CN1054780C - Method of preparing coated superfine powder with metal surfactant by phase transfer - Google Patents
Method of preparing coated superfine powder with metal surfactant by phase transfer Download PDFInfo
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- CN1054780C CN1054780C CN94117468A CN94117468A CN1054780C CN 1054780 C CN1054780 C CN 1054780C CN 94117468 A CN94117468 A CN 94117468A CN 94117468 A CN94117468 A CN 94117468A CN 1054780 C CN1054780 C CN 1054780C
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Abstract
The present invention provides a method for preparing coated ultrafine powder by the phase transfer of metal surface active agents. Mixed metal salts are prepared to be colloid, then, the colloid is transferred in organic solvents after the metal surface active agents are absorbed on the colloid by a phase transfer program, and the coated ultrafine powder is obtained after drying and calcination. In the method, in the process of the phase transfer, the metal surface active agents which are different from metal contained by the colloid, and therefore, the ultrafine powder, in which one kind of metal oxides (derived from the metal surface active agents) is coated on the surface of the other kind of metal oxides or salts (carriers) can be obtained. The covering rate can reach almost 100%, but the content of active constituents is low.
Description
The present invention relates to a kind of preparation method of coated 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.But often a kind of active constituent loading need be made it that intensity and heat endurance are arranged preferably on carrier mass and can save the active component consumption as catalyst and adsorbent, that is to say as catalyst and adsorbent to have bigger specific area also to need big active surface area, and this just needs active component to be dispersed in the surface of carrier uniformly as far as possible.The classical carrying method of active component is an infusion process, promptly at a certain temperature carrier is inserted to reach in the solution that is dissolved with macerate and take out dry calcination behind the certain hour, but the surface tension effects of liquid can cause the uneven distribution of loaded article in the product in dry calcination process.
The object of the present invention is to provide a kind of new superfine powder preparation method that active component is evenly coated at carrier surface.
The method of metal surfactant phase transfer system coated superfine powder of the present invention is carried out as follows:
(1). the preparation of colloid: mixed salt solution is splashed into precipitant solution while stirring, the equivalent concentration 0.01-8.00N of its slaine and precipitating reagent, its final PH is between 5.0-9.0, mixing speed is between 120-480 rev/min, can add deflocculant in the colloid for preparing process, its addition is a 20-4000 gram/mol metal surfactant
(2). phase transfer program: metal surfactant is added organic solvent, the aqueous solution that then this organic solvent is added colloid, stirring makes colloid generation phase transfer, mixing time 1-20 minute, the consumption of organic solvent is in 660ml-3300ml/mol colloid scope, can add synergist in the phase transition behavior, its consumption is at the 0.05-4mol/mol metal surfactant, the demulsifying agent consumption is between the 0.10-10.00mol/mol metal surfactant, its consumption of defoamer is the 0.20-2.00mol/mol metal surfactant, the consumption of metal surfactant between the 0.010-0.900mol/mol colloid, speed of agitator 300-1000 rev/min
(3). the washing and the dehydration and take off organic solvent: after glue and the phase transfer mixture was left standstill 15 minutes-24 hours, this moment, the bottom was removed the bottom aqueous solution for being close to transparent aqueous solution with separatory funnel, add distilled water in the top organic layer and stirred 2-20 minute, rotating speed is 180-780 rev/min, left standstill 15 minutes-24 hours, remove the bottom aqueous solution add again distilled water and repeatedly more than operate 3-10 back filtration
(4). drying: the filter cake 105-160 after the filtration ℃ was dried by the fire 1-8 hour, or airing, but also vacuum drying,
(5). calcination: 0.5-10 ℃/minute was warming up to 300-650 ℃ of calcination by 2-24 hour.
Said metal surfactant can be the carboxylate of non-monovalence in the said method, as laurate copper, zinc laurate, 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 be 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 be lauryl alcohol.
Said stabilizing agent is the non-ionic surface active agent of HLB at 6-13 in the said method, can be Span80.
Said defoamer is that the carbon source subnumber is the carboxylic acid of 3-8 in the said method, can be valeric acid.
