CN114392737B - Preparation method of palladium-carbon catalyst capable of being reused for multiple times - Google Patents
Preparation method of palladium-carbon catalyst capable of being reused for multiple times Download PDFInfo
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- CN114392737B CN114392737B CN202210063107.5A CN202210063107A CN114392737B CN 114392737 B CN114392737 B CN 114392737B CN 202210063107 A CN202210063107 A CN 202210063107A CN 114392737 B CN114392737 B CN 114392737B
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- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000003054 catalyst Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 147
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 124
- 239000000758 substrate Substances 0.000 claims abstract description 50
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000007789 sealing Methods 0.000 claims abstract description 34
- 238000003756 stirring Methods 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000001035 drying Methods 0.000 claims abstract description 25
- 239000007788 liquid Substances 0.000 claims abstract description 22
- 239000002253 acid Substances 0.000 claims abstract description 20
- 238000002791 soaking Methods 0.000 claims abstract description 20
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims abstract description 18
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims abstract description 18
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims abstract description 18
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 18
- 239000001856 Ethyl cellulose Substances 0.000 claims abstract description 17
- 238000011049 filling Methods 0.000 claims abstract description 16
- KSZVHVUMUSIKTC-UHFFFAOYSA-N acetic acid;propan-2-one Chemical compound CC(C)=O.CC(O)=O KSZVHVUMUSIKTC-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003513 alkali Substances 0.000 claims abstract description 13
- 229920002678 cellulose Polymers 0.000 claims abstract description 9
- 239000001913 cellulose Substances 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 8
- 235000010944 ethyl methyl cellulose Nutrition 0.000 claims abstract description 7
- 229920003087 methylethyl cellulose Polymers 0.000 claims abstract description 7
- 238000007747 plating Methods 0.000 claims abstract description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 55
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 42
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 30
- 238000005507 spraying Methods 0.000 claims description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- 229910021529 ammonia Inorganic materials 0.000 claims description 24
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 229910052757 nitrogen Inorganic materials 0.000 claims description 20
- 239000007789 gas Substances 0.000 claims description 19
- 238000006722 reduction reaction Methods 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 12
- 230000010355 oscillation Effects 0.000 claims description 12
- 230000009467 reduction Effects 0.000 claims description 12
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 12
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 11
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 10
- 229920001249 ethyl cellulose Polymers 0.000 claims description 10
- 238000010926 purge Methods 0.000 claims description 10
- 238000004821 distillation Methods 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 239000001863 hydroxypropyl cellulose Substances 0.000 claims description 6
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 5
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims 6
- 239000007864 aqueous solution Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 10
- 239000003610 charcoal Substances 0.000 abstract description 3
- 230000002349 favourable effect Effects 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 230000002035 prolonged effect Effects 0.000 abstract description 3
- 230000002787 reinforcement Effects 0.000 abstract description 3
- 238000004140 cleaning Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract description 2
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- 230000008569 process Effects 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 238000002386 leaching Methods 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- 239000000908 ammonium hydroxide Substances 0.000 description 5
- 230000035699 permeability Effects 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- NXJCBFBQEVOTOW-UHFFFAOYSA-L palladium(2+);dihydroxide Chemical compound O[Pd]O NXJCBFBQEVOTOW-UHFFFAOYSA-L 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- -1 meanwhile Chemical compound 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000017105 transposition 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- B01J35/60—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0217—Pretreatment of the substrate before coating
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0219—Coating the coating containing organic compounds
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
- B01J37/346—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy of microwave energy
Abstract
The invention discloses a preparation method of a palladium-carbon catalyst capable of being reused, which comprises the following steps: adding active carbon into ethanol, ultrasonically cleaning, and soaking in acid and alkali; plating a palladium acetate-acetone solution on the surface of an activated carbon substrate to obtain plated activated carbon; adding hydroxypropyl methyl cellulose and ethyl cellulose into methanol, and distilling to form micro-thick liquid; then, carrying out methanol steam treatment on the coated activated carbon substrate, filling the micro-thick liquid into the coated activated carbon substrate under negative pressure, and drying to obtain a prefabricated sealing block; hydrolyzing the prefabricated sealing block in a wet environment to obtain a palladium-carbon prefabricated sealing block; then adding the mixture into water, stirring, reducing and washing to obtain the palladium-carbon catalyst. The modification of the carbon carrier enriches the groups on the surface area of the carrier, is favorable for the adhesion of palladium active components and improves the activity of the catalyst; through the cellulose reinforcement of secondary for the skeleton of charcoal carrier is more firm, can resist the external force that receives in the use, has prolonged the life of catalyst.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation methods, and particularly relates to a preparation method of a palladium-carbon catalyst capable of being reused.
