CN1031822A - The chance water of adjusting porous structure is the method for making of split silicone not - Google Patents
The chance water of adjusting porous structure is the method for making of split silicone not Download PDFInfo
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- CN1031822A CN1031822A CN 87100996 CN87100996A CN1031822A CN 1031822 A CN1031822 A CN 1031822A CN 87100996 CN87100996 CN 87100996 CN 87100996 A CN87100996 A CN 87100996A CN 1031822 A CN1031822 A CN 1031822A
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- silica gel
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/16—Preparation of silica xerogels
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Abstract
The silica gel that adopts the method for forming oil column to make, easily cracked when being used to prepare support of the catalyst because of meeting water, the catalyst strength that makes is reduced, the particle integrity rate descends, thus influence and limited its industrial application.Use method for making of the present invention, not only can solve silica gel satisfactorily and meet the cracked problem of water, can regulate the pore structure that makes silica gel simultaneously, to adapt to of the different requirements of multiple catalyzer to the carrier hole structure.And open up new purposes for the comprehensive utilization of cracked silica gel.
Description
The invention belongs to the method for making of support of the catalyst.
Silica gel has a wide range of applications as support of the catalyst.Because characteristics such as it has acidproof, wear-resisting, good heat resistance, and surface acidity is low often are used in the catalyzed reactions such as olefin oxidation, olefin hydration, olefine aldehydr hydrogenation, naphthalene oxidation system phthalic anhydride.
The silica gel that adopts the method for forming oil column to make, shortcoming are with it during as the preparation support of the catalyst, and it is easily chipping to run into the aqueous solution, thereby has reduced catalyzer physical strength and particulate percentage of head rice, and make that increase falls in pressure in the catalytic reaction process.During as siccative and sorbent material, similar situation takes place also, this just influences and restriction silica gel is made support of the catalyst, siccative, sorbent material and otherwise industrial application.
Record in the Japanese Patent of announcing on July 10th, 1975 (a day disclosure is speciallyyed permit clear 50-85608), with silica gel powder and inorganic sol hybrid shaping, can make the high surface area of making support of the catalyst through high-temperature calcination, high porosity, the silica gel of powder shaping thing of low bulk density, it has the characteristics that water does not split of meeting.
Use which kind of raw material specification but this patent illustrates, the pore structure that also not have solution how to regulate silica gel by preparation technology is to adapt to the reaction requirement of different catalysts.
The present invention is intended to solve simultaneously chance the water not method for making and the problem of regulating the silica gel pore structure of split silicone, makes it to adapt to the requirement of industry use and adapt to the different requirements of multiple catalyzer to the carrier hole structure.
The chance water that can regulate Different Pore Structures is the method for making of split silicone not, and main points are that as the Powdered silica gel that raw material is used can be the work in-process of handling without calcining and activating, cracked or not cracked silica gel finished product, and its powder size is less than 150 μ.
Spherical silica-gel after being shaped is adopted suitable gelling aging condition and suitable solution pressurized heat treatment condition.Because work in-process or the cracked silica gel pore structure selected for use are not completely fixed as yet, help the adjusting of preparation technology to pore structure.And select different gelling aging conditions and solution pressurized heat treatment condition, can make the silica gel product of required Different Pore Structures.
Concrete preparation method is as follows:
With commercially available gross porosity microsphere silica gel, bead silica gel or amorphous particle silica gel (places of production such as Shanghai and Nanjing, Qingdao) grind to form the fine powder less than 150 μ, and contain SiO
27～25% silicon sol mixes, and on the tumbling disk granulator that keeps certain rotating speed, is rolled onto bead.The per kilogram silica-gel powder uses 0.5-2.5 to rise silicon sol.The bead silica gel of gained is after surperficial polishing, and it is aging to carry out gelling in the immigration encloses container, and the gelling aging temperature is 10-40 ℃, and the gelling digestion time is 24-500 hour.The aging end dried in the immigration dish, and drying envrionment temperature is 10-40 ℃, and drying relative humidity is 60-85%, and flash-off time is 12-500 hour.Dry finish after in 60-110 ℃ of dry 4-24 hour.Dried silica gel was placed in the muffle furnace in 200-800 ℃ of following roasting 1-10 hour, carry out the solution pressurized heat after the cooling and handle.
To put into autoclave with the silica gel that aforesaid method makes, the mixing salt that adding is formed by acetic acid, ammonium acetate, ammonium hydroxide, sodium bicarbonate, sodium sulfate or by lithium chloride, sodium-chlor and saltpetre etc. the formulated concentration of one or more compounds is the normal aqueous solution of 0.05-0.2, every liter of silica gel adds the aqueous solution that 1.2-10 rises, and the solution pH value is 2-10.Pressure build up is to 1-100kg/cm
2, after constant voltage 1-40 hour, take out silica gel and be washed with distilled water to neutrality, through 60-110 ℃ of dry 2-20 hour, place then in the muffle furnace, in 200-800 ℃ of roasting 1-10 hour, promptly get required silica gel after the cooling.
