阅读说明：本技术 一种活性炭上原位合成层状介孔磷酸锆改性铜基乙炔氢氯化催化剂及其制备方法 (In-situ synthesis layered mesoporous zirconium phosphate modified copper-based acetylene hydrochlorination catalyst on activated carbon and preparation method thereof ) 是由 姚炜 黄文学 许平 于霖容 于 2020-06-11 设计创作，主要内容包括：本发明公开了一种活性炭上原位合成层状介孔磷酸锆改性铜基乙炔氢氯化催化剂及其制备方法,属于无汞非贵金属催化剂研制领域。本发明的催化剂以活性炭为载体,经原位合成介孔磷酸锆改性后负载铜盐再经烘干制得。所述催化剂的质量百分比组成为5％～50％的铜盐,0.1％～20％的介孔磷酸锆,余下部分为活性炭载体。本发明所制备的催化剂中介孔磷酸锆孔径控制在1.5～50nm。(The invention discloses a layered mesoporous zirconium phosphate modified copper-based acetylene hydrochlorination catalyst synthesized on activated carbon in situ and a preparation method thereof, belonging to the field of mercury-free non-noble metal catalyst development. The catalyst is prepared by taking activated carbon as a carrier, modifying by in-situ synthesis mesoporous zirconium phosphate, loading copper salt and drying. The catalyst comprises, by mass, 5-50% of a copper salt, 0.1-20% of mesoporous zirconium phosphate, and the balance of an activated carbon carrier. The pore diameter of the mesoporous zirconium phosphate in the catalyst prepared by the invention is controlled to be 1.5-50 nm.)

1. The in-situ synthesis layered mesoporous zirconium phosphate modified copper-based acetylene hydrochlorination catalyst on activated carbon is characterized by comprising the following raw materials in percentage by mass: 5 to 50 percent of copper salt active component, 0.1 to 20 percent of layered mesoporous zirconium phosphate modifier, and the balance of activated carbon carrier.

2. The in-situ synthesized layered mesoporous zirconium phosphate modified copper-based acetylene hydrochlorination catalyst on activated carbon according to claim 1, wherein the pore diameter of the mesoporous zirconium phosphate modifier is 1.5-50 nm.

3. The catalyst for in-situ synthesis of layered mesoporous zirconium phosphate modified copper-based acetylene hydrochlorination on active carbon according to claim 1, wherein the zirconium salt in the in-situ synthesized layered mesoporous zirconium phosphate is one, two or more of zirconium oxychloride, zirconium carbonate and zirconyl sulfate, and the phosphate precursor is one, two or more of phosphoric acid, ammonium phosphate, sodium phosphate and potassium phosphate.

4. The in-situ synthesized layered mesoporous zirconium phosphate modified copper-based acetylene hydrochlorination catalyst on activated carbon according to claim 1, wherein the crystal form of the mesoporous zirconium phosphate is one, two or more than three structure types of alpha, gamma and tau.

5. The in-situ synthesized layered mesoporous zirconium phosphate modified copper-based acetylene hydrochlorination catalyst on activated carbon according to claim 1, wherein the copper salt active component is one, two or more of cupric chloride, cuprous chloride, cupric pyrophosphate, cupric phosphate, cupric methylsulfonate, cupric oxalate and cupric sulfate.

6. The in-situ synthesized layered mesoporous zirconium phosphate modified copper-based acetylene hydrochlorination catalyst on activated carbon according to claim 1, wherein the activated carbon carrier is one, two or more of coal-based activated carbon, coconut shell activated carbon or wood-based activated carbon.

7. The method for preparing the layered mesoporous zirconium phosphate modified copper-based acetylene hydrochlorination catalyst on activated carbon by in-situ synthesis on activated carbon according to any one of claims 1 to 6, which is characterized by comprising the following steps:

(1) dissolving 0.1-20% by mass of zirconium salt in deionized water or dilute hydrochloric acid to prepare an impregnation liquid, impregnating the impregnation liquid and 80-99.9% by mass of an activated carbon carrier by an isometric impregnation method, impregnating for 0.5-12 hours at the temperature of 20-50 ℃, drying for 6-12 hours by blowing at the temperature of 70-100 ℃, and cooling to room temperature to form a spare carrier;

(2) dissolving phosphoric acid accounting for 0.2-15% of the mass of the standby carrier or phosphate accounting for 0.2-15% of the mass of the standby carrier and hydrofluoric acid accounting for 0.3-10% of the mass of the standby carrier into deionized water to prepare impregnation liquid a with the volume same as that of the standby carrier, and impregnating the impregnation liquid a into the standby carrier in the step (1) by an isometric impregnation method; soaking for 0.5-12 hours at the temperature of 20-50 ℃, and then blowing and drying for 6-12 hours at the temperature of 70-100 ℃ to prepare a mesoporous zirconium phosphate activated carbon carrier;

(3) dissolving 5-50% by mass of copper salt in deionized water or dilute hydrochloric acid to prepare a steeping liquid b, steeping the steeping liquid b and 50-95% by mass of the mesoporous zirconium phosphate activated carbon carrier obtained in the step (2) by an isometric steeping method, steeping for 0.5-12 hours at the temperature of 20-50 ℃, drying by blowing at the temperature of 80-150 ℃ for 6-12 hours, and cooling to room temperature to prepare the catalyst.

