CN112892527A - Palladium-carbon catalyst for catalyzing liquid sodium gluconate and production process thereof - Google Patents
Palladium-carbon catalyst for catalyzing liquid sodium gluconate and production process thereof Download PDFInfo
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- CN112892527A CN112892527A CN202110082785.1A CN202110082785A CN112892527A CN 112892527 A CN112892527 A CN 112892527A CN 202110082785 A CN202110082785 A CN 202110082785A CN 112892527 A CN112892527 A CN 112892527A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 119
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 239000007788 liquid Substances 0.000 title claims abstract description 43
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 26
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 239000000176 sodium gluconate Substances 0.000 title claims abstract description 24
- 235000012207 sodium gluconate Nutrition 0.000 title claims abstract description 24
- 229940005574 sodium gluconate Drugs 0.000 title claims abstract description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 196
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 113
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims abstract description 32
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 22
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 22
- 239000011734 sodium Substances 0.000 claims abstract description 22
- 229920001503 Glucan Polymers 0.000 claims abstract description 17
- DYQDPMZRUUOGSZ-UHFFFAOYSA-N Cl.[N+](=O)([O-])[O-].[Bi+3].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] Chemical compound Cl.[N+](=O)([O-])[O-].[Bi+3].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] DYQDPMZRUUOGSZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 39
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical group O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 34
- 229910017604 nitric acid Inorganic materials 0.000 claims description 31
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 28
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 25
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 20
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000012153 distilled water Substances 0.000 claims description 16
- 238000006555 catalytic reaction Methods 0.000 claims description 15
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 13
- 239000008103 glucose Substances 0.000 claims description 13
- 239000003513 alkali Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 239000000706 filtrate Substances 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- 230000004913 activation Effects 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 239000002270 dispersing agent Substances 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 239000000498 cooling water Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 230000007958 sleep Effects 0.000 claims description 5
- 210000003298 dental enamel Anatomy 0.000 claims description 4
- 238000005070 sampling Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 239000002023 wood Substances 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 abstract description 55
- -1 palladium ions Chemical class 0.000 abstract description 24
- 230000003197 catalytic effect Effects 0.000 abstract description 22
- 230000002035 prolonged effect Effects 0.000 abstract description 11
- 229910001451 bismuth ion Inorganic materials 0.000 abstract description 5
- 235000001727 glucose Nutrition 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- 230000000694 effects Effects 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 4
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 3
- 239000000174 gluconic acid Substances 0.000 description 3
- 235000012208 gluconic acid Nutrition 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000003610 charcoal Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000013065 commercial product Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 230000005059 dormancy Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical group [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 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
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/644—Arsenic, antimony or bismuth
- B01J23/6447—Bismuth
-
- 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
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
-
- 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
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
-
- 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
- B01J37/024—Multiple impregnation or coating
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
Abstract
The application relates to the technical field of catalysts, and particularly discloses a palladium-carbon catalyst for catalyzing liquid sodium gluconate and a production process thereof. A production process of a palladium-carbon catalyst for catalyzing liquid sodium gluconate comprises the following steps: bismuth nitrate hydrochloric acid solution reacts with activated carbon, bismuth ions are introduced into the activated carbon, palladium chloride solution is added dropwise, palladium ions are introduced into the activated carbon, and finally a reducing agent is added under an alkaline condition to reduce the palladium ions into palladium, so that the palladium is better loaded on the activated carbon, and the mechanical strength of the activated carbon is enhanced, therefore, a palladium-carbon catalyst with better catalytic activity is obtained, and the service life of the palladium-carbon catalyst is prolonged; the palladium-carbon catalyst for catalyzing the liquid sodium glucan can be used for catalyst production, and has the advantage of long service life; in addition, the preparation method has the advantage of prolonging the service life of the palladium-carbon catalyst.
Description
Technical Field
The application relates to the technical field of catalysts, in particular to a palladium-carbon catalyst for catalyzing liquid sodium glucan and a production process thereof.
Background
In the production process of liquid sodium gluconate, a heterogeneous catalytic oxidation method is usually adopted for production, a common catalyst for producing the liquid sodium gluconate by the heterogeneous catalytic oxidation method is mainly a palladium-carbon catalyst, the palladium-carbon catalyst is a catalyst with active carbon as a carrier and palladium as an active component, the palladium-carbon catalyst can show good catalytic performance when catalyzing and oxidizing glucose, and the palladium-carbon catalyst is the core of catalytic reactions such as hydrofining and the like, and has the value that a homogeneous catalyst cannot replace in the field of chemical synthesis.