Background
Palladium-carbon is used as a novel and efficient noble metal catalyst, and is a perfect application of novel materials in the field of chemical industry. The palladium-carbon catalyst has the main functions of hydrogenation, dehydrogenation, hydrogen transposition and the like in chemical reaction, and can be widely applied to the fields of energy chemical industry, fine chemical industry, environmental protection and the like. At present, palladium-carbon has low activity in the using process or active components are buried due to collapse of a carrier, so that the problems of low application times of the catalyst, easy deactivation and the like are caused.
Disclosure of Invention
The invention aims to provide a preparation method of a palladium-carbon catalyst capable of being reused, which solves the problems of less reuse times and lower activity of the palladium-carbon catalyst prepared by the existing method.
The technical scheme adopted by the invention is that the preparation method of the palladium-carbon catalyst capable of being reused comprises the following steps:
step 1, adding activated carbon into an ethanol water solution for ultrasonic cleaning to obtain a clean activated carbon substrate;
step 2, carrying out acid soaking on the clean activated carbon substrate, and then taking out the substrate for alkali soaking to obtain an activated carbon substrate;
step 3, adding palladium acetate into the acetone solution, uniformly stirring to form palladium acetate-acetone solution, then plating a film of the palladium acetate-acetone solution on the surface of the active carbon substrate by utilizing negative pressure spraying, and drying to obtain coated active carbon;
step 4, adding hydroxypropyl methyl cellulose and ethyl cellulose into methanol, uniformly stirring to form a composite cellulose solution, and then performing reduced pressure distillation to form a micro-thick liquid;
step 5, putting the coated activated carbon substrate into a reaction kettle, treating with methanol vapor for 1-2h, then pouring micro-thick liquid into the coated activated carbon substrate under negative pressure, carrying out microwave oscillation treatment, and drying to obtain a prefabricated sealing block;
step 6, placing the prefabricated sealing block in a humid environment for standing for 2-4 hours, then placing the prefabricated sealing block in an ammonia environment for standing for 3-6 hours, and keeping the temperature for standing and purging for 1-2 hours to obtain a palladium-carbon prefabricated sealing block;
and 7, adding the palladium-carbon prefabricated sealing block into a reaction kettle with water, stirring at normal temperature, introducing hydrogen for reduction, filtering, and washing with water to obtain the palladium-carbon catalyst.
The present invention is also characterized in that,
in the step 1, in the ethanol water solution, the volume concentration of ethanol is 60-80%; the ultrasonic cleaning temperature is 20-40 ℃ and the ultrasonic frequency is 40-80kHz.
In the step 2, hydrochloric acid is adopted for soaking for 10-20min, and the pH value of the hydrochloric acid is 4-5; the alkali soaking is performed with sodium hydroxide solution for 30-50min, and pH is 10-11.
In the step 3, the mass concentration of palladium acetate in acetone is 200-400g/L, the stirring speed is 1000-2000r/min, the negative pressure spraying pressure is 40-60% of the atmospheric pressure, the spraying speed is 5-8mL/min, and the spraying amount is 0.1-0.4mL/cm 2 The temperature is 30-40 ℃; the drying temperature is 60-70 ℃.
In the step 4, the concentration of the hydroxypropyl cellulose in the methanol is 40-50g/L, and the mass ratio of the hydroxypropyl methyl cellulose to the ethyl cellulose is 4:1-2, stirring speed is 1000-3000r/min, pressure of reduced pressure distillation is 70-80% of atmospheric pressure, and temperature is 50-60 ℃.
In the step 5, the methanol steam is a mixed gas consisting of nitrogen and methanol steam, and the volume ratio of the nitrogen to the methanol steam is 5:3-5, the temperature of methanol steam treatment is 60-70 ℃, the pouring speed of negative pressure pouring is 5-10mL/min, the pouring temperature is 20-30 ℃, the pressure is 60-80% of atmospheric pressure, the microwave power of microwave oscillation is 300-500W, and the drying temperature is 80-100 ℃.
In the step 6, the water vapor content in the humid environment is kept at 8-10%, and the temperature is 20-40 ℃; the ammonia gas environment is formed by combining ammonia gas and nitrogen gas, the volume ratio of the ammonia gas is 30-40%, the temperature is 20-30 ℃, the gas purged by standing at constant temperature is nitrogen gas, and the temperature is 100-120 ℃.