8. The method for preparing the layered mesoporous zirconium phosphate modified copper-based acetylene hydrochlorination catalyst on activated carbon by in-situ synthesis on activated carbon according to any one of claims 1 to 6, which is characterized by comprising the following steps:

(1) dissolving 5-50% by mass of copper salt, 0.2-15% by mass of phosphoric acid or 0.2-15% by mass of phosphate and 0.3-10% by mass of hydrofluoric acid in dilute hydrochloric acid to prepare impregnation liquid, impregnating the impregnation liquid and 35-94.5% by mass of activated carbon carrier by an isometric impregnation method, impregnating for 0.5-12 hours at the temperature of 20-50 ℃, drying by blowing at 80-100 ℃ for 6-12 hours, and cooling to room temperature to obtain a spare carrier;

(2) dissolving 0.1-20% by mass of zirconium salt in deionized water or dilute hydrochloric acid to prepare an impregnation liquid a, impregnating the impregnation liquid a and 80-99.9% by mass of the standby carrier in the step (1) by an isometric impregnation method, impregnating for 0.5-12 hours at the temperature of 20-50 ℃, drying by blowing for 6-12 hours at the temperature of 80-150 ℃, and cooling to room temperature to prepare the catalyst.

Technical Field

The invention belongs to the field of mercury-free non-noble metal catalyst development, and particularly relates to a layered mesoporous zirconium phosphate modified copper-based acetylene hydrochlorination catalyst synthesized on activated carbon in situ and a preparation method thereof.

Background

PVC is one of the five major polymers in the world. Because of the characteristics of the resource structure in China, calcium carbide is mostly adopted as a raw material to produce PVC. At present, the process inevitably uses highly toxic mercuric chloride as a catalyst, and causes great harm to the environment and human health due to mercury loss.

At present, the development of mercury-free catalysts mainly focuses on catalytic systems such as noble metals and non-noble metals which mainly comprise gold. The gold catalyst system has the advantages of stable catalytic performance, long service life, high selectivity and the like, but has the defects of high price, high operation cost, inapplicability to a water-cooling heat exchange system and the like, and has great obstacles to industrial application. The non-noble metal catalyst system has the advantages of low cost, small change to the existing process, high selectivity and the like, and although the originally developed catalyst has shorter service life, the service life is greatly improved through continuous optimization.

Application number 201910451132.9 discloses a preparation method of a mercury-free catalyst for synthesizing vinyl chloride by hydrochlorinating acetylene. The catalyst comprises a carrier and a ternary active component. The three active components are respectively: the component A is chloroauric acid, the component B is ruthenium chloride, and the component C is copper chloride. The catalyst has the advantages of high activity, good selectivity, long service life and relatively low price. Application number 201910760660.2 discloses a composite supported catalyst for hydrochlorination of acetylene and application thereof. The catalyst is prepared by depositing nano inorganic oxides of cerium dioxide, zirconium dioxide, titanium dioxide and lanthanum oxide on active carbon, and loading gold or ruthenium or the combination of gold, ruthenium, cobalt and copper on the nano inorganic material modified active carbon. The catalyst can keep the acetylene conversion rate over 97% and the chloroethylene selectivity over 99.5% for a long time. Application No. 201910933364.8 discloses a trivalent copper catalyst and its preparation method and application in hydrochlorination of acetylene. The catalyst is prepared by adding a nitrogen-containing heterocyclic compound and a copper salt into a trichloromethane solution to be mixed to obtain a mixed solution A containing a bivalent copper compound; adding ionic liquid into the mixed solution A, and obtaining mixed solution B containing a trivalent copper compound under the action of an oxidant; and then soaking the porous solid carrier in the B, and drying to obtain the catalyst. The catalyst has high stability and activity and low production cost.

The above patents generally have the disadvantages of expensive catalyst, organic solvent required in the preparation process, and the like.

Disclosure of Invention

The invention provides a layered mesoporous zirconium phosphate modified copper-based acetylene hydrochlorination catalyst synthesized on activated carbon in situ and a preparation method thereof. The lamellar mesoporous zirconium phosphate is synthesized on the activated carbon in situ, so that the copper salt crystal grains are effectively spaced and controlled, and the agglomeration of the crystal grains is relieved, thereby improving the performance of the catalyst. The catalyst has the characteristics of multifunctional layered mesoporous function, strong acid and alkali resistance, large specific surface area, environment-friendly green catalyst or carrier and the like.