In view of the above-mentioned related technologies, the inventors found that after the palladium carbon catalyst is recycled for a certain number of times, the catalytic efficiency is reduced, and even the palladium carbon catalyst has no catalytic activity, so that the palladium carbon catalyst must be scrapped and updated, which results in high production cost of sodium gluconate.
Disclosure of Invention
In order to prolong the service life of the palladium-carbon catalyst, the application provides the palladium-carbon catalyst for catalyzing liquid sodium glucan.
In order to obtain a palladium-carbon catalyst with long service life, the application provides a production process of the palladium-carbon catalyst for catalyzing liquid sodium glucan.
The application provides a palladium carbon catalyst for catalyzing liquid sodium glucan adopts following technical scheme:
in a first aspect, the application provides a production process of a palladium-carbon catalyst for catalyzing liquid sodium gluconate, which adopts the following technical scheme: a production process of a palladium-carbon catalyst for catalyzing liquid sodium glucan comprises the following steps:
s1: adding activated carbon after activation treatment into bismuth nitrate hydrochloric acid solution, controlling the temperature to be 27-29 ℃, and starting stirring for reaction;
s2: after the reaction end point is reached, dropwise adding a palladium chloride solution, controlling the temperature to be 27-29 ℃, starting sampling and filtering after the dropwise adding reaction is finished for 0.9-1.2h, and observing the brightness of the filtrate;
s3: adding alkali liquor after the filtrate is transparent, adjusting the pH value of the solution, adding a reducing agent when the pH value of the solution is 10-11, heating to 75-85 ℃, and keeping the temperature for 0.9-1.2 h;
s4: cooling, and simultaneously continuing stirring by the stirrer until the temperature in the kettle is reduced to 30-33 ℃, stopping injecting cooling water, stopping stirring, allowing the liquid to sleep for 16-24h, and obtaining the palladium-carbon catalyst after the sleep is finished;
the bismuth nitrate hydrochloric acid solution comprises 10-15 parts of bismuth nitrate solution and 13-18 parts of hydrochloric acid, wherein the addition amount of the hydrochloric acid is recorded by HCl,
10-20 parts of distilled water;
the bismuth nitrate solution comprises 4-6 parts of bismuth nitrate,
hydrochloric acid, wherein the addition amount of the hydrochloric acid is recorded as HCl and is 5-7 parts by mass;
the preparation method of the activated carbon comprises the following steps: 20-30 parts of activated carbon and 80-100 parts of distilled water are put into an enamel reaction kettle to be stirred, nitric acid is added, and the addition amount of the nitric acid is HNO38-12 parts by mass, heating to 85-95 ℃, preserving heat for 2-4 hours, cooling, and performing centrifugal filtration to obtain activated carbon;
the alkali liquor is obtained by mixing 8-12 parts of alkali and 30-35 parts of distilled water;
the palladium chloride solution comprises 1.3-2 parts of palladium chloride,
hydrochloric acid, wherein the addition amount of the hydrochloric acid is 0.8-1.5 parts by mass in terms of HCl,
1-3 parts of distilled water.
By adopting the technical scheme, the activated carbon is used as a carrier of the palladium-carbon catalyst, the ash content of the activated carbon can be greatly reduced by adding nitric acid due to the fact that the ash content of the activated carbon is high, the surface of the activated carbon is functionalized, palladium ions can be effectively adsorbed, on the other hand, the pore diameter and the pore volume of the activated carbon are enlarged by adding the nitric acid, the prepared palladium-carbon catalyst has better catalysis effect on the preparation process of liquid sodium gluconate, glucose and gluconic acid with large molecular weights can easily enter macropores of the activated carbon and contact palladium loaded on the activated carbon, the catalytic activity of the palladium-carbon catalyst is improved, and the service life of the palladium-carbon catalyst is prolonged.
Preferably, the palladium chloride solution also comprises 0.5-1.2 parts of a dispersing agent.
By adopting the technical scheme, when the palladium chloride solution is loaded on the active carbon, the palladium chloride solution is easy to infiltrate on the active carbon by the dispersant, and meanwhile, the palladium chloride solution is kept in a good dispersion state when being loaded on the active carbon.
