CN113996320A - Preparation method of copper catalyst - Google Patents
Preparation method of copper catalyst Download PDFInfo
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- CN113996320A CN113996320A CN202111408935.XA CN202111408935A CN113996320A CN 113996320 A CN113996320 A CN 113996320A CN 202111408935 A CN202111408935 A CN 202111408935A CN 113996320 A CN113996320 A CN 113996320A
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- clap
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
- B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
- B01J27/1817—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with copper, silver or gold
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Abstract
The invention discloses a preparation method of a copper catalyst, belonging to the technical field of catalysts. Solves the problem of Cu in the traditional copper catalyst+And Cl‑Poor stability and easy falling. The method comprises the following steps: firstly, preparing HAP; then preparing ClAP; finally, the preparation of the Cu (I) ClAP catalyst is carried out. The invention uses solid ion exchange method and reduction method to react Cl‑、Cu2+The hydroxyapatite is sequentially exchanged to the apatite to prepare chlorapatite ClAP and Cu (II) ClAP, and the NaOH and the hydrazine hydrate are used for reducing the Cu (II) ClAP into Cu (I) ClAP, so that the problem of Cu in the traditional copper catalyst is solved+And Cl‑Poor stability and easy falling. The copper catalyst produced by the method has high activity, is easy to separate and has good recycling effect.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to the technical field of a preparation method of a copper-based catalyst.
Background
Hydroxyapatite (HAP) is a high-temperature resistant, alkali-resistant and water-insoluble multipurpose inorganic material and can be applied to the fields of biomedicine, adsorption, catalysis, fluorescence, laser, semiconductors and the like.
The methanol liquid phase oxidation carbonylation method for preparing DMC has the characteristics of simple process, low cost, little environmental pollution and the like, so the method becomes the key point of research and development at home and abroad, and the development of high-efficiency catalyst is the key point of research-The loss is the main cause of the reduction of the activity of the catalyst and the serious corrosion of equipment.
The traditional copper catalyst is generally prepared by impregnating or coprecipitating Cu2+Supported on a carrier, washed, filtered, dried and calcined, in which case the copper species is present as copper oxide and is thus reacted
Use H first2To the catalyst intoAnd (5) performing row reduction. The active component of the catalyst prepared by the method is mainly metallic copper, and the activity of the catalyst is greatly influenced by experimental conditions and has poor experimental repeatability.
Disclosure of Invention
The invention aims to provide a preparation method of a copper-based catalyst, which solves the problems in the background art.
The invention specifically adopts the following technical scheme for realizing the purpose:
a preparation method of a copper-based catalyst comprises the following steps:
s1, HAP preparation: respectively weighing a certain amount of inorganic calcium salt and phosphate solution, mixing and stirring for 0.5-2 h; adding ammonia water into the solution under stirring to adjust pH to about 10-13, and heating the obtained milky colloid at 50-100 deg.C for 1-10 h; then cooling to room temperature and aging for 1-24 h; performing centrifugal separation, and repeatedly washing with deionized water until the solution is neutral; finally, drying the product in an oven at 60-90 ℃, cooling, grinding and crushing to obtain Hydroxyapatite (HAP);
s2, preparing ClAP: adding CaCl2Mixing with HAP prepared in step S1 at a molar ratio of 0.1-1:1, calcining at 800 deg.C at 300 deg.C for 1-5h, naturally cooling to room temperature, and adding NH4The Cl solution is washed to remove CaO, and is fully washed by distilled water to remove free Cl-Drying at 60-90 ℃ to obtain ClAP;
s3. preparation of Cu (I) ClAP catalyst: the ClAP prepared in the step S2 and CuCl2Mixing, stirring uniformly, reacting at constant temperature for 1-3h to obtain Cu (II) ClAP, adding a certain volume of sodium hydroxide solution into the reaction solution, adding a certain volume of hydrazine hydrate solution after 30-60min, taking out after 1-2h, fully washing with water, centrifuging, drying at 50-80 ℃ in vacuum for 1-5h, and grinding into powder to obtain the Cu (I) ClAP catalyst.
Further, the inorganic calcium salt in step S1 is CaCl2、Ca(OH)2And Ca (N0)3)2·4H20, and the phosphate is K2HPO4、Na3PO4、(NH4)2HPO4And H3PO4One or more of them are mixed.
Further, in the step S1, the inorganic calcium salt and the phosphate solution are mixed according to the molar ratio of Ca to P of 4-5: 3.
Further, NH used in the step S24The concentration of the Cl solution is 0.5-1 mol/L.
Further, CuCl used in the step S32The concentration of (A) is 0.1-1mol/L, the concentration of sodium hydroxide solution is 0.5-1mol/L, and the concentration of hydrazine hydrate solution is 0.5-1 mol/L.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
the invention uses solid ion exchange method and reduction method to react Cl-、Cu2+The hydroxyapatite is sequentially exchanged to the apatite to prepare chlorapatite ClAP and Cu (II) ClAP, and the NaOH and the hydrazine hydrate are used for reducing the Cu (II) ClAP into Cu (I) ClAP, so that the problem of Cu in the traditional copper catalyst is solved+And Cl-Poor stability and easy falling. The copper catalyst produced by the method has high activity, is easy to separate and has good recycling effect.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments.