In the step 7, the stirring time is 30-60min, the reduction reaction pressure is 0.2-0.3MPa, and the reduction temperature is 20-30 ℃.
The beneficial effects of the invention are as follows: the invention enriches the groups on the surface area of the carrier through the modification of the carbon carrier, is favorable for the adhesion of the palladium active component in the later stage and improves the activity of the catalyst; through the cellulose reinforcement of secondary for the skeleton of charcoal carrier is more firm, has higher mechanical strength, can resist the external force that receives in the use, avoids taking place the carrier and collapses, has prolonged the life of catalyst. The strong porous structure of the carrier can keep good water permeability, and can ensure that the reaction substrate smoothly passes through the position reached by the pores of the carrier to contact with the active component in the using process of palladium-carbon, so as to carry out catalytic reaction. After the reaction is finished, the separation time is short and the production efficiency is high due to good water permeability in the solid-liquid separation process.
Detailed Description
The present invention will be described in detail with reference to the following embodiments.
The invention discloses a preparation method of a high-efficiency catalyst capable of being reused repeatedly, which is implemented according to the following steps:
step 1, adding activated carbon into an ethanol water solution for ultrasonic cleaning to obtain a clean activated carbon substrate;
in the ethanol water solution, the volume concentration of ethanol is 60-80%; the temperature of ultrasonic cleaning is 20-40 ℃ and the ultrasonic frequency is 40-80kHz;
the step utilizes the self-washing characteristic of ethanol and water, can completely dissolve most of impurities, ensures that the pores in the activated carbon are completely opened, and is cleaned;
step 2, carrying out acid soaking on the clean activated carbon substrate for 10-20min, then taking out the substrate, and carrying out alkali soaking for 30-50min to obtain an activated carbon substrate;
hydrochloric acid is adopted during acid soaking, and the pH value of the hydrochloric acid is 4-5; sodium hydroxide solution is adopted during alkali soaking, and the pH value is 10-11;
the surface of the activated carbon before cleaning contains a large number of groups, the groups are complex in composition and messy, all the groups can be acidified in the acid soaking process to be preliminarily unified into acid groups, the preliminarily unified acid groups on the surface of the activated carbon are formed, then the unified acid groups are subjected to alkaline treatment to achieve complete unification of the groups, the surface groups of the activated carbon are highly unified, meanwhile, the alkalized activated carbon substrate is influenced by sodium hydroxide to cause aggregation of surface active hydroxyl groups, and the surface activation of the activated carbon is realized;
step 3, adding palladium acetate into the acetone solution, uniformly stirring to form palladium acetate-acetone solution, then plating the palladium acetate-acetone solution on the surface of the active carbon substrate by utilizing negative pressure spraying, and drying at a constant temperature to obtain plated active carbon;
the mass concentration of palladium acetate in acetone is 200-400g/L, the stirring speed is 1000-2000r/min, the negative pressure spraying pressure is 40-60% of the atmospheric pressure, the spraying speed is 5-8mL/min, and the spraying amount is 0.1-0.4mL/cm 2 The temperature is 30-40 ℃; the constant temperature drying temperature is 60-70 ℃;
dissolving palladium acetate in acetone to form stable solution, setting negative pressure at one end of active carbon, and spraying palladium acetate-acetone solution at the other end; under the action of negative pressure, the sprayed palladium acetate-acetone liquid permeates into the activated carbon, the adsorption characteristic and the activation effect in the activated carbon form stable adsorption on the palladium acetate, meanwhile, acetone belongs to volatile liquid, and gas can be gradually generated under the negative pressure condition to compensate the negative pressure condition, so that the separation of the palladium acetate and the acetone is realized; namely palladium acetate is converted into palladium acetate particles in negative pressure spraying, and under the adsorption action and the hydrogen oxidation activity of the activated carbon material, an in-situ solidification effect is formed, and palladium acetate is fixed in the activated carbon substrate;
step 4, adding hydroxypropyl methyl cellulose and ethyl cellulose into methanol, uniformly stirring to form a composite cellulose solution, and then performing reduced pressure distillation to form a micro-thick liquid;
the concentration of the hydroxypropyl cellulose in the methanol is 40-50g/L, and the mass ratio of the hydroxypropyl methyl cellulose to the ethyl cellulose is 4:1-2, wherein the stirring speed is 1000-3000r/min, the pressure of reduced pressure distillation is 70-80% of atmospheric pressure, and the temperature is 50-60 ℃;