Preferably, the dispersant is polyvinyl alcohol.
By adopting the technical scheme, in the catalytic process of the palladium-carbon catalyst, due to mutual friction among palladium-carbon catalyst particles, carrier activated carbon is broken, palladium loss is caused, and finally the palladium-carbon catalyst is inactivated. The polyvinyl alcohol is mixed with a palladium chloride solution and then is introduced into the activated carbon along with palladium ions, the polyvinyl alcohol and the palladium chloride solution can be better dispersed into the activated carbon, meanwhile, the polyvinyl alcohol is adsorbed onto the activated carbon, the polyvinyl alcohol has good film forming property and can promote the palladium ions to be adhered onto the activated carbon, meanwhile, the polyvinyl alcohol has good adsorbability, and after the palladium ions are reduced into palladium, the polyvinyl alcohol adheres the palladium onto the activated carbon, so that the load fastness of the palladium and the activated carbon is enhanced, the mechanical strength of the activated carbon is also enhanced, the loss of the palladium is reduced, and the service life of the catalyst is prolonged.
Preferably, the particle size of the activated carbon is 200-300 meshes.
By adopting the technical scheme, the activated carbon with the granularity of 200-300 meshes has large adsorption capacity and can better support and disperse palladium.
Preferably, the activated carbon is wood charcoal.
By adopting the technical scheme, the proportion of the transition holes and the macropores of the wood charcoal is higher, so that glucose with larger molecular weight can enter more easily during the catalytic reaction of glucose, the contact area between an active center and a reactant is enhanced, the reaction rate and the catalytic activity of the catalyst are improved, and the service life of the catalyst is prolonged.
Preferably, the bismuth nitrate hydrochloric acid solution further comprises nitric acid, and the addition amount of the nitric acid is HNO35 to 10 parts by mass.
By adopting the technical scheme, nitric acid is added into the bismuth nitrate hydrochloric acid solution, the nitric acid can further reduce the hydrolysis of bismuth nitrate, the bismuth nitrate can better enter the activated carbon, bismuth ions are firstly introduced to play a role in protecting palladium ions, and the service life of the prepared palladium carbon catalyst is longer.
Preferably, the reducing agent is formaldehyde.
By adopting the technical scheme, the formaldehyde is a liquid-phase reducing agent, the formaldehyde can reduce palladium ions into palladium under an alkaline condition, and palladium particles in the palladium-carbon catalyst reduced by the formaldehyde have smaller particle size and higher activity, so that the catalyst is more beneficial to prolonging the service life of the catalyst.
In a second aspect, the present application provides a palladium-carbon catalyst for catalyzing liquid sodium gluconate, which adopts the following technical scheme:
a palladium-carbon catalyst for catalyzing liquid sodium gluconate is prepared by the production process of the palladium-carbon catalyst for catalyzing liquid sodium gluconate according to any one of claims 1 to 7.
By adopting the technical scheme, the bismuth nitrate is dissolved in the hydrochloric acid, the dispersibility of the bismuth nitrate is enhanced, the hydrolysis condition of the bismuth nitrate during the previous reaction is reduced by adding the nitric acid, the bismuth nitrate solution and the activated carbon after the activation treatment are fully reacted, then the palladium chloride solution is dropwise added, the activated carbon after the activation treatment by the nitric acid has better adsorption performance, the aperture and the pore volume of the activated carbon are increased, the palladium ions can be favorably adsorbed to enter the activated carbon, the bismuth ions can protect the palladium ions, finally the palladium ions are reduced into palladium by formaldehyde, the palladium has good catalytic activity, meanwhile, the polyvinyl alcohol entering the activated carbon along with the palladium chloride solution enhances the mechanical strength of the activated carbon, the palladium is better bonded on the activated carbon by the polyvinyl alcohol, the catalytic activity of a palladium-carbon catalyst is enhanced, and the service life of the palladium-carbon catalyst is prolonged.
