CN1120987A - Method of preparing composite superfine powder with metal surfactant by phase transfer - Google Patents
Method of preparing composite superfine powder with metal surfactant by phase transfer Download PDFInfo
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- CN1120987A CN1120987A CN 94117470 CN94117470A CN1120987A CN 1120987 A CN1120987 A CN 1120987A CN 94117470 CN94117470 CN 94117470 CN 94117470 A CN94117470 A CN 94117470A CN 1120987 A CN1120987 A CN 1120987A
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Abstract
Mixed metal salt is used to prepare colloid and metal surfactant is adsorbed in colloid particles, which are first phase-transfered to enter organic solvent and then made into composite superfine powder through dewatering, removal of organic solvent, drying and burning. The said method can obtain composite powder with a granularity of 20-30 angstroms and is suitable to produce catalyst, adsorbent, ceramic powder, etc.
Description
The present invention relates to a kind of preparation method of composite superfine powder.
Superfine powder is used extremely wide in chemical process, as is used for controlling catalyst and catalyst carrier, is used for adsorbent etc.Superfine powder also is used to building trade, as is used to make cement.Superfine powder also can be used for aerospace industry in addition, uses also more and more wider at field of medicaments.
The preparation of superfine powder divides physical method and chemical method two big classes.Physical method such as spray drying process, colloid milling, plasma spray pyrolysis etc., products thus obtained granularity is in μ m level.Chemical method has freeze-drying, and supercritical fluid drying, its juche idea are to reduce the interfacial tension of particle.Above method all needs special installation to reach than exacting terms.
SURFACTANT ADSORPTION can reduce its interfacial tension in colloid surface, thus thought set out SersiroIto etc. (Shizai Kyokaishi57 (7) 394-402 (198)) with anion surfactant DBS and organic solvent with ALOH
3Colloid is shifted by water and enters organic facies (we are referred to as phase transfer method) and distill then except that desolvating and water makes the AL that granular size is 100
2O
3Powder, but this preparation method can stay sulfate radical and can not be used to make composite superfine powder in product.The inventor once made the Cu-ZnO/Al that granular size is 30 with the cationic surfactant phase transfer
2O
3Catalyst is only applicable to do with ammoniacal liquor etc. the preparation of precipitating reagent but this method is difficult for washing.(Chinese patent notification number CN1057818A) such as nearest Tang Fangqiong also makes hydrophobic SiO with surfactant, and its method only is to make its hydrophobisation and complicated operation also need special installation existing superfine powder, is difficult to industrialization.
The purpose of this invention is to provide a kind of easy and simple to handlely, easily washing can prepare the method for composite superfine powder.
The method of preparing composite superfine powder with metal surfactant by phase transfer of the present invention comprises the steps:
(1) preparation of colloid and phase transfer program:
A: the preparation of colloid: mixed salt solution is splashed into precipitant solution while stirring, the equivalent concentration of its slaine and precipitating reagent is 0.01-8.00N, final PH5.0-9.0,120 rev/mins-480 rev/mins of mixing speeds, can add deflocculant in the colloid for preparing process, its addition is between 20-4000 gram/mol metal surfactant
B. phase transfer: metal surfactant is added organic solvent, the aqueous solution that then this organic solvent solution is added colloid, stirring makes colloid generation phase transfer, the consumption of organic solvent is in 660ml-3300ml/mol colloid scope, the consumption of metal surfactant is between the 0.010-0.900mol/mol colloid, can add synergist in the phase transition behavior, its consumption is between the 0.2-4.0mol/mol metal surfactant, and the rotating speed of stirring is at 300-1000 rev/min.
(2) washing and dehydration and take off organic solvent.
Above-mentioned mixed liquor was left standstill 15 minutes-24 hours, preferably 1-4 hour, the bottom is close to transparent aqueous solution removes with separatory funnel, add distilled water in the top organic layer and stirred 3-60 minute, rotating speed is 300-1000 rev/min, left standstill 15 minutes-24 hours, and removed the bottom aqueous solution and add distilled water and 3-10 back filtration of above repeatedly operation again.
(3) drying: the filter cake 105-160 after the filtration ℃ was dried by the fire 1-8 hour, or airing, but also vacuum drying.
(4) calcination: 0.5-10 ℃/minute was warming up to 300-650 ℃ of calcination 2-24 hour.
The preparation of said colloid and phase transfer can also be carried out like this in the said method: metal surfactant and deflocculant are added the precipitating reagent aqueous solution, while stirring metal salt solution is splashed into precipitating reagent aqueous solution glue then, synergist is added organic solvent and organic solvent is added stirring generation phase transfer in the colloidal solution.
The preparation of said colloid and phase transfer can also be carried out like this in the said method: aqueous metal salt is splashed into while stirring the precipitating reagent aqueous solution glue that is added with stabilizing agent, synergist and metal surfactant are dissolved in organic solvent, mix two solution and stirring.
The preparation of said colloid and phase transfer can also be carried out like this in the said method: metal surfactant and stabilizing agent are added the precipitating reagent aqueous solution and add organic solvent and synergist, metal water solution is splashed into above liquid while stirring.
