CN104138760A - Stanniferous catalyst promoter - Google Patents
Stanniferous catalyst promoter Download PDFInfo
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- CN104138760A CN104138760A CN201410346117.5A CN201410346117A CN104138760A CN 104138760 A CN104138760 A CN 104138760A CN 201410346117 A CN201410346117 A CN 201410346117A CN 104138760 A CN104138760 A CN 104138760A
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Abstract
Provided is a stanniferous catalyst promoter. The stanniferous catalyst promoter is used for an organosilicone monomer synthetic reaction and preferentially selected as a catalyst promoter in a dimethyl dichlorosilane synthetic reaction copper base catalysis system. Tin is evenly distributed and combined with a carrier, so that on one hand, uniform mixing of tin, silicon and the like in a fluidized bed is facilitated, and reaction efficiency is improved; on the other hand, unnecessary losses of tin in the industrial production are lowered. Compared with the method that tin is added to a fluidized bed reaction system in a granular metal tin powder manner in the prior art, the stanniferous catalyst promoter has the advantages that the content of harmful impurities of tin components is low, purity is high, the tin-assisted catalyst components can be evenly added to a synthetic reaction system when the stanniferous catalyst promoter is used for organosilicone monomer synthesis, the utilization efficiency of tin is improved, oxidation films on silica powder and surfaces of contacts can be well eliminated, activity of the synthetic reaction can be improved, the space time yield of the fluidized bed is increased, cost of industrial production is reduced, and remarkable economical benefits are obtained.
Description
Technical field
The present invention relates to organic silicon monomer synthetic reaction, particularly the co-catalyst field in copper base catalyst system and catalyzing in dimethyldichlorosilane synthetic reaction, more concrete, relates to a kind of containing tin promoter.
Background technology
Dimethyldichlorosilane, industrial diformazan or the M2 of being called again, is a kind of most important organic silicon monomer, and its consumption accounts for the more than 90% of whole monomer total amount, the organosilyl downstream product of preparation, such as the important source material of silicone oil, silicon rubber, silicones and silane coupler etc.
Dimethyldichlorosilane is to add catalyst (containing major catalyst and co-catalyst) by metallic silicon power, chloromethanes, and chemical synthesis in fluid bed under the condition of 300 ℃ of left and right, Gu gas-solid-heterogeneous contact catalytic exothermic reaction that its synthetic reaction belongs to, its reaction mechanism is complicated, except comprising the main reaction that generates diformazan, also there is multiple side reaction simultaneously.
The influence factor of the synthetic reaction process of dimethyldichlorosilane, comprises fluidized-bed structure, raw material silica flour, chloromethanes, catalyst (containing major catalyst and co-catalyst) and catalyst system and catalyzing, technological parameter (as fluidized-bed temperature and temperature homogeneity, gas speed and fluidized state etc.) etc.Wherein, the effective collocation of major catalyst and co-catalyst is used and will be produced important impact to selective, the silica flour conversion ratio of monomer synthetic reaction diformazan and space-time yield etc.
Generally seldom, but it is to suppressing generation of side reaction in dimethyldichlorosilane synthetic reaction, improves the selective of monomer synthetic reaction diformazan for the consumption of co-catalyst, and improves the aspects such as reactivity and all play very important effect.
In organic silicon monomer synthetic reaction, generally adopt copper base catalyst system and catalyzing, copper adds after reaction system, under certain temperature and the condition that has chloromethanes to exist, can be formed with silicon silicon-copper alloy contact of catalytic action, this silicon-copper alloy contact is to methylchlorosilane, and particularly vital effect is played in the generation of diformazan.
Copper-based catalysts system is mainly divided into again Metal Substrate sheet pure copper powder, sheet metal pure copper powder for example, compound copper powder, the sprills such as the alloy sheet such as copper and copper-zinc-Xi, and ternary copper powder, for example Cu-Cu
2copper oxide catalyst three classes of tri-kinds of thing phase compositions of O-CuO.Wherein, in sheet metal pure copper powder and ternary copper powder catalyst system and catalyzing, need other increase auxiliary agent zinc (Zn), tin (Sn), phosphorus (P) etc. to help and urge constituent element, same, in compound copper powder catalyst system, also to help and urge constituent element according to need to add zinc (Zn), tin (Sn), the phosphorus (P) etc. of reaction.