In summary, the present application has the following beneficial effects:
1. because the activated carbon is activated by the nitric acid, the ash content of the activated carbon is high, the ash content of the activated carbon can be greatly reduced by adding the nitric acid, so that the surface of the activated carbon is functionalized, palladium ions can be more effectively adsorbed, and on the other hand, the pore diameter and the pore volume of the activated carbon are enlarged by adding the nitric acid, so that the prepared palladium-carbon catalyst has better catalysis effect on the preparation process of the liquid sodium gluconate, glucose and gluconic acid with larger molecular weights can more easily enter macropores of the activated carbon and contact palladium loaded on the activated carbon, the catalytic activity of the palladium-carbon catalyst is improved, and the service life of the palladium-carbon catalyst is prolonged;
2. polyvinyl alcohol is preferably used in the application, and in the process of catalyzing the palladium-carbon catalyst, particles of the palladium-carbon catalyst are rubbed with each other to cause the breakage of carrier activated carbon, so that palladium is lost, and finally the palladium-carbon catalyst is inactivated. The polyvinyl alcohol is mixed with a palladium chloride solution and then is introduced into the activated carbon along with palladium ions, the polyvinyl alcohol and the palladium chloride solution can be better dispersed into the activated carbon, meanwhile, the polyvinyl alcohol is adsorbed onto the activated carbon, the polyvinyl alcohol has good film forming property and can promote the palladium ions to be adhered onto the activated carbon, meanwhile, the polyvinyl alcohol has good adsorbability, and after the palladium ions are reduced into palladium, the polyvinyl alcohol adheres the palladium onto the activated carbon, so that the load fastness of the palladium and the activated carbon is enhanced, the mechanical strength of the activated carbon is also enhanced, the loss of the palladium is reduced, and the service life of the catalyst is prolonged;
3. according to the method, bismuth nitrate hydrochloric acid solution and activated carbon are reacted, bismuth ions are introduced into the activated carbon, palladium chloride solution is added dropwise, palladium ions are introduced into the activated carbon, and finally a reducing agent is added under an alkaline condition to reduce the palladium ions into palladium, so that the palladium is better loaded on the activated carbon, and the mechanical strength of the activated carbon is enhanced, therefore, a palladium-carbon catalyst with better catalytic activity is obtained, and the service life of the catalyst is prolonged.
Detailed Description
The raw material sources are as follows:
the palladium chloride is a commercial product of Nanjing chemical reagent GmbH, and the mark is 7647-10-1;
nitric acid is a commercial product of Jinconal chemical Co., Ltd, and the brand number is 12033-49-7;
formaldehyde is a product sold in the market of Nanjing chemical reagent GmbH, and the brand number is 50-00-0;
the activated carbon is a product sold in Liyang activated carbon factories of Jiangsu;
the polyvinyl alcohol is a product sold in Shanghai-sourced leaf Biotechnology Co., Ltd, and the mark is 9002-89-5.
The commercially available palladium on carbon catalyst is a commercially available product of Zhengzhou Achrom chemical Co., Ltd.
Example 1
A palladium-carbon catalyst for catalyzing liquid sodium glucan comprises the following raw materials in parts by weight:
50 parts of bismuth nitrate hydrochloric acid solution,
125 parts of activated carbon after the activation treatment,
5 parts of a palladium chloride solution, namely,
11 parts of a reducing agent, namely a sodium hydroxide,
43 parts of an alkali liquor,
wherein the bismuth nitrate hydrochloric acid solution comprises 11 parts of bismuth nitrate solution,
410mL of hydrochloric acid with the concentration of 1mol/L,
130mL of nitric acid with the concentration of 1mol/L,
and 15 parts of distilled water, wherein,
the bismuth nitrate solution comprises 5 parts of bismuth nitrate and 164mL of hydrochloric acid, the concentration is 1mol/l,
the activated carbon comprises 25 parts of activated carbon, 90 parts of distilled water and 158mL of nitric acid, the concentration is 1mol/l, the granularity of the activated carbon is 300 meshes, the activated carbon activation treatment mode is that the activated carbon and the distilled water are placed in an enamel reaction kettle to be stirred, the nitric acid is added, the temperature is increased to 90 ℃, the temperature is kept for 3 hours, the temperature is reduced to 70 ℃, the mixture is placed in a centrifuge with a 1000-mesh filter bag to be centrifugally filtered, the activated carbon is washed by pure water, the pH value of a filtrate is 5.5-6, and the activated carbon is obtained after the washing;
the 43 parts of alkali liquor is obtained by mixing raw materials comprising 10 parts of alkali and 33 parts of distilled water;
the palladium chloride solution includes 1.678 parts of palladium chloride,
27mL of hydrochloric acid with the concentration of 1mol/l,
2 parts of distilled water, namely distilled water,
and 1 part of polyvinyl alcohol;
the reducing agent is formaldehyde.
