powder is pore creating material, changes cellular structure；Citric acid is the 5% of carrier quality；Citric acid is peptization
Agent can improve the crush strength and pore structure of catalyst.
(2) nine nitric hydrate of active component Nickelous nitrate hexahydrate and auxiliary agent of calculation amount is weighed according to the composition of catalyst
Iron is configured to the mixed solution of Nickelous nitrate hexahydrate and Fe(NO3)39H2O with deionized water after mixing, the load of calculation amount is added
Body, homogeneous impregnation, 70~80 DEG C dry, and roast 4~6 hours at 300~600 DEG C of Muffle furnace.Wherein active component accounts for catalyst
The 10~15% of gross mass, auxiliary agent account for the 0.5~3% of catalyst total amount.
(3) manufactured catalyst precursor is activated in fixed bed hydrogen atmosphere, 450~600 DEG C of temperature, the time 1~4
Hour.
The catalyst is suitable for repefral (DMP), diethyl phthalate (DEP), adjacent benzene two
The hydrogenation technique of formic acid dibutyl ester (DBP), dioctyl phthalate (DOP), diisononyl phthalate (DINP) etc..
The utility model has the advantages that
The introducing of auxiliary agent iron improves the dispersion degree of carried metal nickel in catalyst of the present invention, it is made to be more evenly distributed in load
On body, the partial size of metal, while the synergistic effect of iron and nickel are reduced, increases reactivity.And iron can be preferably adjacent benzene two
Formic acid esters is adsorbed on carrier surface, improves the utilization rate of catalyst, to improve the conversion ratio and selectivity of reactant.
Specific implementation method
Below by embodiment, the present invention is described in further detail:
Embodiment 1
0.3030g methylcellulose is weighed, 1.5151g citric acid is dissolved in 9.8g deionized water, weighs 0.3030g sesbania
Powder, 30g boehmite are mixed with above-mentioned solution again after mixing, extrusion after mediating 3 hours, 70 DEG C of drying, 700 DEG C of roastings
4h is burnt, catalyst carrier is obtained.
Embodiment 2
1 carrier 20ml of embodiment is measured, 3.4533gNi (NO is weighed3)2·6H2O, 1.5151gFe (NO3)3·9H2O mixing
After be dissolved in 10.5g deionized water, carrier is added after ultrasonic dissolution, stirs evenly, 70 DEG C of dryings, 300 DEG C of roasting 5h, then normal pressure
Lower hydrogen reducing, 600 DEG C of temperature, time 4h.Ni content is that 10%, Fe content is 3%.
Embodiment 3
1 carrier 20ml of embodiment is measured, 3.4533gNi (NO is weighed3)2·6H2O, 1.0101gFe (NO3)3·9H2O mixing
After be dissolved in 10.5g deionized water, be added in carrier, stir evenly after ultrasonic dissolution, 70 DEG C of dryings, 400 DEG C of roasting 5h, then often
Pressure hydrogen reducing, 500 DEG C of temperature, time 3h.Ni content is that 10%, Fe content is 2%.
Embodiment 4
1 carrier 20ml of embodiment is measured, 5.1800gNi (NO is weighed3)2·6H2O, 1.0101gFe (NO3)3·9H2O mixing
After be dissolved in 10.5g deionized water, be added in carrier, stir evenly after ultrasonic dissolution, 70 DEG C of dryings, 600 DEG C of roasting 5h, then often
Pressure hydrogen reducing, 600 DEG C of temperature, time 2h.Ni content is that 13%, Fe content is 2%.
Embodiment 5
1 carrier 20ml of embodiment is measured, 5.1800gNi (NO is weighed3)2·6H2O, 0.5050gFe (NO3)3·9H2O mixing
After be dissolved in 10.5g deionized water, be added in carrier, stir evenly after ultrasonic dissolution, 70 DEG C of dryings, 300 DEG C of roasting 5h, then often
Pressure hydrogen reducing, 500 DEG C of temperature, time 4h.Ni content is that 13%, Fe content is 1%.
Embodiment 6
1 carrier 20ml of embodiment is measured, 6.9067gNi (NO is weighed3)2·6H2O, 0.5050gFe (NO3)3·9H2O mixing
After be dissolved in 10.5g deionized water, be added in carrier, stir evenly after ultrasonic dissolution, 70 DEG C of dryings, 400 DEG C of roasting 5h, then often
Pressure hydrogen reducing, 450 DEG C of temperature, time 3h.Ni content is that 15%, Fe content is 1%.