In prior art, the co-catalyst tin in copper-based catalysts system normally joins in the reaction system of fluid bed with simple substance graininess tin (Sn) (or claiming metal Sn) or the form of copper-ashbury metal powder (Cu-Sn alloy).Because the amount of the tin adding in fluidized-bed reaction system is original just few, and these tin that join fluid bed are often difficult to realize well-proportioned mixing with silica flour, copper powder, co-catalyst tin constituent element is just difficult to give full play to promoting catalysis, and the synthetic reaction in fluid bed cannot reach best state.In addition, at industrial fluidized bed state, occur that when unstable, the ultra-fine grain in part glass putty, particularly glass putty is easy to take out of or skewness in bed from local channel, this all will make reaction cannot reach optimum efficiency, cannot give full play to tin as the effect of co-catalyst.
Summary of the invention
The present invention is directed in prior art, in organic silicon monomer synthetic reaction, add tin as the above-mentioned particular problem that helps catalysis still to exist, the invention provides a kind of containing tin promoter.
Of the present invention a kind of containing tin promoter, wherein tin is uniformly distributed and is combined on carrier.
The present invention is made to further restriction, as follows,
Described carrier includes but not limited in elemental metals copper and Cu oxide one or more any combination, Cu for example, CuO, Cu
2o, Cu-CuO, Cu-Cu
2o, CuO-Cu
2o, Cu-Cu
2o-CuO etc.;
Described carrier includes but not limited to metallic silicon power;
Described carrier also comprises the mixture of elemental metals copper and Cu oxide, metallic silicon power;
According to the content of Si in described carrier, the mass percent example of described a kind of thing phase containing main component in tin promoter:
(1) in carrier containing Si (mean containing Si lower than 100ppm time), or containing Si seldom time when (meaning containing Si lower than 1000ppm), described a kind of containing in tin promoter:
Cu (5～99.0%), Sn (0.05～90.0%), containing oxygen (0.05～20.0%), the plumbous objectionable impurities content that waits is lower, for example: Pb≤200ppm, Fe≤800ppm, other each metals content impurities individual event≤50ppm, other every nonmetallic inclusion individual event≤100ppm;
(2) while containing Si in carrier, described a kind of containing in tin promoter:
Cu (5～99.0%), Sn (0.05～90.0%), Si (1～99.0%), containing oxygen 0.05～19.8%, the plumbous objectionable impurities content that waits is lower, for example: Pb≤200ppm, Fe≤0.5%, other each metals content impurities individual event≤500ppm, other every nonmetallic inclusion individual event≤100ppm;
According to the composition of described carrier, the mass percent example of described a kind of thing phase containing main component in tin promoter:
(1) when carrier is metallic copper and/or Cu oxide powder, as Cu, CuO, Cu2O, Cu-CuO, Cu-Cu2O, CuO-Cu2O, during Cu-Cu2O-CuO, described a kind of containing in tin promoter:
Cu (5～99.0%), Cu
2o (0.05～90.0%), CuO (0.05～85.0%), Sn and/or containing alloy or the compound 0.05～90.0% of Sn;
(2) when carrier is metallic silicon (Si) powder, described a kind of containing in tin promoter:
Si (1～99.0%), Sn and/or containing alloy or the compound 0.05～90.0% of Sn;
(3) when carrier is the mixture of metallic copper and/or Cu oxide powder, metallic silicon (Si) powder, described a kind of containing in tin promoter:
Cu (5～95.0%), Cu
2o (0.05～85.0%), CuO (0.05～80.0%), Si (1～98.0%), Sn and/or containing alloy or the compound 0.05～90.0% of Sn;
Described is a kind of containing tin promoter, wherein said tin can derive from one or more any combination including but not limited in elemental metals tin, stanniferous alloy, stanniferous compound, wherein said stanniferous alloy includes but not limited to signal bronze (Cu-Sn), Zinc-tin alloy (Zn-Sn), the any combination of one or more in copper-zinc-ashbury metal (Cu-Zn-Sn), wherein said stanniferous compound includes but not limited to that the oxide of tin is as SnO and SnO
2, the hydroxide of tin, the carbonate of tin, the halide of tin, the nitrate of tin, any combination of one or more in the soap of tin and the organic compound of tin.
Preferably, described a kind of granularity containing tin promoter, its D
50=1～300 μ m, D
90=8～1500 μ m;
Preferably, a small amount of inorganic agent is contained on described a kind of surface containing tin promoter particle, protects described particle not to be oxidized and peptizaiton, and its quality percentage composition is between 0.05～1.5%;
Described a kind of containing tin promoter, its granule-morphology include but not limited to as irregularly shaped, near-spherical, spherical in, any combination of sheet, above-mentioned one or more granule-morphologies.