The silica gel that adopts aforesaid method to make is not only met water and is not split, and can make its specific surface area at 50-250m
2/ g.Pore radius is at 80-200
, pore volume is regulated in the 0.4-1.5ml/g scope, to be adapted to prepare the needs of different catalysts carrier.
Reference
(1) day disclosure special permission clear-50-85608 (1975.7.10)
(2) special permission of day disclosure clear-50-84516(1975.7.8)
Example 1
Unfired gross porosity microsphere silica gel after crushing and screening, is got the silica-gel powder of particle diameter less than 85 μ, and placing diameter is in the stainless steel rotating disk of 350mm, and rotating disk rotates with 36 rev/mins speed.To contain SiO
210% silicon sol is sprayed onto on the silica-gel powder by spray gun, adds the minor amount of silicon rubber powder simultaneously, is rolled onto the bead seed.Continue then to add silica-gel powder slowly, and spray into silicon sol, the per kilogram silica-gel powder uses the about 1.3-1.5 liter of silicon sol.When being rolled onto desired particle size, rolled again 30 minutes.Be not less than under 25 ℃, the shaping thing put into dish dry more than 16 hours, be placed in the muffle furnace 650-750 ℃ of roasting 4 hours after 4 hours again, making balling-up silica gel behind the naturally cooling in 80 ℃ of dryings.
Balling-up silica gel has meets the characteristics that water does not split, physical strength is good, and its rerum natura is as follows:
Specific surface area is 300m
2/ g, pore volume are 0.67-0.80ml/g, and tap density is 0.4-0.45g/ml, particle diameter 4.7-5.8mm, and compressive strength is 6-9kg/, wear rate in 8 hours
*(less than the weight of particle and the powder of 2.5mm) is 3%, through three cracked rates of wet dry-cure repeatedly
*Less than 1%.
Example 2
Get a certain amount ofly through crushing and screening the silica-gel powder of particle diameter, and contain SiO less than 85 μ
2Be 11.5 ± 5% silicon sol, soak knead agglomerating.Pressing on agglomerating thing and the 10-12 order metallic sieve, form fine strip shape thing different in size.The immigration diameter is 1300mm, and height is in the rotating disk of 300-320mm rigid PVC system, and rotating disk rotates with 19-24 rev/min speed.In the time of when silica-gel powder blows slowly on the one hand the adding dish from rotary pocket feeder, on the other hand silicon sol in storage tank with 3-4kg/cm
2Pressure be sprayed onto in the dish from spray gun, utilize the effect be contained in rotating disk top one plate washer this moment, make fine strip shape silica gel repeatedly with the plate washer collision, form uniform seed.Add under the situation of powder limit hydrojet and rotation on continuous limit, bead progressively rolls greatly, to forming required globule size.The per kilogram silica-gel powder uses silicon sol 1.3-1.5 liter, moves in the coater making bead silica gel then, carries out polishing with certain rotating speed, lasts 30 minutes, to remove the floating powder in bead surface.Bead is placed in the encloses container, be not less than and carry out gelling under 20 ℃.At this moment, bead silica gel loading height preferably is no more than 300mm, is out of shape with the bead silica gel at the bottom of the preventer.Must reach storage period more than 48 hours, dry in the immigration dish then more than 24 hours, envrionment temperature is 25-35 ℃ when drying, and relative humidity is 70-80%.Bead silica gel more than 12 hours, moved into aforesaid coater interior polishing 10-20 minute in 90-110 ℃ of drying again after drying, and it is interior in 750 ± 10 ℃ of roastings 4 hours to put muffle furnace or tunnel furnace, makes balling-up silica gel after the cooling.
The rerum natura of balling-up silica gel is as follows:
Outward appearance is a White-opalescent garden ball, and particle size diameter is 3-10mm, and compressive strength is more than or equal to 7kg/, and tap density is 0.42-0.46g/ml, and specific surface area is 290-380m
2/ g, pore volume are 0.80-0.95ml/g, through three cracked rates of wet dry-cure repeatedly
*Less than 1%, wear rate
*(less than the weight of 2.5mm particle and powder) less than 3%, balling-up silica gel largest hole dilatation percentage is seen Fig. 1 to average pore diameter distribution plan (desorption).
