CN104190419A - Method for preparing copper-based catalyst - Google Patents

Abstract

The invention discloses a method for preparing a copper-based catalyst, belonging to the technical field of catalysts. The method comprises the following steps: dissolving copper sulfate in hot water, thereby obtaining a copper sulfate solution; adding a sodium carbonate solution into the copper sulfate solution, reacting, filtering, collecting a precipitate, and washing the precipitate with water until inspection with barium chloride proves that no sulfate radical exists in the precipitate solution; and adding zinc oxide into the aqueous solution of the precipitate, filtering, centrifugally separating the obtained filtrate, and drying. Compared with a commercially available basic cupric carbonate catalyst at present, the copper-based catalyst prepared by the invention has the advantages of smaller consumption, higher catalytic efficiency and higher repeated utilization frequency.

Description

The preparation method of copper-based catalysts

Technical field

The invention belongs to catalyst technical field, relate in particular to a kind of preparation method of copper-based catalysts.

Background technology

Camphor, has orifice opening, qi stagnation removing, wards off the symptoms such as foul, the effect of killing parasites to relieve itshing, swelling and pain relieving, mange itch, injuries from falls as well, toothache.Camphor can pass through the continuous rectification under vacuum of multi-tower type, in conjunction with techniques such as freezing, distillations, makes, and also can make by techniques such as isoborneol dehydrogenations.Wherein, in the process at isoborneol Oxidative Dehydrogenation for camphor, conventionally to add basic copper carbonate to make catalyst, in order to the certain embodiments of catalysis isoborneol.Yet the basic carbonate copper catalyst of selling in the market exists the problems such as consumption is large, catalytic efficiency is low, recycling poor activity, make isoborneol dehydrogenating technology prepare that the cost of camphor is high, production efficiency is low.

Summary of the invention

The technical problem that the present invention solves is to provide a kind of preparation method of copper-based catalysts, and this preparation method can solve that the catalyst based consumption of existing copper is large, catalytic efficiency is low and the problem of recycling poor activity.

In order to solve the problems of the technologies described above, the technical solution adopted in the present invention is:

A kind of preparation method of copper-based catalysts comprises the following steps:

A, the sodium carbonate of 6 weight portion～8 weight portions is dissolved in water, makes sodium carbonate liquor, standby;

B, first the copper sulphate of 9 weight portion～11 weight portions is added to the water-soluble solution of 60 ℃～80 ℃, make copper-bath, then under stirring condition, to the sodium carbonate liquor that adds A step to make in described copper-bath, react, when the pH of reactant liquor value reaches 10, stop adding described sodium carbonate liquor, filter, collect the sediment that reaction produces;

C, the sediment that B step is made wash with water, until the described sedimentary aqueous solution checks sulfate radical-free with barium chloride;

D, the zinc oxide of 0.5 weight portion～1.5 weight portion is joined in the sediment aqueous solution after C step process and stirred, then use Bag filter, by the filtrate centrifugation obtaining, the lower floor's precipitum obtaining is dried in the scope of its water content 15%～18% at the temperature of 50 ℃～60 ℃.

Owing to adopting technique scheme, the beneficial effect that the present invention obtains is:

1. the present invention is by preparation process, add the corresponding preparation process of a certain amount of zinc oxide and combination, make the copper-based catalysts making there is higher catalytic activity, thereby it is few to make this copper-based catalysts have consumption, effectively Reaction time shorten and the advantage that can repeatedly utilize.

2. when using the basic carbonate copper catalyst sold in the market as isoborneol Oxidative Dehydrogenation during for the catalyst of camphor, the consumption of this catalyst is 7%, and isoborneol Oxidative Dehydrogenation is 20 hours～24 hours for the time of camphor; And when the copper-based catalysts that uses the present invention to make is as isoborneol Oxidative Dehydrogenation during for the catalyst of camphor, the consumption of the copper-based catalysts that the present invention makes is only 5%, isoborneol Oxidative Dehydrogenation was for the time decreased to 16 of camphor hour～18 hours, and it can reuse number of times has increased by 2 times～3 times than the basic carbonate copper catalyst of selling in the market.

The specific embodiment

Below in conjunction with specific embodiment, the invention will be further described, and protection scope of the present invention is not only confined to following examples.

