CN105056932A - Preparation method of titanium-based catalyst used for producing camphene - Google Patents

Abstract

The invention discloses a preparation method of a titanium-based catalyst used for producing camphene, belonging to the technical field of camphene preparation. The preparation method comprises the following steps: putting metatitanic acid, metasilicic acid and a sodium hydroxide solution with concentration of 40% in a reactor, firstly stirring the materials at room temperature, then heating the materials and continuously stirring the materials, filtering the mixture and collecting a first precipitate; washing the first precipitate with water, then subjecting the first precipitate and an acetic acid solution with concentration of 30% to acidification reaction, filtering the reactant and collecting a second precipitate; washing the second precipitate with water, then stirring the second precipitate, zirconia and rare earth carbonate uniformly, filtering the mixture, carrying out centrifugal separation, then adding magnesium stearate and a titanyl sulfate water solution, mixing the materials and calcining the mixture, thus preparing the titanium-based catalyst. Relative to the titanium-based catalysts sold on the market at present, the titanium-based catalyst prepared by the preparation method has the advantages of lower consumption and higher catalytic activity.

Description

The preparation method of amphene production Ti-base catalyst

Technical field

The invention belongs to amphene preparing technical field, particularly relate to a kind of preparation method of amphene production Ti-base catalyst.

Background technology

Amphene is a kind of bicyclic diterpene vinyl compound, is the composition of the multiple natural volatile oil of turpentine wet goods, main as organic synthesis raw material, can be used for artificial camphor, spices, agricultural chemicals, thiocyanic acid acetic acid different thatch ester, the different thatch ester of acetic acid, toxaphene etc.

Amphene can be obtained by isomery by australene isomery.Tautomerize in the process of amphene, usually using metatitanic acid as catalyst at australene.But the metatitanic acid catalyst sold in the market also exists the deficiencies such as consumption is large, catalytic efficiency is low mostly.

Summary of the invention

The technical problem that the present invention solves is to provide a kind of preparation method of amphene production Ti-base catalyst, and this preparation method can solve existing Ti-base catalyst and there is the problem that consumption is large, catalytic efficiency is low.

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

It comprises the following steps:

A, under agitation, by 0.5 weight portion ~ 0.7 weight portion metatitanic acid, 0.1 weight portion ~ 0.3 weight portion metasilicic acid and 2.4 weight portion ~ 4.0 weight portion concentration be 40% sodium hydroxide solution put into reactor, first stir 1 hour ~ 3 hours at normal temperatures, then be warming up to 120 DEG C ~ 130 DEG C and continue stirring 10 hours ~ 12 hours, filter, collect and obtain the first sediment;

B, the first precipitate washed with water that step A is obtained to the pH value of described first sedimentary rinsing solution in 7.3 ~ 8.0 scopes;

C, in the first sediment after step B process, add 1 weight portion ~ 1.6 weight portion concentration be the acetum of 30%, carries out acidification reaction 6 hours ~ 8 hours, filters, and collects and obtain the second precipitation;

D, the second sediment water washing that step C is obtained to the pH value of described second sediment rinsing solution in 2.5 ~ 3.5 scopes;

E, 0.1 weight portion ~ 0.3 weight portion zirconia and 0.05 weight portion ~ 0.08 weight portion carbonated rare earth are joined D step process after the second sediment solution in stir, then Bag filter is used, by the filtrate centrifugation obtained, the lower floor's precipitum obtained;

F, in the obtained lower floor's precipitum of E step, add 0.2 weight portion ~ 0.4 weight portion dolomol and the 0.04 weight portion ~ 0.08 parts sulfuric acid oxygen titanium aqueous solution, stir, then first at the temperature of 50 DEG C ~ 60 DEG C, its water content is dried in the scope of 15% ~ 18%, again at the temperature lower calcination 4 hours ~ 6 hours of 1100 DEG C ~ 1200 DEG C, obtained.

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

The present invention is by preparation process, add a certain amount of metasilicic acid, concentration be 40% sodium hydroxide solution, zirconia, carbonated rare earth, dolomol and aqueous solution of titanyle sulfate, the Ti-base catalyst obtained is made to have higher catalytic activity, thus it is high to make this Ti-base catalyst have catalytic efficiency, consumption is few, can the advantage of effective Reaction time shorten.

Detailed description of the invention

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 amphene production Ti-base catalyst comprises the following steps:

A, under agitation, by 0.5kg metatitanic acid, 0.1kg metasilicic acid and 2.4kg concentration be 40% sodium hydroxide solution put into reactor, first stir 2 hours at normal temperatures, then be warming up to 120 DEG C and continue stirring 10 hours, filter, collect and obtain the first sediment;

B, the first precipitate washed with water of step A being obtained are 7.3 to the pH value of described first sedimentary rinsing solution;

C, in the first sediment after step B process, add the acetum that 1kg concentration is 30%, carry out acidification reaction 6 hours, filter, collect and obtain the second sediment;

D, the second precipitate washed with water of step C being obtained are 3.5 to the pH value of described second sedimentary rinsing solution;

E, 0.1kg zirconia and 0.08kg carbonated rare earth are joined D step process after the second sediment solution in stir, then use Bag filter, by the filtrate centrifugation obtained, the lower floor's precipitum obtained;

F, in the obtained lower floor's precipitum of E step, add 0.2kg dolomol and 0.08kg aqueous solution of titanyle sulfate, stir, then first at the temperature of 50 DEG C, being dried to its water content is 15%, then calcines 4 hours at 1200 DEG C, obtained.