Embodiment 7
1 carrier 20ml of embodiment is measured, 6.9067gNi (NO is weighed3)2·6H2O, 0.2525gFe (NO3)3·9H2O mixing
After be dissolved in 10.5g deionized water, be added in carrier, stir evenly after ultrasonic dissolution, 70 DEG C of dryings, 500 DEG C of roasting 5h, then often
Pressure hydrogen reducing, 600 DEG C of temperature, time 2h.Ni content is that 15%, Fe content is 0.5%.
Embodiment 8
Using diisononyl phthalate as raw material, 2 catalyst of embodiment, using continuous fixed-bed catalytic hydrogenation technique,
At 160 DEG C of temperature, pressure 3MPa, air speed 0.2h-1, cyclohexane cyclohexanedimethanodibasic ester is prepared, is formed using liquid chromatographic detection product,
Product yield is 99.49%.
Embodiment 9
Using diisononyl phthalate as raw material, 3 catalyst of embodiment, using continuous fixed-bed catalytic hydrogenation technique,
At 150 DEG C of temperature, pressure 4MPa, air speed 0.3h-1, cyclohexane cyclohexanedimethanodibasic ester is prepared, is formed using liquid chromatographic detection product,
Product yield is 99.28%.
Embodiment 10
Using diisononyl phthalate as raw material, 4 catalyst of embodiment, using continuous fixed-bed catalytic hydrogenation technique,
At 140 DEG C of temperature, pressure 5MPa, air speed 0.4h-1, cyclohexane cyclohexanedimethanodibasic ester is prepared, is formed using liquid chromatographic detection product,
Product yield is 99.51%.
Embodiment 11
Using diisononyl phthalate as raw material, 5 catalyst of embodiment, using continuous fixed-bed catalytic hydrogenation technique,
At 130 DEG C of temperature, pressure 6MPa, air speed 0.2h-1, cyclohexane cyclohexanedimethanodibasic ester is prepared, is formed using liquid chromatographic detection product,
Product yield is 99.37%.
Embodiment 12
Using diisononyl phthalate as raw material, 6 catalyst of embodiment, using continuous fixed-bed catalytic hydrogenation technique,
At 120 DEG C of temperature, pressure 7MPa, air speed 0.3h-1, cyclohexane cyclohexanedimethanodibasic ester is prepared, is formed using liquid chromatographic detection product,
Product yield is 99.50%.
Embodiment 13
Using diisononyl phthalate as raw material, 7 catalyst of embodiment, using continuous fixed-bed catalytic hydrogenation technique,
At 110 DEG C of temperature, pressure 6MPa, air speed 0.4h-1, cyclohexane cyclohexanedimethanodibasic ester is prepared, is formed using liquid chromatographic detection product,
Product yield is 99.48%.
Comparative example 1
1 carrier 20ml of embodiment is measured, 2.0802gNi (NO is weighed3)2·6H2O is dissolved in 10.5g deionized water, ultrasound
It is added in carrier, stirs evenly after dissolution, 70 DEG C of dryings, 500 DEG C of roasting 5h, hydrogen reducing under normal pressure, 500 DEG C of temperature, when
Between 3h.Ni content is 6%.
Comparative example 2
1 carrier 20ml of embodiment is measured, 2.7736g Ni (NO is weighed3)2·6H2O is dissolved in 10.5g deionized water, is surpassed
It is added in carrier, stirs evenly, 70 DEG C of dryings, 300 DEG C of roasting 5h, under normal pressure hydrogen reducing, 400 DEG C of temperature after sound dissolution,
Time 3h.Ni content is 8%.
Comparative example 3
1 carrier 20ml of embodiment is measured, 3.4533gNi (NO is weighed3)2·6H2O is dissolved in 10.5g deionized water, ultrasound
It is added in carrier, stirs evenly after dissolution, 70 DEG C of dryings, 400 DEG C of roasting 5h, hydrogen reducing under normal pressure, 500 DEG C of temperature, when
Between 3h.Ni content is 10%.
Comparative example 4
1 carrier 20ml of embodiment is measured, 5.1800gNi (NO is weighed3)2·6H2O is dissolved in 10.5g deionized water, ultrasound
It is added in carrier, stirs evenly after dissolution, 70 DEG C of dryings, hydrogen reducing under 600 DEG C of roastings 5h, then normal pressure, 600 DEG C of temperature, when
Between 2h.Ni content is 13%.