The production process of the palladium-carbon catalyst for catalyzing the liquid sodium glucan comprises the following steps:
s1: adding bismuth nitrate hydrochloric acid solution into an enamel reaction kettle, adding activated carbon after activation treatment, introducing cooling water into a jacket of the reaction kettle, controlling the temperature in the kettle to be reduced to about 28 ℃, stirring for 30 minutes, sampling and filtering, taking samples every 10 minutes, judging a reaction end point by dripping ionic alkali, and if precipitates of two filtrates are close, judging the reaction end point;
s2: after the reaction end point is reached, dropwise adding a palladium chloride solution for about 1h, controlling the temperature to be 28 ℃, starting sampling and filtering after the dropwise adding reaction is finished for 1h, and observing the brightness of the filtrate;
s3: adding alkali liquor after the filtrate is transparent, adjusting the pH value of the solution to be about 11, adding alkali for about 30min, adding formaldehyde when the pH value of the solution is 10-11, heating the solution to about 80 ℃ within 30min, and keeping the temperature for 1 h.
S4: cooling, namely adding cooling water into a jacket of the reaction kettle for cooling, continuously stirring by using a stirrer until the temperature in the kettle is reduced to about 32 ℃, stopping injecting the cooling water, stopping stirring, and allowing the liquid to sleep for 16-24 hours;
s5: and (3) after dormancy is finished, putting the solution into a centrifuge with a filter bag lined with 1000 meshes, starting centrifugal filtration, repeatedly washing with distilled water until the filtrate does not whiten the fibers, finally obtaining the palladium-carbon catalyst, and placing the palladium-carbon catalyst in a closed container filled with distilled water.
Examples 2 to 5
A production process of a palladium-carbon catalyst for catalyzing liquid sodium glucan is based on example 1, and is different in raw material dosage.
The amounts of the raw materials used in examples 1 to 5 are shown in the following table.
TABLE 1 raw material amounts of examples 1 to 5
Example 6
A production process of palladium-carbon catalyst for catalyzing liquid sodium glucan is based on example 1, and is characterized in that activated carbon is not subjected to activation treatment by nitric acid.
The liquid sodium catalysts of examples 1-5 and example 6 were tested with palladium on carbon catalyst.
The test comprises the following steps:
1. service life test
Testing, performing sodium gluconate synthesis reaction without a catalyst, adding 2kg of 15 wt% glucose solution and 1kg of 30 wt% sodium hydroxide solution, reacting at 40 ℃ and a pH value of 8-9, cooling and filtering the reacted solution, distilling and concentrating the filtrate under reduced pressure to about 1/5 of the original volume, crystallizing, and air drying to obtain the sodium gluconate.
The time required for carrying out the sodium gluconate synthesis reaction in the absence of the catalyst is 32 hours, the time for catalytically synthesizing the sodium gluconate reaction after adding a commercially available palladium-carbon catalyst is 16 hours, and the catalyst is judged to be deactivated when the catalytic reaction exceeds 20 hours.
Adding a palladium-carbon catalyst in the production of sodium gluconate, wherein the dosage of glucose and the dosage of the palladium-carbon catalyst are both fixed values in the test, the mass ratio of the glucose to the palladium-carbon catalyst is 2%, and testing the catalytic frequency of the palladium-carbon catalyst when the palladium-carbon catalyst loses activity.
The test results are given in the table below.
TABLE II test results for palladium on carbon catalysts for liquid sodium gluconate catalysis in examples 1-5 and 6
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | |
| Number of times of catalysis | 400 | 395 | 394 | 397 | 398 | 200 |
The catalysis times of the embodiments 1 to 5 are all superior to those of the embodiment 6, so that in the application, due to the fact that the ash content of the activated carbon is high, the addition of nitric acid can greatly reduce the ash content of the activated carbon, the surface of the activated carbon is functionalized, palladium ions can be more effectively adsorbed, on the other hand, the addition of nitric acid enlarges the aperture and the pore volume of the activated carbon, the prepared palladium-carbon catalyst has better catalysis effect on the preparation process of liquid sodium gluconate, glucose and gluconic acid with large molecular weights can more easily enter the macropores of the activated carbon and contact palladium loaded on the activated carbon, the catalytic activity of the palladium-carbon catalyst is improved, and the service life of the palladium-carbon catalyst is prolonged.