Said metal surfactant can be a carboxylate in the said method, and also the method by organic synthesis connects an organic chain and makes with complexing of metal ion then on metal chelating agent, and its organic chain length should can be enuatrol at four more than the carbon.
Said organic solvent can be benzene, dimethylbenzene, industrial crude benzol, benzinum in the said method, also industrial solvent, its solvent oil grade preferably No. 60, No. 120 or No. 210.
In the said method said synergist be carbon chain lengths at fatty alcohol more than 8 or fatty amine, can
Said stabilizing agent is HLB at 6 to 13 non-ionic surface active agent in the said method, can be Span80.
Basic thought of the present invention is: with metal surfactant be adsorbed in colloidal particle surface and with its transfer enter organic solvent and moisture from, the absorption of surfactant has prevented that effectively the gathering of colloidal particle from growing up and crystallization again, can get superfine powder thereby remove organic moiety by dry calcination.Compare with the preparation method of existing superfine powder, the present invention has following advantage:
1. do not need special main equipment.
2. do not need harsh preparation condition such as HTHP.
3. easy industrialization easy and simple to handle.
4. cost low (the solvent major part can reclaim).
Embodiment 1
The preparation 1 of CuZnAl catalyst
1. glue and phase transfer
A. glue: 1.00 gram Span80 (stabilizing agent) are added in the ammonia spirit of 1.6N40 milliliters, splash into while stirring 0.4N nitrate (copper: zinc: aluminium=6: 3: 1) solution is 150 milliliters, about 180 rev/mins of mixing speed, final PH is 7.3,
B. phase transfer: enuatrol (surfactant) 4.17 grams are dissolved in 100 milliliters of benzinums (organic solvent), add 5 milliliters of lauryl alcohols (synergist) again, this mixed liquor is injected above colloidal solution, stirred 60 minutes with 360 rev/mins rotating speeds.
2. washing and dehydration and take off organic solvent
A. washing: left standstill after the phase transfer 10 hours, and removed bottom water, add 300 milliliters of distilled water, stirred 20 minutes, left standstill 10 hours, remove bottom water, repeat above operation 2 times with separatory funnel with 360 rev/mins rotating speeds in the top organic layer with separatory funnel,
B. dewater and take off organic solvent: remove water liquid filtration under diminished pressure then in bottom after having washed.
3. dry: 140 ℃ of bakings 2 hours.
4. calcination: rise surely to 450 ℃ of calcinations 4 hours with 2 ℃/minute.
Product is 140m with the specific area that ST-03 specific area pore size determination instrument records
2/ g.
Embodiment 2
The preparation 2 of CuZnAl catalyst
1. glue and phase transfer
A. glue: silicic acid 1.2000 grams (surfactant) and 0.05 gram Span80 (stabilizing agent) are added in the ammonia spirit of 1.6N 44ml, (copper: zinc: aluminium=6: 3: 1) solution is 150 milliliters to splash into the nitrate of 0.4N while stirring, it stirs speed is about 180 rev/mins, and final PH is 7.3
B. phase transfer: in 100 milliliters of lauryl alcohol (synergist) 5 milliliters of addings benzinums (organic solvent), this mixed liquor is injected above colloidal solution, stirred 60 minutes with 360 rev/mins rotating speeds,
2. washing and dehydration and take off organic solvent
Left standstill after the phase transfer 2 hours, and removed bottom water filtration under diminished pressure then with separatory funnel.
3. dry: 140 ℃ of bakings 2 hours.
4. calcination: rise surely to 350 ℃ of calcinations 4 hours with 2 ℃/minute.
It is 20-30 that product amplifies 100,000 times of its granular sizes of taking pictures with HITACHI H-600 transmission electron microscope.
Embodiment 3
Make super AL
2O
3
Restrain in the ammonia spirit that adds 52 milliliters of 1.6N silicic acid 3.6000 grams (surfactant) and Span80 2.00 (stabilizing agent) and stirring, add 100 milliliters of 5 milliliters of lauryl alcohols (synergist) and benzinums (organic solvent) and splash into 150 milliliters of the aluminum nitrate solutions of 0.4N while stirring, it stirs speed is about 180 rev/mins, its final PH is about 7.3, the rotating speed that continue with 360 rev/mins the intact back of titration stirred 30 minutes
2. washing and dehydration and take off organic solvent
Left standstill after the phase transfer 10 hours, and removed bottom water filtration under diminished pressure then with separatory funnel.
3. dry: 140 ℃ of bakings 2 hours
4. calcination: rise surely to 350 ℃ of calcinations 4 hours with 2 ℃/minute.
It is 20-30A that product amplifies 100,000 times of its granular sizes of taking pictures with HITACHI H-600 transmission electron microscope.
