JPH04187239A - Production of solid acid catalyst - Google Patents

Abstract

PURPOSE:To obtain a catalyst having superior reaction activity in a reaction such as the alkylation or polymn. of hydrocarbon by dehydrating powder of the hydroxide or oxide of a group IV metal of the periodic table and uniformly adding a specified amt. of a soln. contg. sulfuric acid radicals to the dehydrated powder. CONSTITUTION:Powder of the hydroxide or oxide of a group IV metal of the periodic table such as Sn, Ti or Zr is dehydrated and a soln. contg. sulfuric acid radicals such as an aq. sulfuric acid soln. is uniformly added to the dehydrated powder by an amt. equal to the weight of water removed by the dehydration or less to support sulfuric acid radicals by 0.5-12wt.% as sulfur. A solid acid catalyst having superior reaction activity in a reaction such as the alkylation or polymn. of hydrocarbon, not corroding a reactor and ensuring easy separation from a reactant and a reaction product can be produced without carrying out filtration or firing.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for producing a solid acid catalyst used in petroleum refining, petrochemical industry, etc.

rPrior art] Reactions in petroleum refining and petrochemical industry include catalytic cracking, catalytic reforming, hydrodesulfurization, isomerization, alkylation of aliphatic hydrocarbons and aromatic hydrocarbons, polymerization, dehydration, or dehydrogenation. This type of reaction includes sulfuric acid, aluminum chloride, antimony trichloride, hydrogen fluoride,
Acid catalysts such as phosphoric acid are used. However, these acid catalysts corrode metals, so it is necessary to use expensive corrosion-resistant materials or to undergo corrosion-resistant treatment.Also, alkaline cleaning must be performed to remove acids accompanying exhaust gas or products, and waste acid With the recent tightening of environmental regulations, the treatment of waste, including its disposal, is becoming increasingly regulated. Furthermore, even if these catalysts form a homogeneous or separated phase with the reactants, they are liquid and therefore difficult to separate after the reaction.

In addition, solid super strong acid catalysts are known as catalysts that overcome these drawbacks of acid catalysts and have higher activity, that is, stronger acid strength, than the above-mentioned acid catalysts.

For example, a solid super strong acid catalyst (Japanese Patent Publication No. 59-6181 ) or a solid superacid catalyst that increases the catalyst surface area by contacting it with alcohol before and after hydrolyzing a metal salt from Group Ⅰ of the periodic table, and then treating the resulting hydroxide with a sulfuric acid radical-containing solution and then calcining it. (Japanese Unexamined Patent Publication No. 64-43348).

All of these solid super strong acid catalysts develop an acid strength stronger than that of 100% sulfuric acid when fired at a temperature of 300°C or higher, and exhibit high activity in isomerization and alkylation of hydrocarbons. Despite this, there is little corrosion of the equipment.

However, such solid super-strong acid catalysts have extremely high hygroscopicity, and have the disadvantage that absorption of water significantly reduces acid strength. Therefore, catalyst storage, transportation, and moisture management during catalytic reaction are extremely troublesome and impractical. In addition, in all of the solid super acid catalysts mentioned above, after contacting the hydroxide or oxide of a metal from Group I of the periodic table with a solution containing a sulfate group such as dilute sulfuric acid, the excess solution containing a sulfate group is removed by suction filtration or the like. It is then dried and fired. Therefore, not only the filtration process and the calcination process take time, but also the process is complicated and requires neutralization of the filtration waste liquid discharged from these processes and desulfurization of the sulfur compounds contained in the calcination exhaust gas. , and uneconomical.

[Problem that the invention seeks to solve]

The present invention has solved the above-mentioned drawbacks, and the purpose of the present invention is to have excellent reaction activity in reactions such as alkylation and polymerization of hydrocarbons, while not corroding the reaction equipment, and to prevent reactants and reaction products from being damaged. It is an object of the present invention to provide a simple manufacturing method for manufacturing a solid acid catalyst that can be easily separated from a solid acid catalyst without performing filtration or calcination.

[Means for Solving the Problems] As a result of research into a method for producing solid acid catalysts at low cost without worrying about pollution control, the present inventors found that metal hydroxides of Group I of the periodic table or After removing some or all of the adhering water and crystallization water on the oxide, a solution containing sulfate radicals is uniformly sprayed on the oxide to support the sulfate radicals while maintaining the hydroxide or oxide in a powdered state. discovered that a solid acid catalyst produced without filtration or calcination has high reaction activity, leading to the present invention.