Example 7
A production process of palladium-carbon catalyst for catalyzing liquid sodium glucose is based on example 1, and is characterized in that no dispersant is added into palladium chloride solution.
Example 8
A production process of a palladium-carbon catalyst for catalyzing liquid sodium glucan is based on example 1, and is characterized in that a dispersing agent is sodium pyrophosphate.
Example 9
A production process of palladium-carbon catalyst for catalyzing liquid sodium glucan is based on example 1, and the difference is 100 meshes of the particle size of activated carbon.
Example 10
A production process of palladium-carbon catalyst for catalyzing liquid sodium glucan is based on example 1, and the difference is that activated carbon is shell carbon.
Example 11
A production process of palladium-carbon catalyst for catalyzing liquid sodium glucan is based on example 1, and the difference is that activated carbon is coconut shell carbon.
The liquid sodium catalysts of examples 7-11 were tested with palladium on carbon catalysts.
The test results are given in the table below.
TABLE III test results for palladium on carbon catalysts for liquid sodium gluconate catalysis of examples 7-11
| Example 7 | Example 8 | Example 9 | Example 10 | Example 11 | |
| Number of times of catalysis | 351 | 363 | 381 | 382 | 385 |
When the catalyst of example 1 was used for supporting palladium chloride solution on activated carbon, the palladium chloride solution was easily impregnated on the activated carbon, and the palladium chloride solution was maintained in a good dispersion state when the palladium chloride solution was supported on the activated carbon, as can be seen from the combination of example 1 and example 7 in combination with tables two and three.
Combining example 1 and example 8 and combining tables two and three, it can be seen that the catalytic frequency of the catalyst of example 1 is better than that of example 8, in this application, because the palladium carbon catalyst rubs with each other between the palladium carbon catalyst particles during the catalytic process, the carrier activated carbon is broken, the palladium is lost, and finally the palladium carbon catalyst is deactivated. The polyvinyl alcohol is mixed with a palladium chloride solution and then is introduced into the activated carbon along with palladium ions, the polyvinyl alcohol and the palladium chloride solution can be better dispersed into the activated carbon, meanwhile, the polyvinyl alcohol is adsorbed onto the activated carbon, the polyvinyl alcohol has good film forming property and can promote the palladium ions to be adhered onto the activated carbon, meanwhile, the polyvinyl alcohol has good adsorbability, and after the palladium ions are reduced into palladium, the polyvinyl alcohol adheres the palladium onto the activated carbon, so that the load fastness of the palladium and the activated carbon is enhanced, the mechanical strength of the activated carbon is also enhanced, the loss of the palladium is reduced, and the service life of the catalyst is prolonged.
Combining example 1 and example 9 and combining tables two and three, it can be seen that the catalytic times of the catalyst of example 1 are better than that of example 9, and the activated carbon with the particle size of 300 meshes in the application has a large adsorption capacity, and can better support and disperse palladium, thereby being beneficial to improving the activity of the palladium carbon catalyst and prolonging the service life of the palladium carbon catalyst.
Combining example 1 and examples 10-11 and combining tables two and three, it can be seen that the catalytic frequency of the catalyst of example 1 is better than that of examples 10-11, the ratio of transition pores to macropores of the lignocelluloses in the application is higher, glucose with a larger molecular weight can enter more easily when the catalytic reaction of glucose is carried out, the contact area of an active center and a reactant is enhanced, the reaction rate and the catalytic activity of the catalyst are improved, and the service life of the catalyst is prolonged.
Example 12
The production process of palladium-carbon catalyst for catalyzing liquid sodium gluconate is based on example 1 and features that nitric acid is not added into bismuth nitrate hydrochloric acid solution.
Example 13
A production process of palladium-carbon catalyst for catalyzing liquid sodium glucan is based on example 1, and is characterized in that the reducing agent is sodium borohydride.
The liquid sodium catalysts of examples 12-13 were tested with palladium on carbon catalysts.
The test results are given in the table below.
TABLE IV, test results for palladium on carbon catalyst for liquid sodium gluconate catalysis in examples 12-13
| Example 12 | Example 13 | |
| Number of times of catalysis | 371 | 382 |
Combining the example 1 and the example 12 and combining the second and fourth tables, it can be seen that the catalytic frequency of the catalyst in the example 1 is better than that in the example 11, in the application, nitric acid is added into a bismuth nitrate hydrochloric acid solution, the nitric acid can further reduce the hydrolysis of bismuth nitrate, the bismuth nitrate can be ensured to better enter into activated carbon, bismuth ions are firstly introduced to play a role in protecting palladium ions, and the service life of the prepared palladium-carbon catalyst is longer.
