专利摘要:
1525386 Epoxidation SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ BV 4 Nov 1975 [6 Nov 1974] 47991/74 Heading C2C [Also in Division C1] Epoxidation of propylene or alkyl chloride with an organic hydroperoxide is carried out by contracting the reactants in the liquid phase, preferably at elevated temperature and pressure in the presence of a catalyst comprising at least one metal selected from the group Mo, W, Ti, Zr and V, supported on globular silica particles having high water resistance and bulk crushing strength (as defined) which are made by:- (a) mixing an aqueous alkali metal silicate with an aqueous acid; (b) converting the hydrosol into droplets; (c) gelling the droplets in a liquid immiscible with water; (d) removing at least 25% of the water from the hydrogel by evaporation ; (e) decreasing the alkali metal content of the particles in an aqueous medium to less than 1 wt. per cent and (f) drying and calcining.
公开号:SU784751A3
申请号:SU752185806
申请日:1975-11-04
公开日:1980-11-30
发明作者:Ян Лодевийк Ван Бэм Мартинус;Вагстафф Найджел
申请人:Шелл Интернэшнл Рисерч Маатсхаппий Б.В. (Фирма);
IPC主号:
专利说明:

(54) METHOD FOR OBTAINING SPHERICAL PARTICLES OF SILICON DUOXIDE The invention relates to the production of silicon dioxide, in particular to methods for its preparation in the form of spherical particles, used as catalysts or their carriers, adsorbents, drying agents and ion exchangers. It is known to produce silica particles from an alkali metal silicate by precipitating it with an acid, followed by drying the obtained precipitate 1; The known process makes it possible to obtain powdered silicon dioxide of different dispersity due to variations in temperature, time, pH and other precipitation conditions. A method is known for producing spherical silica particles by mixing alkali metal silicate solutions and mineral acid, converting the resulting hydrosol into a droplet form, gelling droplets in a water-immiscible liquid to produce hydrogel particles, removing the alkali metal from these particles, drying them and calcining .2J Known however, it does not allow to obtain a product with high crush strength (more than 12 kgf / cm) and sufficient water resistance. The aim of the invention is to increase the water resistance and crush strength in bulk of spherical silica particles. The goal is achieved by the described method of obtaining spherical silica particles by mixing aqueous solutions of alkali metal silicate and mineral acid, converting the resulting hydrosol into a droplet form, gelling the droplets in a water-immiscible liquid, evaporating at least 25% of the obtained hydrosol particles, removing from dried particles of alkali metal hydrogel and with their subsequent additional drying and calcination. The difference of this method is that the hydrogel particles are subjected to additional drying before removing the alkali metal from them. The process implementation technology of the invention is as follows. An aqueous solution of an alkali metal silicate, for example sodium, is mixed with an aqueous solution of a mineral acid, for example sulfuric, by feeding them separately into a mixing chamber. The mixture is stirred and the resulting hydrosol is gelled in a liquid that is not miscible with water. This process is carried out, for example, by discharging the hydrosol through a small hole in the bottom of the mixing chamber into the upper part of the vertical cutting house filled with mineral oil. Gelation occurs when dropping the hydrosol droplets down through the oil. At the bottom of the tube, the spherical parts of the hydrogel hydrogel get into the water, are separated from the water, for example by filtration, are washed, and then undergo a water removal step that can be carried out in the same oil where gelatinization takes place. Removal of water from the spherical particles is possible by means of, for example: a) heating the hydrogel particles to under reduced pressure; b) heating the hydrogel particles to a temperature above 100 ° C in an air stream; c) heating particles g of drogel to a temperature of about 100 ° C under reduced pressure, followed by heating the lamella e to a temperature of about 500 ° C in an air stream, d) heating the hydrogel particles to a temperature of 100 ° C in an autoclave with pressure, e a) by heating hydrogel particles in air or steam flow. After removing at least 25% of the water contained in the hydrogel particles by evaporation, the alkali metal content in the hydrogel particle in an aqueous medium is reduced to values less than 1 wt.%, calculated on the dry matter. . Removal of the alkali metal can be easily accomplished by treating the hydrogel particles with an aqueous solution of ammonium nitrate to achieve the desired alkali metal content. In conclusion, the hydrogel particles are dried and calcined, for example, by heating the particles for a certain time to a temperature of 100200 and 450-550С, respectively. According to the invention, it is possible to introduce silicon dioxide particles into a filler, such as alumina, with the aim of increasing the porosity of the final part of silicon dioxide / and also to reduce their cost. The introduction of the filler into the silica particles can be easily accomplished by adding a filler to the aqueous solution of alkali metal silicate and / or to the aqueous solution of the acid, by mixing which the hydrosol is obtained. Examples of suitable fillers are kaolin, montmorillonite, bentonite, precipitated silica fillers, clays, zeolites and amorphous precipitated aluminosilicates .. Since the presence of filler in the final silica particles can reduce