in the step, hydroxypropyl methyl cellulose and ethyl cellulose are fully mixed in a compatible manner in the stirring process, so that the effect of uniform mixing is achieved, and meanwhile, methanol is removed, so that the content of a solvent in a dissolution system can be effectively reduced, and the viscosity of a mixed cellulose solution is greatly improved;
step 5, putting the coated activated carbon substrate into a reaction kettle, treating with methanol vapor for 1-2h, then pouring micro-thick liquid into the coated activated carbon substrate under negative pressure, carrying out microwave oscillation treatment, and drying to obtain a prefabricated sealing block;
the methanol steam is a mixed gas consisting of nitrogen and methanol steam, and the volume ratio of the nitrogen to the methanol steam is 5:3-5, wherein the temperature of methanol steam treatment is 60-70 ℃, the filling speed of negative pressure filling is 5-10mL/min, the filling temperature is 20-30 ℃, the pressure is 60-80% of atmospheric pressure, the microwave power of microwave oscillation is 300-500W, and the drying temperature is 80-100 ℃;
based on the characteristic of methanol vapor treatment, forming a stable methanol vapor film on the surface of an active carbon substrate by combining high permeability of methanol with permeability of gas, and forming a liquid film in subsequent treatment, wherein palladium acetate is insoluble in methanol, which is a requirement of being capable of forming a film and blocking in sequence, otherwise, palladium acetate is secondarily dissolved, namely the liquid film is covered on the surface of palladium acetate; in the process of negative pressure pouring, the tail end of the activated carbon is provided with negative pressure, and the front section is used for pouring micro-thick liquid and continuously pushing inwards under the pushing of the negative pressure, so that the effect of complete pouring is achieved; the liquid film formed by the methanol on the surface of the active carbon substrate has solubility to the solute of the micro-thick liquid and is the same as the solute of the micro-thick liquid. Therefore, in the negative pressure pouring process, the hydroxypropyl methylcellulose and the ethyl cellulose are tightly attached to the specific surface of the activated carbon, and the palladium acetate is fixed in situ, so that the palladium acetate is not only adsorbed and pulled by the activated carbon, but also positioned and extruded by the hydroxypropyl methylcellulose and the ethyl cellulose to form immobilization;
step 6, placing the prefabricated sealing block in a humid environment for standing for 2-4 hours, then placing the prefabricated sealing block in an ammonia environment for standing for 3-6 hours, and keeping the temperature for standing and purging for 1-2 hours to obtain a palladium-carbon prefabricated sealing block;
the water vapor content in the humid environment is kept at 8-10%, and the temperature is 20-40 ℃; the ammonia environment is formed by combining ammonia and nitrogen, the volume ratio of the ammonia is 30-40%, the temperature is 20-30 ℃, the gas purged by standing at constant temperature is nitrogen, the temperature is 100-120 ℃, and the purged gas absorbs the ammonia in a mode of cooling and recycling acid liquor; the hydroxypropyl methylcellulose has moisture absorption, can absorb water vapor in air, and can absorb water molecules along with the extension of standing time, so that the internal and external equilibrium humidity is realized, and meanwhile, the characteristic of the ethyl cellulose that the ethyl cellulose is insoluble in water ensures that the ethyl cellulose forms an internal frame supporting structure, and an internal system is not broken up due to the moisture absorption of the hydroxypropyl methylcellulose; the hydroxypropyl methyl cellulose absorbing water molecules can absorb ammonia by utilizing water molecules in an ammonia environment, and form ammonium hydroxide molecules under the condition of the water molecules, meanwhile, based on the permeability of the water molecules, the ammonium hydroxide molecules are inwards transferred until the ammonium hydroxide molecules are completely distributed in the whole prefabricated sealing block, palladium acetate at the moment reacts with the ammonium hydroxide molecules to form a palladium hydroxide material of an insoluble system, and the product is completely dissolved, so that the effect of in-situ precipitation is realized; in the constant-temperature purging process, excessive ammonium hydroxide and generated acetic acid molecules are volatilized while water molecules are released at the temperature, so that the in-situ separation of palladium hydroxide is realized, simultaneously, the purging gas is absorbed by acid liquor, the pollution of ammonia gas is reduced, and meanwhile, the dissolubility of water to acetic acid is utilized to form solidification, so that the exhaust emission is reduced;
and 7, adding the palladium-carbon prefabricated sealing block into a reaction kettle with water, stirring for 30-60min at normal temperature, introducing hydrogen for reduction, filtering, and washing with water to obtain the palladium-carbon catalyst.