Combining example 1 and example 13 and combining tables two and four, it can be seen that the catalytic frequency of the catalyst of example 1 is better than that of example 12, formaldehyde is a liquid phase reducing agent in the present application, formaldehyde can reduce palladium ions into palladium under alkaline conditions, and palladium carbon catalyst reduced by formaldehyde has smaller palladium particle size and higher activity, which is more conducive to prolonging the service life of the catalyst.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (8)
1. A production process of a palladium-carbon catalyst for catalyzing liquid sodium glucan is characterized by comprising the following steps:
s1: adding activated carbon after activation treatment into bismuth nitrate hydrochloric acid solution, controlling the temperature to be 27-29 ℃, and starting stirring for reaction;
s2: after the reaction end point is reached, dropwise adding a palladium chloride solution, controlling the temperature to be 27-29 ℃, starting sampling and filtering after the dropwise adding reaction is finished for 0.9-1.2h, and observing the brightness of the filtrate;
s3: adding alkali liquor after the filtrate is transparent, adjusting the pH value of the solution, adding a reducing agent when the pH value of the solution is 10-11, heating to 75-85 ℃, and keeping the temperature for 0.9-1.2 h;
s4: cooling, and simultaneously continuing stirring by the stirrer until the temperature in the kettle is reduced to 30-33 ℃, stopping injecting cooling water, stopping stirring, allowing the liquid to sleep for 16-24h, and obtaining the palladium-carbon catalyst after the sleep is finished;
the bismuth nitrate hydrochloric acid solution comprises 10-15 parts of bismuth nitrate solution,
hydrochloric acid, wherein the addition amount of the hydrochloric acid is 13-18 parts by mass in terms of HCl,
10-20 parts of distilled water;
the bismuth nitrate solution comprises 4-6 parts of bismuth nitrate,
hydrochloric acid, wherein the addition amount of the hydrochloric acid is recorded as HCl and is 5-7 parts by mass;
the preparation method of the activated carbon comprises the following steps: 20-30 parts of activated carbon and 80-100 parts of distilled water are put into an enamel reaction kettle to be stirred, nitric acid is added, and the addition amount of the nitric acid is HNO38-12 parts by mass, heating to 85-95 ℃, preserving heat for 2-4 hours, cooling, and performing centrifugal filtration to obtain activated carbon;
the alkali liquor is obtained by mixing 8-12 parts of alkali and 30-35 parts of distilled water;
the palladium chloride solution comprises 1.3-2 parts of palladium chloride,
hydrochloric acid, wherein the addition amount of the hydrochloric acid is 0.8-1.5 parts by mass in terms of HCl,
1-3 parts of distilled water.
2. The process of claim 1, wherein the palladium-on-carbon catalyst is prepared by the following steps: the palladium chloride hydrochloric acid solution also comprises 0.5-1.2 parts of a dispersing agent.
3. The process for producing palladium-on-carbon catalyst for liquid sodium gluconate catalysis as claimed in claim 2, wherein: the dispersing agent is polyvinyl alcohol.
4. The process of claim 1, wherein the palladium-on-carbon catalyst is prepared by the following steps: the particle size of the activated carbon is 200-300 meshes.
5. The process of claim 1, wherein the palladium-on-carbon catalyst is prepared by the following steps: the active carbon is wood carbon.
6. The process of claim 1, wherein the palladium-on-carbon catalyst is prepared by the following steps: the bismuth nitrate hydrochloric acid solution also comprises nitric acid, and the addition amount of the nitric acid is HNO35 to 10 parts by mass.
7. The process of claim 1, wherein the palladium-on-carbon catalyst is prepared by the following steps: the reducing agent is formaldehyde.
8. A palladium-carbon catalyst for catalyzing liquid sodium glucan is characterized in that: prepared by the production process of the palladium-carbon catalyst for catalyzing liquid sodium glucose as described in any one of claims 1-7.
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| CN115990485A (en) * | 2023-03-23 | 2023-04-21 | 农业农村部环境保护科研监测所 | Bimetallic composite biochar catalyst for sugar-acid synthesis, sugar-acid synthesis method and application |
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