their crush strength in bulk. It is impractical to increase more than 25% of the silicon dioxide content in the hydrosol. This method thus makes it possible to increase the water resistance of spherical silica particles by a factor of 2-3 compared with the known product and to increase their crush strength to a maximum value that can be measured by existing methods for determining this characteristic. Example 1. An aqueous solution of sodium liquid glass containing 12 wt. % SiO, with a molar ratio of 3, is stirred for a long time in a mixing chamber with an aqueous 1.2N. a solution of sulfuric acid at a volume ratio of acid solution: 0.75 liquid glass solution. The mixture is left for a few seconds in the mixing chamber, after which the resulting hydrosol is converted into droplets, which are fed into a vertical cylindrical tube 1.8 m long filled with paraffin oil with at a temperature of 25 ° C and they are gelled when the tube is dropped. The resulting spherical hydrogel particles at the bottom of the tube are fed when they fall into water with a temperature of 25 ° C, from which they are separated by filtration, then washed with water. The resulting hydrogel particles are analyzed for moisture content by heating them from room temperature to 600 ° C. A part of the obtained particles with a moisture content of 90% by weight is further dried for 2 hours under reduced pressure until the moisture in them decreases to 18% by weight, after which the particles are treated with an aqueous solution of ammonium nitrate, dried for 2 hours at 100c and calcined at 500 ° C for 3 hours. The resulting spherical particles have a water resistance of 95% and a crush strength in bulk form of more than 16.7 kgf / cm. Example 2. The process is carried out analogously to example 1, but on condition that the particles are dried before being treated with ammonium nitrate at 120 ° C in air flow for 3 hours. The resulting spherical particles have a water resistance of 93% and a crush strength of more than 16.7 kgf / cm. Example 3 The process is carried out analogously to example 1, but under the condition that they are processed by a glass before being treated with ammonium nitrate by drying for 2 hours under reduced pressure followed by calcining for 3 hours under air flow until the moisture in them decreases to 3 wt.% .
The properties of the resulting particles are similar to those described in example 1.
Example 4 The process is carried out as in Example 1, but with the condition that water is removed from the particles by contacting them with paraffinic carbohydrate oil for 6 hours at up to a content of 12% by weight of moisture.
The resulting spherical particles have a water resistance of 96% and crushing strength of more than 16.7 kgf / cm.
Example 5. The process is carried out as in Example 1, but when the particles are heated for 4 hours in an autoclave under pressure until the water is reduced to 60 wt.%, Followed by treatment with alumina hydrate,
The water resistance of the spherical particles obtained is 98% and the crush strength in bulk is more than 16.7 kgf / cm.
The process is carried out as in example 1, but provided that sodium liquid glass is introduced into an aqueous solution of 12 g of powdered kaolin filler per 1 liter of solution.
The final spherical particles have a water resistance of 91% and crushing strength of more than 15 kgf / cm.
The optimality of the proposed conditions for the production of spherical particles by double silicon is determined by the following substantiation.
When water is removed from hydrogel particles, before reducing the alkali metal according to the invention in them, for example (TO 67%, but not by evaporation, or when water is removed by evaporation, but to a value less (v20%) than according to isoretenia, water resistance strength of the resulting spherical
particles are much lower than particles obtained according to the invention and described in IB examples, n is 43% and SKrc / cf fi50% and 8 kgf / cm, respectively.
The high water resistance and crush strength in bulk of the proposed spherical silica particles greatly expand its range of application in catalytic technology. They can be used as
0 catalysts in various processes of the chemical and petrochemical industry, especially as catalyst carriers for hydrodemetallization of heavy mineral oils and for epoxidation of ethylenically unsaturated compounds with organic hydroperoxide.
权利要求:
Claims (2)
[1]
1. Dealer RK, Colloidal silica and silicates. M., izdat, 1959, p. 137-141.
[2]
2. US patent number 2386810, g class. 252-45.1, publ. 1915.
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同族专利:
公开号 | 公开日
FR2290395B1|1980-05-16|
NL7512900A|1976-05-10|
ES442322A0|1977-04-01|
FR2290395A1|1976-06-04|
SE7512343L|1976-05-07|
AU8630875A|1977-05-12|
NO753687L|1976-05-07|
DE2549411C2|1988-09-29|
BE834924A|1976-04-28|
NO139678B|1979-01-15|
CA1064008A|1979-10-09|
IT1048821B|1980-12-20|
JPS5823329B2|1983-05-14|
SE411542B|1980-01-14|
JPS5168497A|1976-06-14|
NO139678C|1979-04-25|
DE2549411A1|1976-05-13|
ZA756937B|1976-10-27|
GB1525386A|1978-09-20|
引用文献:
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US2385217A|1942-10-09|1945-09-18|Socony Vacuum Oil Co Inc|Gel pellets|
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EP0834348B1|1996-10-07|2004-03-31|Kabushiki Kaisha Toyota Chuo Kenkyusho|Composite oxide, composite oxide carrier and catalyst|
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法律状态:
优先权:
申请号 | 申请日 | 专利标题
GB47991/74A|GB1525386A|1974-11-06|1974-11-06|Process for the preparation of globular silica particles|
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