That is, the present invention dehydrates a powder of a metal hydroxide or oxide of Group I of the periodic table, and then adds an amount equal to the weight of the dehydrated water or The group I metals of the periodic table used in the present invention, which is a method for producing a solid acid catalyst in which 0.5 to 12% by weight of sulfuric acid radicals are supported as sulfur by uniformly adding a solution containing sulfuric acid radicals in an amount less than Sn, Pb, Ti, Zr, H
f, Sn, Ti, and Zr are particularly preferred, and these hydroxides and oxides can be prepared by precipitation, generation, and drying of hydroxides by addition of alkali to group (I) metal salts, or oxides by thermal decomposition. It can be obtained by commonly used methods such as the production of Examples of the alkali used for precipitating the hydroxide include common potassium hydroxide, sodium hydroxide, and aqueous ammonia, and aqueous ammonia is particularly preferred since it does not leave behind metal ions that can become impurities. The hydroxide thus obtained is usually traded in the form of a powder containing water of crystallization and some adhering water.

As the sulfuric acid group-containing solution used in the present invention, a solution prepared by dissolving sulfuric acid, sulfate of an amine, etc. in water or an organic solvent such as alcohol or carboxylic acid can be used, but an aqueous sulfuric acid solution is particularly preferred. The sulfuric acid group is supported as sulfur in an amount of 0.5 to 12% by weight on the catalyst. 0.
If it is less than 5% by weight, there will be a lack of acid and no activity will be obtained, and if it is more than 12% by weight, the specific surface area will be extremely small and the activity will be reduced.

The dehydration treatment of the present invention can be carried out by a known method in which the powder of the Group I metal hydroxide or oxide is brought into contact with hot air while stirring. The water of crystallization of the hydroxide or oxide powder is volatilized and desorbed over a sufficient period of time even at a low temperature of 30°C in a dry atmosphere, but at temperatures between 30°C and 120°C
When drying is carried out for several hours at a temperature range of ℃, the entire amount of water of crystallization is volatilized and eliminated. After that, when left in the air at room temperature, it absorbs moisture and returns to hydroxide with water of crystallization. The compound form between these is amorphous. The drying treatment is preferably carried out at 80 to 100°C for 3 to 6 hours; if the treatment temperature is too high, crystallization will proceed and the specific surface area will decrease significantly.
Drying at temperatures above 120°C must be avoided.

Next, a sulfate radical-containing solution such as dilute sulfuric acid is added uniformly to the powder by spraying a sulfuric acid radical-containing solution such as dilute sulfuric acid while stirring the dried and dehydrated Group I metal hydroxide or oxide powder. to carry. If the amount sprayed or added is too large, even locally, for the Group I metal hydroxide or oxide, the grains will become coarse or gelatinous, and the sulfate groups will not be supported uniformly.

If the amount is even higher, an excessive amount of the sulfate radical-containing solution will be produced, and a filtration step and a neutralization step of the filtered waste liquid will be required.

In order not to generate an excessive amount of the sulfate group-containing solution and to support it uniformly, an amount of water approximately equal to or more than the amount of the sulfate group-containing solution to be supported is previously dried and dehydrated from the powder, and this amount of dry dehydration is, in other words, The sulfate radicals may be supported by uniformly spraying a solution containing sulfate radicals in an amount equal to or less than the amount of water absorbed by the powder. In particular, it is preferable to dehydrate the solution in an amount equal to the amount of the sulfate group-containing solution to be supported, or to adjust the concentration of the sulfate group and uniformly spray the sulfate group-containing solution in an amount equal to the amount of dehydration.

The amount of dehydration of the Group I metal hydroxide or oxide powder can be controlled by appropriately selecting the temperature and time within the above-mentioned temperature range of 80 DEG to 100 DEG C. and treatment time of 3 to 6 hours. In addition, the amount of sulfate group-containing solution to be supported and the concentration of sulfate groups are as follows:
It is preferable to use an appropriate method according to the amount of sulfate radicals supported on the powder.

Group (I) metal hydroxides or oxides are usually in the form of powder, and in some cases, they are already commercially available in a somewhat dry state. In such a case, the sulfate group-containing solution can be added in an amount of about 10% by weight without drying. In the case of ZrQ(OH), Zr0(0)(),
If the sum of adhering water and crystallized water exceeds about 180 parts by weight per 100 parts by weight, the powders begin to bond with each other and become coarse particles. Therefore, by using a solution containing sulfate radicals with a low concentration, -
If the specified amount of sulfate roots cannot be achieved with multiple applications,
It is possible to dry the powder carrying sulfate radicals again to restore its water absorption ability, and repeat the spraying and drying within the moisture content range that does not cause grain coarsening until the predetermined amount of powder is carried. Not even.

The powder of the sulfate group-carrying group (I) metal compound thus prepared can be used as it is as a solid acid catalyst without being subjected to any filtration or calcination treatment. Of course, even if a drying treatment is performed after supporting the sulfate group, the effects of the present invention will not be particularly impaired.

