阅读说明：本技术 一种合成1,1,2,3,3-五氯丙烷用的负载型催化剂的制备方法 (Preparation method of supported catalyst for synthesizing 1,1,2,3, 3-pentachloropropane ) 是由 胡淇翔 王晓东 徐庆瑞 徐煜 于 2019-09-24 设计创作，主要内容包括：本发明公开了一种合成1,1,2,3,3-五氯丙烷用的负载型催化剂的制备方法,具体包括以下步骤：(1)金属氯化物或金属硝酸化物的选择：金属氯化物和金属硝酸化物中的金属元素为Ⅷ族或ⅠB族或ⅢA族或ⅣA族中的一种或两种以上的组合；(2)活性炭的选择：活性炭为椰壳活性炭或果壳活性炭或木质活性炭中的一种；(3)先将活性炭用去离子水清洗,再用无水乙醇清洗,晾干,放入烘箱中,在100-120℃条件下干燥2-3h,然后将步骤(1)选择的金属氯化物或金属硝酸化物通过气相沉积法或浸渍法负载于干燥后的活性炭上,制得负载型催化剂。本发明制备工艺简单,操作方便,在1,1,2,3,3-五氯丙烷的制备工艺中加入本发明的催化剂,可明显提高产品的转化率和选择性。(The invention discloses a preparation method of a supported catalyst for synthesizing 1,1,2,3, 3-pentachloropropane, which specifically comprises the following steps: (1) selection of metal chloride or metal nitrate: the metal elements in the metal chloride and the metal nitrate are one or the combination of more than two of VIII family, IB family, IIIA family or IVA family; (2) selection of activated carbon: the active carbon is one of coconut shell active carbon, fruit shell active carbon or wood active carbon; (3) firstly, washing the activated carbon with deionized water, then washing with absolute ethyl alcohol, airing, placing in an oven, drying for 2-3h at the temperature of 100-120 ℃, and then loading the metal chloride or metal nitrate selected in the step (1) on the dried activated carbon by a vapor deposition method or an impregnation method to prepare the supported catalyst. The preparation process is simple and convenient to operate, and the catalyst is added in the preparation process of the 1,1,2,3, 3-pentachloropropane, so that the conversion rate and the selectivity of the product can be obviously improved.)

1. A preparation method of a supported catalyst for synthesizing 1,1,2,3, 3-pentachloropropane is characterized by comprising the following steps: the method specifically comprises the following steps:

(1) selection of metal chloride or metal nitrate: the metal elements in the metal chloride and the metal nitrate are one or the combination of more than two of VIII family, IB family, IIIA family or IVA family;

(2) selection of activated carbon: the active carbon is one of coconut shell active carbon, fruit shell active carbon or wood active carbon;

(3) firstly, washing the activated carbon with deionized water, then washing with absolute ethyl alcohol, airing, placing in an oven, drying for 2-3h at the temperature of 100-120 ℃, and then loading the metal chloride or metal nitrate selected in the step (1) on the dried activated carbon by a vapor deposition method or an impregnation method to prepare the supported catalyst.

2. The method for preparing the supported catalyst for synthesizing 1,1,2,3, 3-pentachloropropane according to claim 1, which is characterized in that: the operation steps of the vapor deposition method in the step (3) are as follows: the supported catalyst is obtained by roasting metal chloride or metal nitrate as an active component and active carbon as a carrier in a fixed bed device at the temperature of 220-260 ℃ under the protection of nitrogen.

3. The method for preparing the supported catalyst for synthesizing 1,1,2,3, 3-pentachloropropane according to claim 1, which is characterized in that: the impregnation method in the step (3) comprises the following operation steps: weighing metal chloride or metal nitrate, adding anhydrous acetone into the metal chloride or metal nitrate, stirring and dissolving, adding activated carbon after dissolving, sealing and soaking for 8-10h, filtering, then placing in an electric heating constant-temperature air blast drying oven, drying for 8h at 80-110 ℃, and roasting for 6-8h at 400-450 ℃ under the protection of nitrogen to obtain the supported catalyst.

4. The method for preparing the supported catalyst for synthesizing 1,1,2,3, 3-pentachloropropane according to claim 1, which is characterized in that: the metal element in the metal chloride and the metal nitrate is aluminum, iron, copper, nickel, tin, palladium or cobalt.

