CN102302946A

CN102302946A - Preparation and application of mesoporous molecular sieve supported noble metal catalyst

Info

Publication number: CN102302946A
Application number: CN201110150288A
Authority: CN
Inventors: 李伟; 王寰; 韩冲; 傅斌
Original assignee: 李伟
Priority date: 2011-06-07
Filing date: 2011-06-07
Publication date: 2012-01-04

Abstract

The invention discloses a mesoporous molecular sieve MCM-41 supported noble metal catalyst and application thereof in vinyl chloride synthesis by an acetylene method. In the catalyst, silane coupling agent modified MCM-41 is taken as a vector to load 0.1 to 5 percent of gold chloride and 0.5 to 10 percent of non-noble auxiliaries through ultrasonic immersion. The catalyst has good catalytic activity in vinyl chloride synthesis by the acetylene method, has the capability of deactivation and regeneration, and has remarkable advantages compared with an activated carbon vector catalyst.

Description

A kind of preparation of mesoporous molecular sieve carried noble metal catalyst and application

Technical field

The present invention relates to a kind of preparation and application of mesoporous molecular sieve carried noble metal catalyst, the preparation method of the mesoporous molecular sieve carried noble metal catalyst of a kind of MCM-41 of saying so more specifically and the application in the reaction of acetylene method synthesizing chloroethylene thereof.

Background technology

Polyvinyl chloride (PVC) is one of the world's five large-engineering plastics, all has very in every profession and trade and uses widely.Vinyl chloride is the monomer of synthesizing polyvinyl chloride.At present, the synthetic method of VCM mainly contains ethane method, ethylene process and acetylene method in the world wide.In China, restricted by special energy resource structure, about 70% VCM adopts acetylene method production., this process route adopts the mercury chloride of activated carbon supported severe toxicity as catalyst always, and this catalyst not only endangers operator ' s health, and global environment is done great damage.Launch more and more harsh mercury restrictive policy in the world at present.In addition this catalyst causes to be prone to the efflorescence loss in the catalyst use, and can't burn carbon distribution regeneration behind the catalyst carbon deposition inactivation owing to adopt active carbon as carrier, has quickened the loss and the consumption of mercury.Be directed to this; Researchers also study its carrier in the exploitation catalyst without mercury; Attempt to use that mechanical strength is high, the silica of high temperature resistant sintering or aluminium oxide be as carrier; But the result is all undesirable, and these carriers compare with active carbon that all there is a big difference at aspects such as specific area, abundant pore passage structure and surface functional groups.Find a kind of bigger serface that has, suitable pore passage structure, excellent high-temperature stability carrier possibly be important breakthroughs of novel acetylene method synthesizing chloroethylene catalyst research and development.

The MCM-41 molecular sieve is a kind of novel mesoporous molecular sieve, has high-specific surface area (>=900m ²/ g), big adsorption capacity (>=09cm ³/ g), and the characteristics such as mesoporous aperture of high-temperature stability and homogeneous, it mainly consists of silica, and can add other metallic elements adjusting surface acidities.More help the rapid diffusion of organic molecule than common zeolite and other poromerics, this makes it to select shaped reaction for heavy oil organic molecule in the big molecule especially petrochemical process unrivaled favourable space is provided.This molecular sieve analog has sizable potential value at catalytic fields such as RFCC, heavy-oil hydrogenation, lube oil hydrogenation, alkylation, olefinic polymerizations.

The present invention introduces acetylene method synthesizing chloroethylene catalyst without mercury with MCM-41 as carrier first and prepares in the process; With the noble metal is main active component; And the MCM-41 carrier surface is carried out suitable modification handle; The novel mercury-free catalyst that makes has catalytic activity and stability preferably through evaluation, has potential industrial application value.

Summary of the invention

The objective of the invention is to; A kind of high activity, high stability that is used for acetylene hydrochlorination synthesizing chloroethylene reaction is provided, and deactivatable regenerated catalyst, this catalyst with novel mesoporous MCM-41 molecular sieve as carrier; Pass through surface modification treatment; Improve its hydrophily, form new active function groups on its surface simultaneously, thereby more help the absorption and the dispersion of its active component ion in catalyst preparation process.This catalyst noble metal active component ions is selected Au for use ³⁺, the auxiliary agent active component is Cu ²⁺, Fe ³⁺, Bi ³⁺, Ba ²⁺In one or more, this catalyst not only has active and stable preferably in acetylene hydrochlorination reaction, more possesses the ability of burning carbon distribution regeneration behind the inactivation simultaneously, has important potential using value.