The solid acid catalyst obtained by the present invention as described above is effective as a catalyst for hydrocarbon alkylation reactions, polymerization reactions, dehydration reactions, etc., and the catalyst manufacturing method is extremely simple compared to conventional solid acid catalysts, making it practical. It is true.

Examples of the alkylation reaction include obtaining a high octane gasoline base material from isobutane and lower olefins, or modifying wax.

Further, polymerization reactions include polymerization of lower olefins such as ethylene, propylene, and butene, or polymerization of middle and higher olefins, and dehydration reactions include dehydration of alcohols, esterification, etc.

[Example] Production example 1 Zirconium chloride (ZrOCl, .8H,O) 0
．． After gradually adding 5 mol (162 g) to sewage IQ at room temperature while stirring and dissolving the entire amount, 1. 8α was added gradually to form zirconium hydroxide. Next, stirring was stopped and the mixture was allowed to stand overnight, and the generated zirconium hydroxide was filtered and then thoroughly washed with pure water. The obtained zirconium hydroxide was dried at 100° C. for 2 hours to obtain about 70 g of dried product from which almost all of the water of crystallization had been removed. Next, 32 g of 98 wt % sulfuric acid was sprinkled on this dried product to obtain a solid acid catalyst A.

Production example 2 Zirconium hydroxide (ZrO(0)(), 11.81
(,0) 100g of powder was dried at 10℃ for 30 minutes,
A portion of 16 g of crystallization water was removed by volatilization, and then 16 g of 75 wt % sulfuric acid was sprinkled on this dried product to obtain a solid acid catalyst B.

Production Example 3 100g of zirconium hydroxide powder, the same as the raw material used in Production Example 2, was dried at 80°C for 6 hours to remove 54g of water by volatilization, and then 50g of 12wt% sulfuric acid was sprinkled on the dried product to prepare a solid acid catalyst Ct. /Obtained.

Production Example 4 The sulfate group-supported zirconium hydroxide produced in the same manner as in Production Example 2 was dried at 120°C for 3 hours to obtain a solid acid catalyst.

Production Example 5 To the dried zirconium hydroxide powder that was dried in the same manner as in Production Example 2, 1. 14 g of sulfuric acid was sprayed to obtain solid acid catalyst E.

Production Example 6 A solid acid catalyst F was obtained by spraying 49 g of 75 wt % sulfuric acid onto a dried zirconium hydroxide powder that had been dried in the same manner as in Production Example 3.

Examples 1 to 6 (Alkylation reaction) For each of the solid acid catalysts A to F, a 100+nα glass autoclave was cooled with dry ice-ethanol refrigerant, then 1mα of l-butene and 69m0 of isobutane were charged, and then the solid acid catalyst was charged. , the reaction system was sealed and gradually heated while stirring to maintain the reaction temperature at 0°C.
Allowed to react for minutes. The reaction results are calculated as 0 for the raw material 1-butene.
Table 1 shows the yields of 6-CIl fractions.

Example 7.8 (Polymerization reaction) For each of solid acid catalysts C and D, 30 mQ of isopentene and 70 mQ of isopentane were placed in a 200 mQ autoclave, and after the solid acid catalyst was introduced, the reaction was carried out at 80° C. for 3 hours. The reaction results are shown in Table 1 in terms of isopentene conversion.

, Comparative Example 1 (Alkylation reaction) The reaction was carried out in the same manner as in Examples 1 to 6 except that 98% sulfuric acid was used as the catalyst. The results are shown in Table 1.

Comparative Example 2 (Polymerization Reaction) A reaction was carried out in the same manner as in Example 7.8 except that silica alumina was used as the catalyst. The results are shown in Table 1.

(The following is a blank space) 112= [Effects of the Invention] As described above, the present invention dehydrates a powder of a Group I metal hydroxide or oxide of the periodic table, and removes sulfuric acid radicals in an amount equal to or less than the dehydrated amount. Since the solid acid catalyst is produced by adding the containing solution, no waste acid is generated and the filtration process,
It is practical and can be produced by a simple method that does not require a calcination process, and the obtained solid acid catalyst can be used for alkylation of hydrocarbons,
Since it shows high activity in polymerization reactions, it is useful in fields such as petroleum refining and petrochemical industry.

Claims (1)

[Claims] A powder of a metal hydroxide or oxide of Group IV of the Periodic Table is dehydrated, and then a sulfate group-containing solution is added to the dehydrated powder in an amount equal to or less than the weight of the dehydrated water. 1. A method for producing a solid acid catalyst, which comprises uniformly adding sulfuric acid groups to support 0.5 to 12% by weight of sulfuric acid radicals as sulfur.