5. The method for preparing the supported catalyst for synthesizing 1,1,2,3, 3-pentachloropropane according to claim 4, wherein the method comprises the following steps: the copper chloride is cupric chloride and cuprous chloride, the copper nitrate is cupric nitrate, the iron oxide is ferric chloride and ferrous chloride, and the iron nitrate is ferric nitrate and ferric nitrite.

6. The method for preparing the supported catalyst for synthesizing 1,1,2,3, 3-pentachloropropane according to claim 1, which is characterized in that: the shape of the active carbon is cylindrical or spherical.

7. The method for preparing the supported catalyst for synthesizing 1,1,2,3, 3-pentachloropropane according to claim 1, which is characterized in that: in the supported catalyst prepared in the step (3), the content of the metal chloride or the metal nitrate is 20-70%.

8. The method for preparing the supported catalyst for synthesizing 1,1,2,3, 3-pentachloropropane according to claim 7, wherein the method comprises the following steps: the content of the metal chloride or the metal nitrate is 30 to 55 percent.

9. The method for preparing the supported catalyst for synthesizing 1,1,2,3, 3-pentachloropropane according to claim 8, wherein the method comprises the following steps: the content of the metal chloride or the metal nitrate is 45 to 50 percent.

Technical Field

The invention relates to the field of preparation of polychlorinated hydrocarbon, in particular to a preparation method of a supported catalyst for synthesizing 1,1,2,3, 3-pentachloropropane.

Background

Chlorinated hydrocarbon compounds are often used as raw materials for the preparation of refrigerants, blowing agents, sprays, biopesticides and polymers. 1,1,1,2, 3-pentachloropropane is an important intermediate for the preparation of 1,1,2, 3-tetrachloropropene. Meanwhile, 1,1,2, 3-tetrachloropropene is a main intermediate for synthesizing a new generation of environment-friendly refrigerant HFO-1234yf and preparing pesticide herbicide avenantha. How to efficiently and environmentally prepare 1,1,1,2, 3-pentachloropropane is receiving wide attention. Currently, there are mainly two routes, depending on the preparation of 1,1,1,2, 3-pentachloropropane precursor: (1) trichloropropene (including 1,1, 3-trichloropropene or 3,3, 3-trichloropropene or a mixture thereof) is used as a preparation precursor, and 1,1,1,2, 3-pentachloropropane is synthesized through chlorination; (2) 1,1,1, 3-tetrachloropropane is taken as a preparation precursor, and the 1,1,1,2, 3-pentachloropropane is synthesized by direct chlorination. Currently, the preparation of 1,1,1,2, 3-pentachloropropane is mainly carried out by adopting a traditional kettle type or tower type reactor.

For example, chinese patent publication No. CN104058925A, title of the invention: 1,1,1,2, 3-pentachloropropane. Filling a certain amount of filler in a tubular reactor, and carrying out liquid phase chlorination reaction on raw materials of trichloropropene (1,1, 3-trichloropropene or 3,3, 3-trichloropropene or a mixture thereof) and chlorine gas at 25 ℃ for 0.5h to generate 1,1,1,2, 3-pentachloropropane, wherein the conversion rate is 99.1 percent, the highest selectivity is 98.5 percent, and the reaction does not need illumination or a catalyst. Although the method has simpler operation conditions, the reaction residence time is overlong, the device occupies a large area, and the production efficiency is lower.

For example, chinese patent publication No. CN107001190A discloses a process for preparing a high purity 1,1,1,2, 3-pentachloropropane product. The reaction steps comprise: a) carrying out gas phase catalytic dehydrochlorination on 1,1,1, 3-tetrachloropropane, collecting a product, and carrying out purification and separation to obtain 1,1, 3-trichloropropene; b) the obtained 1,1, 3-trichloropropene and chlorine gas are subjected to liquid phase chlorination under the conditions of illumination, 26-31 ℃ and 30-300 min of retention time to obtain the high-purity 1,1,1,2, 3-pentachloropropane. The method requires complex operation conditions, requires light for liquid phase chlorination, and requires separation and purification of 1,1, 3-trichloropropene. Meanwhile, the reaction has longer residence time and the like, and is not produced by an industrial device.