Embodiment 2

The preparation method of this amphene production Ti-base catalyst comprises the following steps:

A, under agitation, by 0.6kg metatitanic acid, 0.6kg metasilicic acid and 3.2kg concentration be 40% sodium hydroxide solution put into reactor, first stir 1 hour at normal temperatures, then be warming up to 125 DEG C and continue stirring 11 hours, filter, collect and obtain the first sediment;

B, the first precipitate washed with water of step A being obtained are 7.6 to the pH value of described first sedimentary rinsing solution;

C, in the first sediment after step B process, add the acetum that 1.3kg concentration is 30%, carry out acidification reaction 7 hours, filter, collect and obtain the second sediment;

D, the second precipitate washed with water of step C being obtained are 3.0 to the pH value of described second sedimentary rinsing solution;

E, 0.2kg zirconia and 0.06kg carbonated rare earth are joined D step process after the second sediment solution in stir, then use Bag filter, by the filtrate centrifugation obtained, the lower floor's precipitum obtained;

F, in the obtained lower floor's precipitum of E step, add 0.3kg dolomol and 0.06kg aqueous solution of titanyle sulfate, stir, then first at the temperature of 55 DEG C, being dried to its water content is 16%, then at the temperature lower calcination 6 hours of 1100 DEG C, obtained.

Embodiment 3

The preparation method of this amphene production Ti-base catalyst comprises the following steps:

A, under agitation, by 0.7kg metatitanic acid, 0.3kg metasilicic acid and 4.0kg concentration be 40% sodium hydroxide solution put into reactor, first stir 3 hours at normal temperatures, then be warming up to 130 DEG C and continue stirring 12 hours, filter, collect and obtain the first sediment;

B, the first precipitate washed with water of step A being obtained are 8.0 to the pH value of described first sedimentary rinsing solution;

C, in the first sediment after step B process, add the acetum that 1.6kg concentration is 30%, carry out acidification reaction 8 hours, filter, collect and obtain the second sediment;

D, the second precipitate washed with water of step C being obtained are 2.5 to the pH value of described second sedimentary rinsing solution;

E, 0.3kg zirconia and 0.05kg carbonated rare earth are joined D step process after the second sediment solution in stir, then use Bag filter, by the filtrate centrifugation obtained, the lower floor's precipitum obtained;

F, in the obtained lower floor's precipitum of E step, add 0.4kg dolomol and 0.04kg aqueous solution of titanyle sulfate, stir, then first at the temperature of 60 DEG C, being dried to its water content is 18%, then at the temperature lower calcination 5 hours of 1100 DEG C, obtained.

Ti-base catalyst obtained for embodiment 1 ~ 3 is used separately as with the Ti-base catalyst sold in the market the catalyst that australene tautomerizes to amphene, their each comfortable australenes are tautomerized to the consumption in amphene process, time that australene tautomerizes to amphene compares, its result is as table 1.

Table 1

As can be seen from above-mentioned table 1, relative to the Ti-base catalyst sold in the market, the Ti-base catalyst that the present invention obtains has the advantage that consumption is less, catalytic activity is higher.

Claims (1)

1. a preparation method for amphene production Ti-base catalyst, is characterized in that comprising the following steps:

A, under agitation, by 0.5 weight portion ~ 0.7 weight portion metatitanic acid, 0.1 weight portion ~ 0.3 weight portion metasilicic acid and 2.4 weight portion ~ 4.0 weight portion concentration be 40% sodium hydroxide solution put into reactor, first stir 1 hour ~ 3 hours at normal temperatures, then be warming up to 120 DEG C ~ 130 DEG C and continue stirring 10 hours ~ 12 hours, filter, collect and obtain the first sediment;

B, the first precipitate washed with water that step A is obtained to the pH value of described first sedimentary rinsing solution in 7.3 ~ 8.0 scopes;

C, in the first sediment after step B process, add 1 weight portion ~ 1.6 weight portion concentration be the acetum of 30%, carries out acidification reaction 6 hours ~ 8 hours, filters, and collects and obtain the second precipitation;

D, the second sediment water washing that step C is obtained to the pH value of described second sediment rinsing solution in 2.5 ~ 3.5 scopes;

E, 0.1 weight portion ~ 0.3 weight portion zirconia and 0.05 weight portion ~ 0.08 weight portion carbonated rare earth are joined D step process after the second sediment solution in stir, then Bag filter is used, by the filtrate centrifugation obtained, the lower floor's precipitum obtained;

F, in the obtained lower floor's precipitum of E step, add 0.2 weight portion ~ 0.4 weight portion dolomol and the 0.04 weight portion ~ 0.08 parts sulfuric acid oxygen titanium aqueous solution, stir, then first at the temperature of 50 DEG C ~ 60 DEG C, its water content is dried in the scope of 15% ~ 18%, again at the temperature lower calcination 4 hours ~ 6 hours of 1100 DEG C ~ 1200 DEG C, obtained.