Claims (8)
1. the method for a preparing composite superfine powder with metal surfactant by phase transfer is characterized in that comprising the steps:
(1) preparation of colloid and phase transfer
A. the preparation of colloid: mixed salt solution is splashed into precipitant solution while stirring, the equivalent concentration 0.01-8.00N of slaine and precipitating reagent, final PH5.0-9.0, mixing speed 120-480 rev/min, can add deflocculant in the colloid for preparing process, addition is a 20-4000 gram/mol metal surfactant
B. phase transfer: metal surfactant is added organic solvent, the aqueous solution that then this organic solvent is added colloid, stirring makes colloid generation phase transfer, the consumption of organic solvent is in 660ml-3300ml/mol colloid scope, the consumption of metal surfactant is the 0.010-0.900mol/mol colloid, can add synergist in the phase transition behavior, and consumption is the 0.2-4.0mol/mol metal surfactant, speed of agitator 300-100 rev/min
(2) washing and dehydration and take off organic solvent.
Above-mentioned mixed liquor was left standstill 15 minutes-24 hours, preferably 1-4 hour, the bottom is close to transparent aqueous solution removes with separatory funnel, add distilled water in the top organic layer and stirred 3-60 minute, rotating speed 300-1000 rev/min, left standstill 15 minutes-24 hours, and removed the bottom aqueous solution and add distilled water and 3-10 back filtration of above repeatedly operation again
(3) drying: the filter cake after the filtration was 105-160 ℃ of baking 1-8 hour, or airing, but also vacuum drying.
(4) calcination: 0.5-10 ℃/minute was warming up to 300-650 ℃ of calcination 2 to 24 hours.
2. according to the said method of claim 1, the preparation and the phase transfer that it is characterized in that described colloid can also be to be undertaken by following program: metal surfactant and deflocculant are added the precipitating reagent aqueous solution, while stirring metal salt solution is splashed into precipitating reagent aqueous solution glue then, synergist is added organic solvent and organic solvent is added stirring generation phase transfer in the colloidal solution.
3. method according to claim 1, the preparation and the phase transfer that it is characterized in that described colloid can also be to be undertaken by following program: metal surfactant and stabilizing agent are added the precipitating reagent aqueous solution and add organic solvent and synergist, aqueous metal salt is splashed into above liquid while stirring.
4. method according to claim 1, the preparation and the phase transfer that it is characterized in that described colloid can also be to be undertaken by following program: aqueous metal salt is splashed into while stirring the precipitating reagent aqueous solution glue that is added with stabilizing agent, synergist and metal surfactant are dissolved in organic solvent, mix two solution and stirring.
5. method according to claim 1, it is characterized in that metal surfactant is a carboxylate, also can be that method by organic synthesis connects an organic chain and makes with complexing of metal ion then on metal chelating agent, the organic chain length of metal surfactant should can be enuatrol at four more than the carbon.
6. method according to claim 1 is characterized in that organic solvent can be benzene, dimethylbenzene, industrial crude benzol, benzinum, also can be industrial solvent, its solvent oil grade preferably No. 60, No. 120 or No. 210.
7. method according to claim 1, it is characterized in that synergist be carbon chain lengths at fatty alcohol more than 8 or fatty amine, can be lauryl alcohol.
8. method according to claim 1 is characterized in that stabilizing agent is HLB at 6 to 13 non-ionic surface active agent, can be Span80.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94117470A CN1051524C (en) | 1994-10-20 | 1994-10-20 | Method of preparing composite superfine powder with metal surfactant by phase transfer |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94117470A CN1051524C (en) | 1994-10-20 | 1994-10-20 | Method of preparing composite superfine powder with metal surfactant by phase transfer |
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| Publication Number | Publication Date |
|---|---|
| CN1120987A true CN1120987A (en) | 1996-04-24 |
| CN1051524C CN1051524C (en) | 2000-04-19 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94117470A Expired - Fee Related CN1051524C (en) | 1994-10-20 | 1994-10-20 | Method of preparing composite superfine powder with metal surfactant by phase transfer |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1060703C (en) * | 1996-05-30 | 2001-01-17 | 北京有色金属研究总院 | Method for preparing nanometre metal powder |
| CN1108858C (en) * | 1999-01-04 | 2003-05-21 | 北京大学 | Nanometer grade transtion metal and its alloy colloid and prepn. method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2623791B1 (en) * | 1987-11-30 | 1990-04-06 | Rhone Poulenc Chimie | PROCESS FOR THE PREPARATION OF GRANULES BASED ON ALUMINUM OXIDE AND PRODUCTS THUS OBTAINED |
| JPH01290508A (en) * | 1988-05-18 | 1989-11-22 | Tosoh Corp | Production of metal oxide |
-
1994
- 1994-10-20 CN CN94117470A patent/CN1051524C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1060703C (en) * | 1996-05-30 | 2001-01-17 | 北京有色金属研究总院 | Method for preparing nanometre metal powder |
| CN1108858C (en) * | 1999-01-04 | 2003-05-21 | 北京大学 | Nanometer grade transtion metal and its alloy colloid and prepn. method thereof |
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| Publication number | Publication date |
|---|---|
| CN1051524C (en) | 2000-04-19 |
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