For example, chinese patent publication No. CN104163750A, title of the invention: 1,1,1,2, 3-pentachloropropane and 1,1,2, 3-tetrachloropropene. Disclosed is a method for synthesizing 1,1,1,2, 3-pentachloropropane, which takes trichloropropene or 1,1,1, 3-tetrachloropropane as a precursor, and leads oxygen and HCl to prepare the 1,1,1,2, 3-pentachloropropane with the selectivity lower than 82 percent under the action of an oxychlorination catalyst (main active ingredient CuCl 2). The method has low reaction selectivity and short service life of the used catalyst, and is not beneficial to environmental protection and industrial production application.

That is to say, the existing process for preparing 1,1,1,2, 3-pentachloropropane generally has low production efficiency, relatively long reaction time and unsatisfactory industrial production, and aiming at the defects, the invention develops a preparation method of a supported catalyst for synthesizing 1,1,2,3, 3-pentachloropropane, and the 1,1,2,3, 3-pentachloropropane prepared by the catalyst is used for replacing the 1,1,1,2,3, 3-pentachloropropane.

Disclosure of Invention

The invention aims to provide a preparation method of a supported catalyst for synthesizing 1,1,2,3, 3-pentachloropropane.

In order to solve the technical problems, the invention is realized by the following technical scheme:

a preparation method of a supported catalyst for synthesizing 1,1,2,3, 3-pentachloropropane specifically comprises the following steps:

(1) selection of metal chloride or metal nitrate: the metal elements in the metal chloride and the metal nitrate are one or the combination of more than two of VIII family, IB family, IIIA family or IVA family;

(2) selection of activated carbon: the active carbon is one of coconut shell active carbon, fruit shell active carbon or wood active carbon;

(3) firstly, washing the activated carbon with deionized water, then washing with absolute ethyl alcohol, airing, placing in an oven, drying for 2-3h at the temperature of 100-120 ℃, and then loading the metal chloride or metal nitrate selected in the step (1) on the dried activated carbon by a vapor deposition method or an impregnation method to prepare the supported catalyst.

Preferably, the vapor deposition method described in the above step (3) is operated by: the supported catalyst is obtained by roasting metal chloride or metal nitrate as an active component and active carbon as a carrier in a fixed bed device at the temperature of 220-260 ℃ under the protection of nitrogen.

Preferably, the impregnation method described in the above step (3) comprises the following steps: weighing metal chloride or metal nitrate, adding anhydrous acetone into the metal chloride or metal nitrate, stirring and dissolving, adding activated carbon after dissolving, sealing and soaking for 8-10h, filtering, then placing in an electric heating constant-temperature air blast drying oven, drying for 8h at 80-110 ℃, and roasting for 6-8h at 400-450 ℃ under the protection of nitrogen to obtain the supported catalyst.

Preferably, the metal element in the metal chloride and the metal nitrate is aluminum, iron, copper, nickel, tin, palladium or cobalt.

Preferably, the copper chloride is cupric chloride and cuprous chloride, the copper nitrate is cupric nitrate, the iron oxide is ferric chloride and ferrous chloride, and the iron nitrate is ferric nitrate and ferric nitrite.

Preferably, the activated carbon has a cylindrical or spherical shape.

Preferably, in the supported catalyst prepared in the step (3), the content of the metal chloride or the metal nitrate is 20-70%.

Preferably, the content of the metal chloride or metal nitrate is 30 to 55%.

Preferably, the content of the metal chloride or the metal nitrate is 45 to 50 percent.

The invention has the beneficial effects that: the invention adopts metal chloride or metal nitrate as a main body of the catalyst, and loads the metal chloride on the active carbon through a vapor deposition method and an immersion method to prepare the load type catalyst, the process is simple, the operation is convenient, the conversion rate and the selectivity of the product can be obviously improved by adding the catalyst in the preparation process of the 1,1,2,3, 3-pentachloropropane, and the 1,1,2,3, 3-pentachloropropane is an important intermediate for synthesizing HFO series novel refrigerants, so the catalyst of the invention has important significance for the development of the novel refrigerants.

Detailed Description

The following further describes the embodiments of the present invention. It should be noted that the description of the embodiments is provided to help understanding of the present invention, but the present invention is not limited thereto. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.