Different as metal surfactant institute containing metal in phase transition behavior with colloid institute containing metal, then can make the superfine powder that a kind of metal oxide (coming from metal surfactant) is coated on another kind of metal oxide or salt surface (carrier).The thickness that coats is 1 to several atomic layers.Because metal surfactant is adsorbed on colloid surface, so metal surfactant has stronger affinity on colloid in the dry run of phase transfer, and is especially all the more so when the excessive and colloid surface of precipitating reagent is adsorbed with the precipitating reagent anion.The surface tension of organic solvent is more much smaller than water in addition, so dry run can not cause the uneven distribution of adsorbate.It is nearly 100% to adopt the coverage rate of its active component of the prepared coated superfine powder of method of the present invention on carrier to reach, but the content of active component can be very little, the peculiar meaning of this preparation to noble metal catalyst.In addition, active component covers evenly at carrier surface, and is strong with carrier interactions, and this to the preparation of catalyst, adsorbent, sensing material all highly significant.
The preparation of cupric oxide coated aluminum oxide carrier superfine catalyst
1. glue: 5.37ml ammoniacal liquor is added 45ml water and add 1.00 gram Span80, the aluminum nitrate solution with 50ml0.36M splashes in the above ammonia spirit while stirring then, and mixing speed is 180 rev/mins,
2. phase transfer: the petroleum ether solution of cinnamic acid copper surfactant is joined in the colloidal solution, add lauryl alcohol (synergist) 2 milliliters, n-hexyl alcohol (demulsifying agent) 4ml, valeric acid 0.30mol/mol metal surfactant, stirred 20 minutes with 600 rev/mins rotating speeds
The washing and the dehydration and take off organic solvent: left standstill after the phase transfer 2 hours, and removed bottom water with separatory funnel and filter then,
4. dry: be warmed up to 140 ℃ with 1 ℃/minute and dried by the fire 2 hours,
5. calcination: be warming up to 350 ℃ of calcinations 4 hours with 2 ℃/minute.
Product amplifies 100,000 times with HITACHI H-600 Electronic Speculum microscope, and single particle can be as small as 20-30 as can be seen.
The preparation of cupric oxide and zinc oxide bag alumina support superfine catalyst
4.72ml ammoniacal liquor and 0.040 gram Span80 are added in the 70ml water, aluminum nitrate solution with 75ml 0.30M splashes in the above ammonia spirit while stirring then, mixing speed is 180 rev/mins, phase transfer is made surfactant with laurate copper and zinc laurate (1: 1), and other condition is all with embodiment 1.
Product amplifies 100,000 times with HITACHI H-600 Electronic Speculum microscope, and single particle can be as small as 20 as can be seen, and the specific area of this sample is 478m
2/ g, Fig. 1 distributes in conjunction with the footpath that argon ion loses the elemental copper zinc that records mutually for XPS, growth elemental copper zinc along with etch period reduces gradually as can be seen, it is that XPS is the information of about 100 what this detected that elemental copper zinc content is not kept to zero reason, and product particle 20-30 only, the carrying out of putting along with etching constantly has new particle to come out.
The ultra-fine preparation of urging the agent powder of alumina-coated Zirconia carrier
1. glue: 2.00 gram Span80 are added 73ml 0.30M and Na
2CO
3The aqueous solution and splash into the zirconyl nitrate aqueous solution of 75ml 0.30M while stirring, mixing speed is 180 rev/mins,
2. phase transfer joins the petroleum ether solution of copper oleate surfactant in the colloidal solution, adds lauryl alcohol (synergist) 6 milliliters, and positive ethanol (demulsifying agent) 6ml stirred 20 minutes with 600 rev/mins rotating speeds,
The washing and the dehydration and take off organic solvent: left standstill after the phase transfer 2 hours, remove bottom water with separatory funnel, adding distilled water 300ml then stirred 20 minutes with 600 rev/mins rotating speed, left standstill 2 hours, remove bottom water with separatory funnel, add distilled water 300ml then again, 5 times so repeatedly, filter
4. dry: be warmed up to 140 ℃ with 1 ℃/minute and dried by the fire 2 hours,
5. calcination: be warming up to 350 ℃ of calcinations 4 hours with 2 ℃/minute.