Example 1
A preparation method of a copper-based catalyst comprises the following steps:
s1, HAP preparation: respectively weighing a certain amount of inorganic calcium salt and phosphate solution according to the molar ratio of Ca to P of 4-5:3 (4: 3,4.5:3 and 5:3 are respectively considered in the test), mixing and stirring for 0.5-2h (0.5, 1 and 2h are respectively considered in the test), wherein the inorganic calcium salt is CaCl2、Ca(OH)2And Ca (N0)3)2·4H20, and phosphate is K2HPO4、Na3PO4、(NH4)2HPO4And H3PO4One or more of the components are mixed; under the condition of stirringAdding ammonia water into the mixed solution to adjust the pH value of the solution to about 10-13 (10, 11 and 13 are respectively considered in the test), and heating the obtained milky colloid for 1-10h at 50-100 ℃ (50, 80 and 100 ℃ are respectively considered in the test) (1, 5 and 10h are respectively considered in the test); then cooling to room temperature and aging for 1-24h (1, 12 and 24h are respectively considered in the test); performing centrifugal separation, and repeatedly washing with deionized water until the solution is neutral; finally, drying the product in an oven at 60-90 ℃ (60, 70 and 90 ℃ are respectively considered in the test), cooling, grinding and crushing to obtain hydroxyapatite HAP;
under the above various test conditions, a HAP with the best performance is selected and used as a precursor for the subsequent synthesis of the composite material.
S2, preparing ClAP: adding CaCl2Mixing with HAP prepared in step S1 at a molar ratio of 0.1-1:1, calcining at 800 deg.C at 300 deg.C for 1-5h, naturally cooling to room temperature, and adding NH at a concentration of 0.5-1mol/L4The Cl solution is washed to remove CaO, and is fully washed by distilled water to remove free Cl-Drying at 60-90 ℃ to obtain ClAP;
s3. preparation of Cu (I) ClAP catalyst: ClAP prepared in the step S2 and CuCl with the concentration of 0.1-1mol/L2Mixing, stirring uniformly, reacting at constant temperature for 1-3h to obtain Cu (II) ClAP, adding a certain volume of sodium hydroxide solution with the concentration of 0.5-1mol/L into the reaction solution, adding a certain volume of hydrazine hydrate solution with the concentration of 0.5-1mol/L after 30-60min, taking out after 1-2h, washing with water fully, centrifuging, drying at 50-80 ℃ in vacuum for 1-5h, and grinding into powder to obtain the Cu (I) ClAP catalyst.
The above description is only exemplary of the invention, and any modification, equivalent replacement, and improvement made within the spirit and principle of the invention should be included in the protection scope of the invention.
Claims (5)
1. A preparation method of a copper catalyst is characterized by comprising the following steps:
s1, HAP preparation: respectively weighing a certain amount of inorganic calcium salt and phosphate solution, mixing and stirring for 0.5-2 h; adding ammonia water into the solution under stirring to adjust pH to about 10-13, and heating the obtained milky colloid at 50-100 deg.C for 1-10 h; then cooling to room temperature and aging for 1-24 h; performing centrifugal separation, and repeatedly washing with deionized water until the solution is neutral; finally, drying the product in an oven at 60-90 ℃, cooling, grinding and crushing to obtain Hydroxyapatite (HAP);
s2, preparing ClAP: adding CaCl2Mixing with HAP prepared in step S1 at a molar ratio of 0.1-1:1, calcining at 800 deg.C at 300 deg.C for 1-5h, naturally cooling to room temperature, and adding NH4The Cl solution is washed to remove CaO, and is fully washed by distilled water to remove free Cl-Drying at 60-90 ℃ to obtain chlorapatite ClAP;
s3. preparation of Cu (I) ClAP catalyst: the ClAP prepared in the step S2 and CuCl2Mixing, stirring uniformly, reacting at constant temperature for 1-3h to obtain Cu (II) ClAP, adding a certain volume of sodium hydroxide solution into the reaction solution, adding a certain volume of hydrazine hydrate solution after 30-60min, taking out after 1-2h, fully washing with water, centrifuging, drying at 50-80 ℃ in vacuum for 1-5h, and grinding into powder to obtain the Cu (I) ClAP catalyst.
2. The method for preparing a copper-based catalyst according to claim 1, wherein: the inorganic calcium salt in the step S1 is CaCl2、Ca(OH)2And Ca (N0)3)2·4H20, and the phosphate is K2HPO4、Na3PO4、(NH4)2HPO4And H3PO4One or more of them are mixed.
3. The method for preparing a copper-based catalyst according to claim 1, wherein: in the step S1, the inorganic calcium salt and the phosphate solution are mixed according to the molar ratio of Ca to P of 4-5: 3.
4. The method for preparing a copper-based catalyst according to claim 1, wherein: NH used in the step S24The concentration of the Cl solution is 0.5-1 mol/L.
5. The method for preparing a copper-based catalyst according to claim 1, wherein: CuCl used in the step S32The concentration of (A) is 0.1-1mol/L, the concentration of sodium hydroxide solution is 0.5-1mol/L, and the concentration of hydrazine hydrate solution is 0.5-1 mol/L.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115894213A (en) * | 2022-10-26 | 2023-04-04 | 辽宁圣德华星化工有限公司 | Method for catalytically synthesizing calcium lactate and hydrogen by Cu/apatite nano-catalyst |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105983427A (en) * | 2015-01-30 | 2016-10-05 | 中国科学院大连化学物理研究所 | Apatite loaded platinum catalyst as well as preparation method and application thereof |
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- 2021-11-24 CN CN202111408935.XA patent/CN113996320A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105983427A (en) * | 2015-01-30 | 2016-10-05 | 中国科学院大连化学物理研究所 | Apatite loaded platinum catalyst as well as preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 程庆彦等: "磷灰石型催化剂的合成及其催化性能研究" * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115894213A (en) * | 2022-10-26 | 2023-04-04 | 辽宁圣德华星化工有限公司 | Method for catalytically synthesizing calcium lactate and hydrogen by Cu/apatite nano-catalyst |
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