Background technology
As everyone knows, polyvinyl chloride (PVC) is as one of five big synthetic resin, the very important role of performer in daily life and in producing, and along with the continuous progress of society with to develop its demand in rising trend year by year.The most vinyl chloride of China are to adopt the preparation of acetylene hydrochlorination method at present, because the scarcity of current China mercury pollution and mercury resource, catalyst without mercury is produced the heat subject that vinyl chloride has become present research.Research to catalyst without mercury production vinyl chloride at present mainly concentrates on the production technology that changes vinyl chloride, mainly is that existing production technology and equipment are transformed, and has so just caused the huge waste of the resources of production.Therefore research and development is used for the catalyst without mercury that the acetylene hydrochlorination legal system is equipped with vinyl chloride under the constant situation of existing process conditions, has very important in theory and realistic meaning.Support type Cu among the present invention
3The P catalyst is applied to the acetylene hydrochlorination legal system and is equipped with in the vinyl chloride reaction, and has shown good active and selectivity.
Summary of the invention
The present invention proposes a kind of phosphorized copper catalyst that is used to produce vinyl chloride, it is characterized in that: the carrier of this catalyst is an active carbon, and active component is Cu
3P, auxiliary agent are one or more in copper chloride, nickel chloride, the barium chloride.
Phosphorized copper Preparation of catalysts step:
At first, under the stirring at room state, copper chloride and hypophosphites are dissolved in the deionized water, afterwards with solution impregnation in absorbent charcoal carrier, and in 60 ℃ of down oven dry; Precursor after will drying is then packed in the reactor, in temperature required roasting down, and drops to room temperature at nitrogen atmosphere and obtains catalyst precarsor in the nitrogen atmosphere of static state; At last compounding agent solution is impregnated in the catalyst precarsor, and oven dry obtains required catalyst under 120 ℃.
H described in the preparation process
2PO
2 -: Cu
2+Mol ratio is in 1.5~2.0 scopes; Described Cu
3The quality percentage composition of P component is 2-20%; Described hypophosphites comprises analyzes pure sodium hypophosphite, ammonium hypophosphite; Described precursor sintering temperature is 250~400 ℃; Described precursor roasting time is 10-120min; The quality percentage composition of described auxiliary agent is 2-20%.
The specific embodiment
Below the Preparation of catalysts scheme is carried out more detailed specific description.
Embodiment one:
At first, under the stirring at room state, the copper chloride of 3.44g and the sodium hypophosphite of 4.28g are dissolved in the 25.0g deionized water, afterwards with solution impregnation in the 23g absorbent charcoal carrier, and 60 ℃ of down oven dry; Precursor after will drying is then packed in the reactor, at 250 ℃ of following roasting 60min, and drops to room temperature at nitrogen atmosphere and obtains catalyst precarsor in nitrogen atmosphere; Be 5% BaCl at last with 20g concentration
2Solution for vacuum is impregnated in the precursor, and oven dry gained sample is named as A under 120 ℃.Catalyst A is used for the preparing chloroethylene by acetylene hydrochlorination reaction, and 170 ℃ of following conversion of alkyne are 64%, and the vinyl chloride selectivity is 53%.
Embodiment two:
Preparation process is identical with the preparation process of catalyst A, and the amount that only changes sodium hypophosphite is 6.43g, and other condition is constant, and the gained sample is named as B.Catalyst B is used for the preparing chloroethylene by acetylene hydrochlorination reaction, and 170 ℃ of following conversion of alkyne are 64%, and the vinyl chloride selectivity is 53%.
Embodiment three:
Preparation process is identical with the preparation process of catalyst A, and only changing the precursor sintering temperature is 400 ℃, and other condition is constant, and the gained sample is named as C.Catalyst C is used for the preparing chloroethylene by acetylene hydrochlorination reaction, and 170 ℃ of following conversion of alkyne are 66%, and the vinyl chloride selectivity is 56%.
Embodiment four:
Preparation process is identical with the preparation process of catalyst A, and only changing quality of activated carbon is 11.5g, and other condition is constant, and the gained sample is named as D.Catalyst D is used for the preparing chloroethylene by acetylene hydrochlorination reaction, and 170 ℃ of following conversion of alkyne are 71%, and the vinyl chloride selectivity is 60%.
Embodiment five:
Preparation process is identical with the preparation process of catalyst A, only changes auxiliary agent and for 20g concentration be 5% NiCl
2Solution, other condition is constant, and the gained sample is named as E.Catalyst E is used for the preparing chloroethylene by acetylene hydrochlorination reaction, and 170 ℃ of following conversion of alkyne are 67%, and the vinyl chloride selectivity is 55%.
Embodiment six:
Preparation process is identical with the preparation process of catalyst A, only changes auxiliary agent and for 20g concentration be 5% CuCl
2Solution, other condition is constant, and the gained sample is named as F.Catalyst F is used for the preparing chloroethylene by acetylene hydrochlorination reaction, and 170 ℃ of following conversion of alkyne are 68%, and the vinyl chloride selectivity is 57%.