Example 3
Get the ammonium acetate 1334.9g of content 98%, content is the aqueous solution that 99% acetic acid 351.5ml and distilled water 243.1 liters are made into, and placing diameter is 700mm, and height is in the stainless steel autoclave of 900mm, stirs with nitrogen, and at this moment, the solution pH value is 5 ± 0.1.Other gets balling-up silica gel 130 liters that example 2 makes and drops in the still, is warming up to 165 ± 2 ℃ with autoclave is airtight then, and gauge pressure is 6kg/cm
2The time, constant voltage is after 10 hours, and normal pressure is reduced in cooling, emits balling-up silica gel.At this moment, mother liquor PH is 5.4-6.2 in the still.Treated balling-up silica gel distilled water flushing is cooled to 20-30 ℃, and moving into rotating speed is 22-28 rev/min of wet wheeling machine wet-milling 15-20 minute.Again balling-up silica gel put into hang basket moisture eliminator with 60 ℃ of distilled water with 400 liters/hour flow velocity flushing, the solution ph that stays after the flushing is 7.Used cold distilled water immersion again 4 hours, same soak solution PH is 7.At last, with discharging after distilled water immersion 6-8 hour, balling-up silica gel shifts out and hangs basket, send into moisture eliminator in 110-120 ℃ dry 7-8 hour down, place muffle furnace or high temperature rotating disk baking oven in 300 ℃ of thermal treatments 1 hour again, the rerum natura that the chance water that makes Different Pore Structures after the cooling is not cleaved into ball silica gel is as follows:
Outward appearance is a White-opalescent garden ball, and particle diameter is 4.8-5.8mm, and compressive strength is greater than 6kg/, and tap density is 0.43-0.47g/ml, and specific surface area is 160-190m
2/ g, pore volume 0.80-0.95ml/g is through three cracked rates of wet dry-cure repeatedly
*Less than 1%, wear rate
*(less than the weight of 2.5mm particle and powder) less than 3%, average pore radius is 102
Largest hole dilatation percentage is seen Fig. 2 to average pore diameter distribution plan (desorption).
Note:
*Through three cracked rates of wet dry-cure repeatedly:
The cracked amount of particle accounts for the percentage ratio of total amount behind the imitated catalyst soakage that is equipped with, dry process repeated treatments three times.
*Wear rate:
It is that 56 rev/mins tube grinds after 8 hours the percentage ratio that accounts for total amount less than the weight of the particle of 2.5mm and powder that balling-up silica gel is put into rotating speed.
Example 4
Press the method and the operational condition of example 3, change solution pressurized heat processing pressure, the balling-up silica gel that can make different specific surface areas and aperture is referring to table 1
The relation of table 1 balling-up silica gel pore structure characteristic and solution pressurized heat processing pressure
Example 5
Adopt the method for three wet dry-cure repeatedly, bead silica gel that forming oil column is made and the chance water that makes with the inventive method not ripper have the balling-up silica gel of certain pore structure, oppose than test, and data are listed in table 2.
Example 6
Handle and handle balling-up silica gel without the solution pressurized heat and make carrier through the solution pressurized heat, after making noble metal component and be the catalyzer that shell distributes, with ethene, oxygen and acetic acid is in the reaction of raw material synthesizing vinyl acetate, in comparing test on the single hose system under the same process condition, test-results is listed in table 3.
Test conditions:
Reaction pressure: 8kg/cm
2;
Air speed: 2100hr
-1
Reactant ratio: C
2H
4: O
2: CH
3COOH: H
2O
=74.8: 5.2: 20: the 1-1.5(volume ratio)
Illustrate that the silica-gel carrier that adopts the inventive method gained prepares the catalyzer of ethylene process vinyl acetate between to for plastic, can satisfy to reach the pore structure that reaction requires, obviously improve the selectivity of reaction product.
Example 7
Handle and handle balling-up silica gel without the solution pressurized heat and make carrier through the solution pressurized heat, make phosphoric acid-silica-gel catalyst, be used for the reaction of propylene direct hydration preparing isopropanol and the results are shown in table 4.