Comparative example 5
1 carrier 20ml of embodiment is measured, 6.9067gNi (NO is weighed3)2·6H2O is dissolved in 10.5g deionized water, ultrasound
It is added in carrier, stirs evenly after dissolution, 70 DEG C of dryings, hydrogen reducing under 400 DEG C of roastings 5h, then normal pressure, 450 DEG C of temperature, when
Between 3h.Ni content is 15%.
Comparative example 6
1 carrier 20ml of embodiment is measured, 3.4533gNi (NO is weighed3)2·6H2O, 0.7985gCu (NO3)2·3H2O mixing
After be dissolved in 10.5g deionized water, be added in carrier, stir evenly after ultrasonic dissolution, 70 DEG C of dryings, 600 DEG C of roasting 5h, then often
Pressure hydrogen reducing, 600 DEG C of temperature, time 2h.Ni content is that 10%, Cu content is 3%.
Comparative example 7
1 carrier 20ml of embodiment is measured, 6.9067gNi (NO is weighed3)2·6H2O, 0.1331gCu (NO3)2·3H2O mixing
After be dissolved in 10.5g deionized water, be added in carrier, stir evenly after ultrasonic dissolution, 70 DEG C of dryings, 300 DEG C of roasting 5h, then often
Depress hydrogen reducing, 500 DEG C of 4h of temperature.Ni content is that 15%, Cu content is 0.5%.
Comparative example 8
1 carrier 20ml of embodiment is measured, 3.4533gNi (NO is weighed3)2·6H2O, 1.6154gCu (NO3)2·3H2O mixing
After be dissolved in 10.5g deionized water, be added in carrier, stir evenly after ultrasonic dissolution, 70 DEG C of dryings, 400 DEG C of roasting 5h, then often
Pressure hydrogen reducing, 450 DEG C of temperature, time 3h.Ni content is that 10%, Cr content is 3%.
Comparative example 9
1 carrier 20ml of embodiment is measured, 6.9067gNi (NO is weighed3)2·6H2O, 0.2692gCu (NO3)2·3H2O mixing
After be dissolved in 10.5g deionized water, be added in carrier, stir evenly after ultrasonic dissolution, 70 DEG C of dryings, 500 DEG C of roasting 5h, then often
Depress hydrogen reducing, 600 DEG C of 3h of temperature.Ni content is that 15%, Cr content is 0.5%.
Comparative example 10
Using diisononyl phthalate as raw material, 1 catalyst of comparative example adds hydrogen work using continuous fixed-bed catalytic
Skill, at 150 DEG C of temperature, pressure 4MPa, air speed 0.3h-1 prepare cyclohexane cyclohexanedimethanodibasic ester, using liquid chromatographic detection product group
At product yield 96.54%.
Comparative example 11
Using diisononyl phthalate as raw material, 2 catalyst of comparative example adds hydrogen work using continuous fixed-bed catalytic
Skill, at 140 DEG C of temperature, pressure 5MPa, air speed 0.4h-1 prepare cyclohexane cyclohexanedimethanodibasic ester, using liquid chromatographic detection product group
At product yield 96.77%.
Comparative example 12
Using diisononyl phthalate as raw material, 3 catalyst of comparative example adds hydrogen work using continuous fixed-bed catalytic
Skill, at 160 DEG C of temperature, pressure 3MPa, air speed 0.2h-1 prepare cyclohexane cyclohexanedimethanodibasic ester, using liquid chromatographic detection product group
At product yield 97.12%.
Comparative example 13
Using diisononyl phthalate as raw material, 4 catalyst of comparative example adds hydrogen work using continuous fixed-bed catalytic
Skill, at 150 DEG C of temperature, pressure 4MPa, air speed 0.3h-1 prepare cyclohexane cyclohexanedimethanodibasic ester, using liquid chromatographic detection product group
At product yield 97.83%.
Comparative example 14
Using diisononyl phthalate as raw material, 5 catalyst of comparative example adds hydrogen work using continuous fixed-bed catalytic
Skill, at 140 DEG C of temperature, pressure 5MPa, air speed 0.4h-1 prepare cyclohexane cyclohexanedimethanodibasic ester, using liquid chromatographic detection product group
At product yield 98.01%.
Comparative example 15
Using diisononyl phthalate as raw material, 6 catalyst of comparative example adds hydrogen work using continuous fixed-bed catalytic
Skill, at 150 DEG C of temperature, pressure 5MPa, air speed 0.4h-1, cyclohexane cyclohexanedimethanodibasic ester is prepared, using liquid chromatographic detection product group
At product yield 96.36%.