Claims (10)
1. the method for a metal surfactant phase transfer system coated superfine powder is characterized in that comprising the steps:
(1) preparation of colloid: mixed salt solution is splashed into precipitant solution while stirring, the equivalent concentration of its slaine and precipitating reagent is between 0.01-8.00N, its final PH is between 5.0-9.0, mixing speed is between 120-480 rev/min, can add deflocculant in the colloid for preparing process, its addition is between 20-4000 gram/mol metal surfactant
(2) phase transfer program: metal surfactant is added organic solvent, the aqueous solution that then this organic solvent is added colloid, stirring makes colloid generation phase transfer, mixing time 1-20 minute, the consumption of organic solvent is in 660-3300ml/mol colloid scope, can add synergist in the phase transition behavior, its consumption is at the 0.05-4mol/mol metal surfactant, the demulsifying agent consumption is between the 0.10-10.00mol/mol metal surfactant, the defoamer consumption is the 0.20-2.00mol/mol metal surfactant, the consumption of metal surfactant between the 0.010-0.900mol/mol colloid, speed of agitator 300-1000 rev/min
(3) washing and the dehydration and take off organic solvent: after glue and the phase transfer mixture was left standstill 15 minutes-24 hours, this moment, the bottom was removed the bottom aqueous solution for being close to transparent aqueous solution with separatory funnel, add people's distilled water in the top organic layer and stirred 2-20 minute, rotating speed is 180-780 rev/min, left standstill 15 minutes-24 hours, remove the bottom aqueous solution and add distilled water and 3-10 back filtration of above repeatedly operation again
(4) drying: the filter cake after the filtration was 105-160 ℃ of baking 1-8 hour, or airing, but also vacuum drying,
(5) calcination: 0.5-10 ℃/minute programming rate rises to 300-650 ℃ of calcination 2-24 hour.
2. method according to claim 1, it is characterized in that metal surfactant is the metal carboxylate of non-monovalence, the method by organic synthesis connects an organic chain and makes with complexing of metal ion then on metal chelating agent, its organic chain length should be at four more than the carbon.
3. method according to claim 2 is characterized in that metal surfactant is laurate copper or zinc laurate.
4. method according to claim 1 is characterized in that organic solvent is benzene, dimethylbenzene, industrial crude benzol, benzinum or industrial solvent.
5. method according to claim 1 is characterized in that synergist is a carbon chain lengths at the fatty alcohol more than 8 or carbon chain lengths at the fatty amine more than 8.
6. method according to claim 1 is characterized in that stabilizing agent is the non-ionic surface active agent of HLB at 6-13.
7. method according to claim 1 is characterized in that defoamer is that carbon number is the carboxylic acid of 3-8.
8. method according to claim 1 is characterized in that synergist is a lauryl alcohol.
9. method according to claim 1 is characterized in that stabilizing agent is Span80.
10. method according to claim 1 is characterized in that defoamer is a valeric acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94117468A CN1054780C (en) | 1994-10-20 | 1994-10-20 | Method of preparing coated superfine powder with metal surfactant by phase transfer |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94117468A CN1054780C (en) | 1994-10-20 | 1994-10-20 | Method of preparing coated superfine powder with metal surfactant by phase transfer |
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| Publication Number | Publication Date |
|---|---|
| CN1120978A CN1120978A (en) | 1996-04-24 |
| CN1054780C true CN1054780C (en) | 2000-07-26 |
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| CN94117468A Expired - Fee Related CN1054780C (en) | 1994-10-20 | 1994-10-20 | Method of preparing coated superfine powder with metal surfactant by phase transfer |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1067967C (en) * | 1998-09-11 | 2001-07-04 | 清华大学 | Superfine titanium white surface cladding tech. and reactor thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS64209A (en) * | 1987-06-22 | 1989-01-05 | Tanaka Kikinzoku Kogyo Kk | Production of fine gold particles |
| JPH0215101A (en) * | 1988-07-04 | 1990-01-18 | Matsushita Electric Ind Co Ltd | Ultra fine particle and manufacture thereof |
| EP0370939A2 (en) * | 1988-11-24 | 1990-05-30 | Universidad De Santiago De Compostela | Process to obtain fine magnetic Nd-Fe-B particles of various sizes |
| JPH04280814A (en) * | 1991-03-11 | 1992-10-06 | Hayashi Kinzoku Kogyosho:Kk | Production of ultrafine particulate zinc white |
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1994
- 1994-10-20 CN CN94117468A patent/CN1054780C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS64209A (en) * | 1987-06-22 | 1989-01-05 | Tanaka Kikinzoku Kogyo Kk | Production of fine gold particles |
| JPH0215101A (en) * | 1988-07-04 | 1990-01-18 | Matsushita Electric Ind Co Ltd | Ultra fine particle and manufacture thereof |
| EP0370939A2 (en) * | 1988-11-24 | 1990-05-30 | Universidad De Santiago De Compostela | Process to obtain fine magnetic Nd-Fe-B particles of various sizes |
| JPH04280814A (en) * | 1991-03-11 | 1992-10-06 | Hayashi Kinzoku Kogyosho:Kk | Production of ultrafine particulate zinc white |
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