Claims (3)
1, a kind of with silica gel of powder and silicon sol, rolling balling-up preparation can be regulated Different Pore Structures, and the method for the silica gel that chance water does not split is characterized in that the raw material silica gel that uses can be the work in-process without calcining and activating, cracked or not cracked finished product, its powder size is less than 150 μ.With contain certain density silicon sol and mix, put on the tumbling disk granulator, control a certain proportion of silica-gel powder and silicon sol, the rolling balling-up.After surperficial polishing, it is aging to carry out gelling in the immigration encloses container, and the gelling aging temperature is 10-40 ℃, the gelling digestion time is 24-500 hour, dries in the immigration dish again, and drying envrionment temperature is 10-40 ℃, drying relative humidity is 60-85%, and flash-off time is 12-500 hour.Then, drying, high-temperature roasting, cooling makes the silica gel finished product.This silica gel is put into autoclave, carrying out the solution pressurized heat handles, the mixing salt that the aqueous solution that adds is formed by acetic acid, ammonium acetate, ammonium hydroxide, ammonium chloride, sodium bicarbonate, sodium sulfate or by lithium chloride, sodium-chlor, saltpetre etc. one or more compounds are formulated, and the concentration of the maintenance aqueous solution is the 0.05-0.2 equivalent.Every liter of silica gel adds the aqueous solution that 1.2-10 rises, and keeping aqueous ph value is 2-10, and pressure build up, carries out the solution pressurized heat and handles, and pressure is 1-100kg/cm
2, after the solution pressurized heat treatment time is 1-40 hour, takes out balling-up silica gel and be washed with distilled water to neutrality, drying, the high temperature roasting is watered, and cooling makes to have the water of chance and not to split the silica gel of certain pore structure.
2, according to the described method for preparing silica gel of claim 1, it is characterized in that preparing used condition, with the silica gel of powder granularity less than 85 μ, the gelling aging temperature is not less than 20 ℃, the gelling digestion time is more than 48 hours, flash-off time is more than 24 hours, and envrionment temperature is 25-35 ℃ when drying, and relative humidity is 70-80% the best when drying.
3, according to the described method for preparing silica gel of claim 1, it is characterized in that the used condition of solution pressurized heat processing, with aqueous ph value 5-6, solution pressurized heat processing pressure 6kg/cm
2, 10 hours solution pressurized heat treatment times the best.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN87100996.XA CN1005404B (en) | 1987-03-02 | 1987-03-02 | Method for preparing silica gel with adjustable pore structure and without cracking when meeting water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN87100996.XA CN1005404B (en) | 1987-03-02 | 1987-03-02 | Method for preparing silica gel with adjustable pore structure and without cracking when meeting water |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1031822A true CN1031822A (en) | 1989-03-22 |
| CN1005404B CN1005404B (en) | 1989-10-11 |
Family
ID=4813094
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN87100996.XA Expired CN1005404B (en) | 1987-03-02 | 1987-03-02 | Method for preparing silica gel with adjustable pore structure and without cracking when meeting water |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1005404B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1090589C (en) * | 1995-10-24 | 2002-09-11 | 水泽化学工业株式会社 | Macropore amplifying spherical silica-gel and its manufacturing method |
| CN102300636A (en) * | 2009-01-30 | 2011-12-28 | 旭化成化学株式会社 | Method for producing silica-supported catalyst, and method for producing unsaturated carboxylic acid or unsaturated nitrile |
| CN101884916B (en) * | 2009-05-13 | 2012-05-30 | 中国石油化工股份有限公司 | Method for preparing catalyst carrier used for preparing vinyl acetate by fluidized bed process |
| CN102701225A (en) * | 2012-03-20 | 2012-10-03 | 中国科学院山西煤炭化学研究所 | Preparation method of starch modified silicon dioxide material |
-
1987
- 1987-03-02 CN CN87100996.XA patent/CN1005404B/en not_active Expired
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1090589C (en) * | 1995-10-24 | 2002-09-11 | 水泽化学工业株式会社 | Macropore amplifying spherical silica-gel and its manufacturing method |
| CN102300636A (en) * | 2009-01-30 | 2011-12-28 | 旭化成化学株式会社 | Method for producing silica-supported catalyst, and method for producing unsaturated carboxylic acid or unsaturated nitrile |
| US8772195B2 (en) | 2009-01-30 | 2014-07-08 | Asahi Kasei Chemicals Corporation | Method for producing silica-supported catalyst, and method for producing unsaturated carboxylic acid or unsaturated nitrile |
| CN102300636B (en) * | 2009-01-30 | 2015-01-07 | 旭化成化学株式会社 | Method for producing silica-supported catalyst, and method for producing unsaturated carboxylic acid or unsaturated nitrile |
| US9000207B2 (en) | 2009-01-30 | 2015-04-07 | Asahi Kasei Chemicals Corporation | Method for producing silica-supported catalyst, and method for producing unsaturated carboxylic acid or unsaturated nitrile |
| CN101884916B (en) * | 2009-05-13 | 2012-05-30 | 中国石油化工股份有限公司 | Method for preparing catalyst carrier used for preparing vinyl acetate by fluidized bed process |
| CN102701225A (en) * | 2012-03-20 | 2012-10-03 | 中国科学院山西煤炭化学研究所 | Preparation method of starch modified silicon dioxide material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1005404B (en) | 1989-10-11 |
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