The invention is realized by the following technical scheme:

the invention provides a layered mesoporous zirconium phosphate modified copper-based acetylene hydrochlorination catalyst synthesized on activated carbon in situ, which comprises the following raw materials in percentage by mass: 5 to 50 percent of copper salt active component, 0.1 to 20 percent of mesoporous zirconium phosphate modifier, and the balance of activated carbon carrier.

Further, in the technical scheme, the pore diameter of the mesoporous zirconium phosphate modifier is 1.5-50 nm.

Further, in the above technical scheme, the zirconium salt in the mesoporous zirconium phosphate is one, two or more than two of zirconium oxychloride, zirconium carbonate and zirconyl sulfate, and the precursor of the phosphate is one, two or more than two of phosphoric acid, ammonium phosphate, sodium phosphate and potassium phosphate.

Further, in the above technical scheme, the crystal form of the mesoporous zirconium phosphate is one, two or more than three structure types of α, γ and τ.

Further, in the above technical scheme, the copper salt active component is one, two or more than two of cupric chloride, cuprous chloride, cupric pyrophosphate, cupric phosphate, copper methylsulfonate, cupric oxalate and cupric sulfate.

Further, in the above technical scheme, the activated carbon carrier is one, two or more than two of coal-based activated carbon, coconut shell activated carbon or wood-based activated carbon.

The invention also provides a preparation method of the layered mesoporous zirconium phosphate modified copper-based acetylene hydrochlorination catalyst synthesized on activated carbon in situ, which comprises the following steps:

(1) dissolving 0.1-20% by mass of zirconium salt in deionized water or dilute hydrochloric acid to prepare an impregnation liquid, impregnating the impregnation liquid and 80-99.9% by mass of an activated carbon carrier by an isometric impregnation method, impregnating for 0.5-12 hours at the temperature of 20-50 ℃, drying for 6-12 hours by blowing at the temperature of 70-100 ℃, and cooling to room temperature to form a spare carrier;

(2) dissolving phosphoric acid accounting for 0.2-15% of the mass of the standby carrier or phosphate accounting for 0.2-15% of the mass of the standby carrier and hydrofluoric acid accounting for 0.3-10% of the mass of the standby carrier into deionized water to prepare impregnation liquid a with the volume same as that of the standby carrier, and impregnating the impregnation liquid a into the standby carrier in the step (1) by an isometric impregnation method; soaking for 0.5-12 hours at the temperature of 20-50 ℃, and then blowing and drying for 6-12 hours at the temperature of 70-100 ℃ to prepare a mesoporous zirconium phosphate activated carbon carrier;

(3) dissolving 5-50% by mass of copper salt in deionized water or dilute hydrochloric acid to prepare a steeping liquid b, steeping the steeping liquid b and 50-95% by mass of the mesoporous zirconium phosphate activated carbon carrier obtained in the step (2) by an isometric steeping method, steeping for 0.5-12 hours at the temperature of 20-50 ℃, drying by blowing at the temperature of 80-150 ℃ for 6-12 hours, and cooling to room temperature to prepare the catalyst.

The invention also provides another preparation method of the layered mesoporous zirconium phosphate modified copper-based acetylene hydrochlorination catalyst synthesized on activated carbon in situ, which comprises the following steps:

(1) dissolving 5-50 wt% of copper salt, 0.2-15 wt% of phosphoric acid or 0.2-15 wt% of phosphate and 0.3-10 wt% of hydrofluoric acid in dilute hydrochloric acid to prepare impregnation liquid, impregnating the impregnation liquid and 50-95 wt% of activated carbon carrier by an isometric impregnation method, impregnating for 0.5-12 hours at the temperature of 20-50 ℃, drying by blowing at 80-100 ℃ for 6-12 hours, and cooling to room temperature to obtain a spare carrier;

(2) dissolving 0.1-20% by mass of zirconium salt in deionized water or dilute hydrochloric acid to prepare an impregnation liquid a, impregnating the impregnation liquid a and 80-99.9% by mass of the standby carrier in the step (1) by an isometric impregnation method, impregnating for 0.5-12 hours at the temperature of 20-50 ℃, drying by blowing for 6-12 hours at the temperature of 80-150 ℃, and cooling to room temperature to prepare the catalyst.

Has the advantages that: the catalyst prepared by the method has good performance, the preparation process of the catalyst is simple, an organic solvent is not required, and the preparation process has good economical efficiency.

Detailed Description

The following non-limiting examples will allow one of ordinary skill in the art to more fully understand the present invention, but are not intended to limit the invention in any way.