The reduction reaction pressure is 0.2-0.3MPa, and the reduction temperature is 20-30 ℃.
The invention enriches the groups on the surface area of the carrier through the modification of the carbon carrier, is favorable for the adhesion of the palladium active component in the later stage and improves the activity of the catalyst; through the cellulose reinforcement of secondary for the skeleton of charcoal carrier is more firm, has higher mechanical strength, can resist the external force that receives in the use, avoids taking place the carrier and collapses, has prolonged the life of catalyst.
Example 1
The invention discloses a preparation method of a palladium-carbon catalyst capable of being reused for multiple times, which is implemented according to the following steps:
step 1, adding activated carbon into an ethanol water solution for ultrasonic cleaning to obtain a clean activated carbon substrate;
in the ethanol water solution, the volume concentration of ethanol is 60; the temperature of ultrasonic cleaning is 20 ℃ and the ultrasonic frequency is 40kHz;
step 2, carrying out acid leaching on the clean activated carbon substrate for 10min, then taking out the substrate, and carrying out alkali leaching for 30min to obtain an activated carbon substrate;
hydrochloric acid is adopted during acid soaking, and the pH value of the hydrochloric acid is 4; sodium hydroxide solution is adopted during alkali soaking, and the pH value is 10;
step 3, adding palladium acetate into the acetone solution, uniformly stirring to form palladium acetate-acetone solution, then plating the palladium acetate-acetone solution on the surface of the active carbon substrate by utilizing negative pressure spraying, and drying at a constant temperature to obtain plated active carbon;
the mass concentration of palladium acetate in acetone is 200g/L, the stirring speed is 1000r/min, the negative pressure spraying pressure is 40% of the atmospheric pressure, the spraying speed is 5mL/min, and the spraying amount is 0.1mL/cm 2 The temperature is 30 ℃; the constant temperature drying temperature is 60 ℃;
step 4, adding hydroxypropyl methyl cellulose and ethyl cellulose into methanol, uniformly stirring to form a composite cellulose solution, and then performing reduced pressure distillation to form a micro-thick liquid;
the concentration of the hydroxypropyl cellulose in the methanol is 40g/L, and the mass ratio of the hydroxypropyl methyl cellulose to the ethyl cellulose is 4:1, stirring speed is 1000r/min, pressure of reduced pressure distillation is 70% of atmospheric pressure, and temperature is 50 ℃;
step 5, putting the coated activated carbon substrate into a reaction kettle, treating with methanol vapor for 1-2h, then pouring micro-thick liquid into the coated activated carbon substrate under negative pressure, carrying out microwave oscillation treatment, and drying to obtain a prefabricated sealing block;
the methanol steam is a mixed gas consisting of nitrogen and methanol steam, and the volume ratio of the nitrogen to the methanol steam is 5:3, the temperature of methanol steam treatment is 60 ℃, the filling speed of negative pressure filling is 5mL/min, the filling temperature is 20 ℃, the pressure is 60% of atmospheric pressure, the microwave power of microwave oscillation is 300W, and the drying temperature is 80 ℃;
step 6, placing the prefabricated sealing block in a humid environment for standing for 2 hours, then placing the prefabricated sealing block in an ammonia environment for standing for 3 hours, and keeping the temperature for standing and purging for 1 hour to obtain a palladium-carbon prefabricated sealing block;
the water vapor content in the humid environment is kept at 8 percent, and the temperature is 20 ℃; the ammonia environment is formed by combining ammonia and nitrogen, the volume ratio of the ammonia is 30%, the temperature is 20 ℃, the nitrogen is the gas which is subjected to constant-temperature standing and purging, the temperature is 100 ℃, and the purged gas absorbs the ammonia in a mode of cooling and recycling acid liquor;
and 7, adding the palladium-carbon prefabricated sealing block into a reaction kettle with water, stirring for 30min at normal temperature, introducing hydrogen for reduction, filtering, and washing with water to obtain the palladium-carbon catalyst.
The reduction reaction pressure was 0.2MPa and the reduction temperature was 20 ℃.