Embodiment 1

The preparation method of this copper-based catalysts comprises the following steps:

A, 60g sodium carbonate is dissolved in water, makes sodium carbonate liquor, standby;

B, first 90g copper sulphate is added to 60 ℃ of water-soluble solutions, make copper-bath, then under stirring condition, to the sodium carbonate liquor that adds A step to make in described copper-bath, react, when the pH of reactant liquor value reaches 10, stop adding described sodium carbonate liquor, filter, collect the sediment that reaction produces;

C, the sediment that B step is made wash with water, until the described sedimentary aqueous solution checks sulfate radical-free with barium chloride;

D, 5g zinc oxide is joined in the sediment aqueous solution after C step process and stirred, then use Bag filter, by the filtrate centrifugation obtaining, it is 15% that the lower floor's precipitum obtaining is dried to its water content at the temperature of 50 ℃.

Embodiment 2

The preparation method of this copper-based catalysts comprises the following steps:

A, 70g sodium carbonate is dissolved in water, makes sodium carbonate liquor, standby;

B, first 100g copper sulphate is added to the water-soluble solution of 70 ℃, make copper-bath, then under stirring condition, to the sodium carbonate liquor that adds A step to make in described copper-bath, react, when the pH of reactant liquor value reaches 10, stop adding described sodium carbonate liquor, filter, collect the sediment that reaction produces;

C, the sediment that B step is made wash with water, until the described sedimentary aqueous solution checks sulfate radical-free with barium chloride;

D, 10g zinc oxide is joined in the sediment aqueous solution after C step process and stirred, then use Bag filter, by the filtrate centrifugation obtaining, it is 17% that the lower floor's precipitum obtaining is dried to its water content at the temperature of 55 ℃.

Embodiment 3

The preparation method of this copper-based catalysts comprises the following steps:

A, 80g sodium carbonate is dissolved in water, makes sodium carbonate liquor, standby;

B, first 110g copper sulphate is added to the water-soluble solution of 80 ℃, make copper-bath, then under stirring condition, to the sodium carbonate liquor that adds A step to make in described copper-bath, react, when the pH of reactant liquor value reaches 10, stop adding described sodium carbonate liquor, filter, collect the sediment that reaction produces;

C, the sediment that B step is made wash with water, until the described sedimentary aqueous solution checks sulfate radical-free with barium chloride;

D, 15g zinc oxide is joined in the sediment aqueous solution after C step process and stirred, then use Bag filter, by the filtrate centrifugation obtaining, it is 18% that the lower floor's precipitum obtaining is dried to its water content at the temperature of 60 ℃.

The copper-based catalysts that embodiment 1～3 is made is used separately as isoborneol Oxidative Dehydrogenation for the catalyst of camphor with the basic carbonate copper catalyst of selling in the market, to them each comfortable isoborneol Oxidative Dehydrogenation for the consumption in camphor process, catalytic activity, reuse number of times and compare, its result is as table 1.

Table 1

From above-mentioned table 1, can find out, with respect to the basic carbonate copper catalyst of selling in the market, the copper-based catalysts that the present invention makes have consumption still less, catalytic activity is higher, can reuse the more advantage of number of times.

Claims (1)

1. a preparation method for copper-based catalysts, is characterized in that comprising the following steps:

A, the sodium carbonate of 6 weight portion～8 weight portions is dissolved in water, makes sodium carbonate liquor, standby;

B, first the copper sulphate of 9 weight portion～11 weight portions is added to the water-soluble solution of 60 ℃～80 ℃, make copper-bath, then under stirring condition, to the sodium carbonate liquor that adds A step to make in described copper-bath, react, when the pH of reactant liquor value reaches 10, stop adding described sodium carbonate liquor, filter, collect the sediment that reaction produces;

C, the sediment that B step is made wash with water, until the described sedimentary aqueous solution checks sulfate radical-free with barium chloride;

D, the zinc oxide of 0.5 weight portion～1.5 weight portion is joined in the sediment aqueous solution after C step process and stirred, then use Bag filter, by the filtrate centrifugation obtaining, the lower floor's precipitum obtaining is dried in the scope of its water content 15%～18% at the temperature of 50 ℃～60 ℃.