Catalyst its preparation method according to the invention is following:

1, a certain amount of MCM-41 carrier is joined in the ethanol solution of certain density silane coupler, behind the 20-60 ℃ of following stirring impregnation process 2-6h, suction filtration, oven dry.

2, a certain amount of active component is dissolved in the deionized water, the MCM-41 carrier that a certain amount of above-mentioned silane coupler was handled adds wherein impregnation process 1-4h under the ultrasonic wave condition.Suction filtration, oven dry.

Catalyst according to the invention is used for acetylene method, and to prepare the reaction evaluating and the analysis condition of vinyl chloride following:

Valuator device: fixed bed reactors, reaction temperature: 150-200 ℃, reaction velocity: 80-160h ^-1, hydrogen chloride and acetylene molar ratio: 1.2: 1.

Analytical equipment: online gas-chromatography.

Catalyst according to the invention has good catalytic activity and stability in acetylene method prepares vinyl chloride reaction.

Through the mode of instance the present invention is explained more specifically below, but the present invention is not limited thereto.

Description of drawings:

Fig. 1

embodiment

1,2,3,4, evaluating catalyst result in 5.

The specific embodiment

Embodiment 1

Get 100g MCM-41 carrier, join 300g and contain in the ethanol solution of 10%KH-560 silane coupler, 40 ℃ are stirred impregnation process 2h down, and suction filtration is dried 4h down for 120 ℃ then.Get 0.5g HAuCl ₄4H ₂O is dissolved in the 250g deionized water, stirring and dissolving, and the MCM-41 carrier 100g of adding KH-560 modification floods 2h under the ultrasonic wave condition, and back suction filtration was dried 6 hours for 120 ℃.Promptly obtain the Au catalyst of MCM-41 load.This catalyst is at 160 ℃, 160h ^-1Air speed, hydrogen chloride and acetylene molar ratio condition under are carried out catalytic activity and estimation of stability at 1.2: 1, and analysis result is seen Fig. 1.

Embodiment 2

HAuCl ₄4H ₂The addition of O is 1.0g, and all the other are with embodiment 1, and analysis result is seen Fig. 1.

Embodiment 3

In active component solution, add 5.0g CuCl ₂, all the other are with embodiment 1, and analysis result is seen Fig. 1.

Embodiment 4

In active component solution, add 5.0g BiCl ₃, all the other are with embodiment 4, and analysis result is seen Fig. 1.

Embodiment 5

In active component solution, add 3.0g FeCl ₃, all the other are with embodiment 4, and analysis result is seen Fig. 1.

Claims

1. molecular sieve carried noble metal catalyst of MCM-41; It is characterized in that it is is carrier with silane coupler modified mesopore molecular sieve MCM-41; A certain amount of noble metal active component of load and base metal auxiliary agent; Described noble metal active component is a chlorauride, and auxiliary agent is one or more in bismuth chloride, copper chloride, the iron chloride.

2. the molecular sieve carried noble metal catalyst of MCM-41 as claimed in claim 1 is characterized in that described MCM-41 carrier, and its specific area is greater than 800m ²/ g.

3. the molecular sieve carried noble metal catalyst of MCM-41 as claimed in claim 1 is characterized in that described its load capacity of noble metal active component chlorauride is 0.1%-5%.

4. the molecular sieve carried noble metal catalyst of MCM-41 as claimed in claim 1 is characterized in that its load capacity of described auxiliary agent is 0.5%-10%.

5. the molecular sieve carried Nobel-metal catalyst preparation method of MCM-41 as claimed in claim 1 is characterized in that it comprises to be prepared as follows step:

(1), a certain amount of MCM-41 carrier is joined in the ethanol solution of certain density silane coupler, 20-60 ℃ stir impregnation process 2-6h down after, suction filtration, oven dry.

(2), a certain amount of active component is dissolved in the deionized water, the MCM-41 carrier of a certain amount of above-mentioned silane coupler being handled adds wherein impregnation process 1-4h under the ultrasonic wave condition.Suction filtration, oven dry.

6. the molecular sieve carried Nobel-metal catalyst preparation method of MCM-41 as claimed in claim 5 is characterized in that described silane coupler is KH-550, KH-560, KH-570, KH792, DL602, one or more among the DL171.

7. the molecular sieve carried Nobel-metal catalyst preparation method of MCM-41 as claimed in claim 5 is characterized in that described ultrasonic frequency is 25-60KHz.

8. the application of the molecular sieve carried noble metal catalyst of MCM-41 as claimed in claim 1 in the acetylene method synthesizing chloroethylene.