Example 2
The invention discloses a preparation method of a palladium-carbon catalyst capable of being reused for multiple times, which is implemented according to the following steps:
step 1, adding activated carbon into an ethanol water solution for ultrasonic cleaning to obtain a clean activated carbon substrate;
in the ethanol water solution, the volume concentration of ethanol is 70%; the temperature of ultrasonic cleaning is 30 ℃ and the ultrasonic frequency is 50kHz;
step 2, carrying out acid leaching on the clean activated carbon substrate for 15min, then taking out the substrate, and carrying out alkali leaching for 35min to obtain an activated carbon substrate;
hydrochloric acid is adopted during acid soaking, and the pH value of the hydrochloric acid is 4.5; sodium hydroxide solution is adopted during alkali soaking, and the pH value is 11;
step 3, adding palladium acetate into the acetone solution, uniformly stirring to form palladium acetate-acetone solution, then plating the palladium acetate-acetone solution on the surface of the active carbon substrate by utilizing negative pressure spraying, and drying at a constant temperature to obtain plated active carbon;
the mass concentration of palladium acetate in acetone is 300g/L, the stirring speed is 1500r/min, the negative pressure spraying pressure is 50% of the atmospheric pressure, the spraying speed is 6mL/min, and the spraying amount is 0.3mL/cm 2 The temperature is 35 ℃; the constant temperature drying temperature is 65 ℃;
the concentration of the hydroxypropyl cellulose in the methanol is 45g/L, and the mass ratio of the hydroxypropyl methyl cellulose to the ethyl cellulose is 4:2, stirring at 2000r/min, distilling under reduced pressure at 75% of atmospheric pressure and at 55deg.C;
step 5, putting the coated activated carbon substrate into a reaction kettle, treating with methanol vapor for 1-2h, then pouring micro-thick liquid into the coated activated carbon substrate under negative pressure, carrying out microwave oscillation treatment, and drying to obtain a prefabricated sealing block;
the methanol steam is a mixed gas consisting of nitrogen and methanol steam, and the volume ratio of the nitrogen to the methanol steam is 5:4, the temperature of methanol steam treatment is 70 ℃, the filling speed of negative pressure filling is 8mL/min, the filling temperature is 25 ℃, the pressure is 70% of atmospheric pressure, the microwave power of microwave oscillation is 400W, and the drying temperature is 90 ℃;
step 6, placing the prefabricated sealing block in a humid environment for standing for 3 hours, then placing the prefabricated sealing block in an ammonia environment for standing for 5 hours, and keeping the temperature for standing and purging for 2 hours to obtain a palladium-carbon prefabricated sealing block;
the water vapor content in the humid environment is kept at 9 percent, and the temperature is 30 ℃; the ammonia environment is formed by combining ammonia and nitrogen, the volume ratio of the ammonia is 35%, the temperature is 25 ℃, the nitrogen is the gas which is subjected to constant-temperature standing and purging, the temperature is 110 ℃, and the purged gas absorbs the ammonia in a mode of cooling and recycling acid liquor;
and 7, adding the palladium-carbon prefabricated sealing block into a reaction kettle with water, stirring for 40min at normal temperature, introducing hydrogen for reduction, filtering, and washing with water to obtain the palladium-carbon catalyst.
The reduction reaction pressure was 0.25MPa and the reduction temperature was 25 ℃.
Example 3
The invention discloses a preparation method of a palladium-carbon catalyst capable of being reused for multiple times, which is implemented according to the following steps:
step 1, adding activated carbon into an ethanol water solution for ultrasonic cleaning to obtain a clean activated carbon substrate;
in the ethanol water solution, the volume concentration of ethanol is 80%; the temperature of ultrasonic cleaning is 40 ℃ and the ultrasonic frequency is 80kHz;
step 2, carrying out acid leaching on the clean activated carbon substrate for 20min, then taking out the substrate, and carrying out alkali leaching for 30min to obtain an activated carbon substrate;
hydrochloric acid is adopted during acid soaking, and the pH value of the hydrochloric acid is 5; sodium hydroxide solution is adopted during alkali soaking, and the pH value is 11;
step 3, adding palladium acetate into the acetone solution, uniformly stirring to form palladium acetate-acetone solution, then plating the palladium acetate-acetone solution on the surface of the active carbon substrate by utilizing negative pressure spraying, and drying at a constant temperature to obtain plated active carbon;
the mass concentration of palladium acetate in acetone is 400g/L, the stirring speed is 2000r/min, the negative pressure spraying pressure is 60% of the atmospheric pressure, the spraying speed is mL/min, and the spraying amount is 0.4mL/cm 2 The temperature is 40 ℃; the constant temperature drying temperature is 70 ℃;