Comparative example 16
Using diisononyl phthalate as raw material, 7 catalyst of comparative example adds hydrogen work using continuous fixed-bed catalytic
Skill, at 140 DEG C of temperature, pressure 6MPa, air speed 0.2h-1, cyclohexane cyclohexanedimethanodibasic ester is prepared, using liquid chromatographic detection product group
At product yield 95.81%.
Comparative example 17
Using diisononyl phthalate as raw material, 8 catalyst of comparative example adds hydrogen work using continuous fixed-bed catalytic
Skill, at 130 DEG C of temperature, pressure 7MPa, air speed 0.3h-1, cyclohexane cyclohexanedimethanodibasic ester is prepared, using liquid chromatographic detection product group
At product yield 97.4%.
Comparative example 18
Using diisononyl phthalate as raw material, 9 catalyst of comparative example adds hydrogen work using continuous fixed-bed catalytic
Skill, at 120 DEG C of temperature, pressure 6MPa, air speed 0.4h-1, cyclohexane cyclohexanedimethanodibasic ester is prepared, using liquid chromatographic detection product group
At product yield 97.25%.
The above, preferable specific embodiment only of the invention, the scope of protection of the present invention is not limited to this, any ripe
Know those skilled in the art within the technical scope of the present disclosure, the technical solution that can obviously obtain it is simple
Variation or equivalence replacement are fallen within the scope of protection of the present invention.
Claims (5)
1. a kind of method for preparing cyclohexane cyclohexanedimethanodibasic ester as raw material using phthalic acid ester, which is characterized in that in nickel catalyst
Under the action of agent, using continuous fixed-bed catalytic hydrogenation technique, cyclohexane cyclohexanedimethanodibasic ester is prepared；Wherein, nickel-base catalyst presses matter
Percentage is measured consisting of: active component nickel is 10%~15%, auxiliary agent iron is 0.5%~3%, remaining is carrier gamma oxidation
Aluminium.
2. the method according to claim 1 for preparing cyclohexane cyclohexanedimethanodibasic ester as raw material using phthalic acid ester, feature
It is, using continuous fixed-bed catalytic hydrogenation technique, reaction condition are as follows: 110~160 DEG C of temperature, 3~7MPa of pressure, air speed
For 0.2~0.4h-1。
3. the method according to claim 1 for preparing cyclohexane cyclohexanedimethanodibasic ester as raw material using phthalic acid ester, feature
It is, steps are as follows for the preparation method of the nickel-base catalyst:
(1) methylcellulose, citric acid, sesbania powder and the boehmite of calculation amount are weighed, after mixing extrusion, 70~80
DEG C drying, 3~6h is roasted at 600~800 DEG C of Muffle furnace, obtains gamma-aluminium oxide carrier；
(2) Nickelous nitrate hexahydrate and Fe(NO3)39H2O for weighing calculation amount respectively are configured to six nitric hydrates with deionized water
The mixed solution of nickel and Fe(NO3)39H2O uniformly mixes, and the carrier of calculation amount, homogeneous impregnation, 70~80 DEG C of drying, horse is added
It not roasts 4~6 hours for 300~600 DEG C of furnace, obtains catalyst precursor；
(3) catalyst precursor made of above-mentioned steps is put into atmospheric hydrogen in tube furnace to restore, 450~600 DEG C of temperature, when
Between 1~4 hour.
4. the method according to claim 3 for preparing cyclohexane cyclohexanedimethanodibasic ester as raw material using phthalic acid ester, feature
It is, step (1) methylcellulose and sesbania powder are the 1% of carrier quality, and citric acid is the 5% of carrier quality.
5. the method according to claim 1 for preparing cyclohexane cyclohexanedimethanodibasic ester as raw material using phthalic acid ester, feature
It is, the catalyst is suitable for dimethyl hexahydrophthalate, cyclohexane cyclohexanedimethanodibasic diethylester, two fourth of cyclohexane cyclohexanedimethanodibasic
The preparation of ester, cyclohexane cyclohexanedimethanodibasic dioctyl ester, cyclohexane cyclohexanedimethanodibasic dinonyl plasticizer.
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| CN115532265A (en) * | 2022-09-22 | 2022-12-30 | 河北大学 | Halloysite-loaded nickel-based nano catalyst and preparation method and application thereof |
| CN115532265B (en) * | 2022-09-22 | 2023-10-24 | 河北大学 | Halloysite-loaded nickel-based nano catalyst and preparation method and application thereof |
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Application publication date: 20190802 |