step 4, adding hydroxypropyl methyl cellulose and ethyl cellulose into methanol, uniformly stirring to form a composite cellulose solution, and then performing reduced pressure distillation to form a micro-thick liquid;
the concentration of the hydroxypropyl cellulose in the methanol is 50g/L, and the mass ratio of the hydroxypropyl methyl cellulose to the ethyl cellulose is 4:2, stirring at 3000r/min, distilling under reduced pressure at 80% of atmospheric pressure and at 60deg.C;
step 5, putting the coated activated carbon substrate into a reaction kettle, treating with methanol vapor for 1-2h, then pouring micro-thick liquid into the coated activated carbon substrate under negative pressure, carrying out microwave oscillation treatment, and drying to obtain a prefabricated sealing block;
the methanol steam is a mixed gas consisting of nitrogen and methanol steam, and the volume ratio of the nitrogen to the methanol steam is 5:5, the temperature of methanol steam treatment is 70 ℃, the filling speed of negative pressure filling is 10mL/min, the filling temperature is 30 ℃, the pressure is 80% of atmospheric pressure, the microwave power of microwave oscillation is 500W, and the drying temperature is 100 ℃;
step 6, placing the prefabricated sealing block in a wet environment for standing for 4 hours, then placing the prefabricated sealing block in an ammonia environment for standing for 6 hours, and keeping the temperature for standing and purging for 2 hours to obtain a palladium-carbon prefabricated sealing block;
the water vapor content in the humid environment is kept at 10 percent, and the temperature is 40 ℃; the ammonia environment is formed by combining ammonia and nitrogen, the volume ratio of the ammonia is 40%, the temperature is 30 ℃, the gas purged by standing at constant temperature is nitrogen, the temperature is 120 ℃, and the purged gas absorbs the ammonia in a mode of cooling and recycling acid liquor;
and 7, adding the palladium-carbon prefabricated sealing block into a reaction kettle with water, stirring for 60min at normal temperature, introducing hydrogen for reduction, filtering, and washing with water to obtain the palladium-carbon catalyst.
The reduction reaction pressure was 0.3MPa and the reduction temperature was 30 ℃.
Claims (5)
1. The preparation method of the palladium-carbon catalyst capable of being reused for multiple times is characterized by comprising the following steps:
step 1, adding activated carbon into an ethanol water solution for ultrasonic cleaning to obtain a clean activated carbon substrate;
step 2, carrying out acid soaking on the clean activated carbon substrate, and then taking out the substrate for alkali soaking to obtain an activated carbon substrate;
step 3, adding palladium acetate into the acetone solution, uniformly stirring to form palladium acetate-acetone solution, then plating a film of the palladium acetate-acetone solution on the surface of the active carbon substrate by utilizing negative pressure spraying, and drying to obtain coated active carbon;
the mass concentration of palladium acetate in acetone is 200-400g/L, the stirring speed is 1000-2000r/min, the negative pressure spraying pressure is 40-60% of the atmospheric pressure, the spraying speed is 5-8mL/min, and the spraying amount is 0.1-0.4mL/cm 2 The temperature is 30-40 ℃; the drying temperature is 60-70 ℃;
step 4, adding hydroxypropyl methyl cellulose and ethyl cellulose into methanol, uniformly stirring to form a composite cellulose solution, and then performing reduced pressure distillation to form a micro-thick liquid;
the concentration of the hydroxypropyl cellulose in the methanol is 40-50g/L, and the mass ratio of the hydroxypropyl methyl cellulose to the ethyl cellulose is 4:1-2, wherein the stirring speed is 1000-3000r/min, the pressure of reduced pressure distillation is 70-80% of atmospheric pressure, and the temperature is 50-60 ℃;
step 5, putting the coated activated carbon substrate into a reaction kettle, treating with methanol vapor for 1-2h, then pouring micro-thick liquid into the coated activated carbon substrate under negative pressure, carrying out microwave oscillation treatment, and drying to obtain a prefabricated sealing block;
the methanol steam is a mixed gas consisting of nitrogen and methanol steam, and the volume ratio of the nitrogen to the methanol steam is 5:3-5, wherein the temperature of methanol steam treatment is 60-70 ℃, the filling speed of negative pressure filling is 5-10mL/min, the filling temperature is 20-30 ℃, the pressure is 60-80% of atmospheric pressure, the microwave power of microwave oscillation is 300-500W, and the drying temperature is 80-100 ℃;
step 6, placing the prefabricated sealing block in a humid environment for standing for 2-4 hours, then placing the prefabricated sealing block in an ammonia environment for standing for 3-6 hours, and keeping the temperature for standing and purging for 1-2 hours to obtain a palladium-carbon prefabricated sealing block;
and 7, adding the palladium-carbon prefabricated sealing block into a reaction kettle with water, stirring at normal temperature, introducing hydrogen for reduction, filtering, and washing with water to obtain the palladium-carbon catalyst.
2. The method for preparing a palladium-carbon catalyst for multiple applications according to claim 1, wherein in the step 1, the volume concentration of ethanol in the ethanol aqueous solution is 60-80%; the ultrasonic cleaning temperature is 20-40 ℃ and the ultrasonic frequency is 40-80kHz.
3. The method for preparing the palladium-carbon catalyst which can be reused for multiple times according to claim 1, wherein in the step 2, hydrochloric acid is adopted for soaking for 10-20min, and the pH of the hydrochloric acid is 4-5; the alkali soaking is performed with sodium hydroxide solution for 30-50min, and pH is 10-11.
4. The method for preparing a palladium-carbon catalyst which can be reused for multiple times according to claim 1, wherein in the step 6, the water vapor content in the humid environment is kept at 8-10%, and the temperature is 20-40 ℃; the ammonia gas environment is formed by combining ammonia gas and nitrogen gas, the volume ratio of the ammonia gas is 30-40%, the temperature is 20-30 ℃, the gas purged by standing at constant temperature is nitrogen gas, and the temperature is 100-120 ℃.
5. The method for preparing a palladium-carbon catalyst for multiple applications according to claim 1, wherein in the step 7, the stirring time is 30-60min, the reduction reaction pressure is 0.2-0.3MPa, and the reduction temperature is 20-30 ℃.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4239653A (en) * | 1978-11-27 | 1980-12-16 | Chinoin Gyogyszer | Process for the preparation of non-pyrophoric palladium catalysts |
| CN110201664A (en) * | 2019-06-26 | 2019-09-06 | 陕西瑞科新材料股份有限公司 | A kind of preparation method of bamboo charcoal plated film palladium catalyst |
| CN112675839A (en) * | 2021-01-11 | 2021-04-20 | 浙江工业大学上虞研究院有限公司 | High-performance palladium-carbon catalyst and preparation method thereof |
| CN112675840A (en) * | 2021-01-11 | 2021-04-20 | 浙江工业大学上虞研究院有限公司 | Catalyst for nitroaniline and preparation method thereof |
| CN113600167A (en) * | 2021-09-13 | 2021-11-05 | 刘毅毅 | Preparation method of palladium-carbon catalyst based on ectoine |
| CN113769736A (en) * | 2021-09-06 | 2021-12-10 | 陕西瑞科新材料股份有限公司 | Preparation method of palladium hydroxide carbon carrier catalyst |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7396795B2 (en) * | 2005-08-31 | 2008-07-08 | Headwaters Technology Innovation, Llc | Low temperature preparation of supported nanoparticle catalysts having increased dispersion |
-
2022
- 2022-01-19 CN CN202210063107.5A patent/CN114392737B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4239653A (en) * | 1978-11-27 | 1980-12-16 | Chinoin Gyogyszer | Process for the preparation of non-pyrophoric palladium catalysts |
| CN110201664A (en) * | 2019-06-26 | 2019-09-06 | 陕西瑞科新材料股份有限公司 | A kind of preparation method of bamboo charcoal plated film palladium catalyst |
| CN112675839A (en) * | 2021-01-11 | 2021-04-20 | 浙江工业大学上虞研究院有限公司 | High-performance palladium-carbon catalyst and preparation method thereof |
| CN112675840A (en) * | 2021-01-11 | 2021-04-20 | 浙江工业大学上虞研究院有限公司 | Catalyst for nitroaniline and preparation method thereof |
| CN113769736A (en) * | 2021-09-06 | 2021-12-10 | 陕西瑞科新材料股份有限公司 | Preparation method of palladium hydroxide carbon carrier catalyst |
| CN113600167A (en) * | 2021-09-13 | 2021-11-05 | 刘毅毅 | Preparation method of palladium-carbon catalyst based on ectoine |
Non-Patent Citations (2)
| Title |
|---|
| 一种钯炭催化剂的制备方法;王小菊;;化工管理(第05期);第24页 * |
| 无机物负载型钯催化剂的研究进展;焦建丽;黄龙江;滕大为;;化学与生物工程(第03期);第4-8页 * |
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