Inventive point of the present invention and beneficial effect be, tin is uniformly distributed and is combined on carrier, is conducive on the one hand tin and evenly mixes with silicon etc. in fluid bed, raising reaction efficiency; Reduced on the other hand the unnecessary loss of tin in industrial production.
The invention has the beneficial effects as follows for the drawback of prior art and the deficiency still existing embodies, the present invention and prior art are used granular metal glass putty that tin is joined to the method contrast in fluidized-bed reaction system, described a kind of containing tin promoter, make tin constituent element objectionable impurities content low, purity is high, when synthetic for organic silicon monomer, tin can be helped catalysis constituent element evenly make an addition to synthetic reaction system, improve the utilization ratio of tin, eliminate the oxide-film on silica flour and contact surface, and the improvement that is conducive to synthetic reaction activity, improved the space-time yield of fluid bed, reduce industrial cost, remarkable in economical benefits.
Specific embodiment
Specific embodiment 1
The mass percent example of described a kind of thing phase containing main component in tin promoter:
Preferably, described a kind of containing in tin promoter:
Cu (20.5%), Cu
2o (45.2%), CuO (23.5%), Al (9.2%), oxygen content (10.3%), wherein, Pb (56ppm), Fe (350ppm), other each metal impurities individual events < 45ppm;
Preferably, described a kind of containing tin promoter, its particle surface inorganic agent service property (quality) percentage amounts (0.6%), other each nonmetallic inclusion individual events < 50ppm;
Preferably, described a kind of containing tin promoter, its granularity D
50=25.7 μ m, D
90=95.4 μ m;
Preferably, described a kind of containing tin promoter, its granule-morphology is irregularly shaped and one or both any combination of sheet.
Specific embodiment 2
The mass percent example of described a kind of thing phase containing main component in tin promoter:
Preferably, described a kind of containing in tin promoter:
Cu (15.6%), Cu
2o (34.5%), CuO (18.5%), Si (20.5%), Sn (9.3%), oxygen content (7.9%), wherein, Pb (58ppm), Fe (0.10%), other each metal impurities individual events < 500ppm;
Preferably, described a kind of containing tin promoter, its particle surface inorganic agent service property (quality) percentage amounts (0.4%), other each nonmetallic inclusion individual events < 50ppm
Preferably, described a kind of containing tin promoter, its granularity D
50=56.5 μ m, D
90=286.3 μ m;
Preferably, described a kind of containing tin promoter, its granule-morphology is one or both any combination of irregularly shaped and curling sheet.
Specific embodiment 3
The mass percent example of described a kind of thing phase containing main component in tin promoter:
Preferably, described a kind of containing in tin promoter:
Cu (29.5%), Si (60.5%), Sn (8.5%), oxygen content (0.3%), wherein, Pb (56ppm), Fe (0.28%), other each metal impurities individual events < 500ppm;
Preferably, described a kind of containing tin promoter, its particle surface inorganic agent service property (quality) percentage amounts (0.7%), other each nonmetallic inclusion individual events < 50ppm
Preferably, described a kind of containing tin promoter, its granularity D
50=59.3 μ m, D
90=324.3 μ m;
Preferably, described a kind of containing tin promoter, its granule-morphology is one or both any combination of irregularly shaped and curling sheet.
Above-described is only the preferred embodiment of patent of the present invention, it should be noted that, for a person skilled in the art, do not departing under the prerequisite of structure of the present invention and thinking, still exist and make some distortion and room for improvement, these all will can not affect effect of the invention process and practical applicability and coverage.
Claims (10)
1. containing a tin promoter, it is characterized in that tin is uniformly distributed and is combined on carrier.
2. according to claim 1 a kind of containing tin promoter, it is characterized in that it is one or more any combination in elemental metals copper, Cu oxide that described carrier includes but not limited to.
3. according to claim 1 a kind of containing tin promoter, it is characterized in that described carrier includes but not limited to metallic silicon power.
4. according to claim 1 a kind of containing tin promoter, it is characterized in that described carrier can be one or more any combination in elemental metals copper, Cu oxide, metallic silicon power.
5. a kind of tin promoter that contains according to claim 1, is characterized in that according to the content of Si in described carrier, the mass percent example of described a kind of thing phase containing main component in tin promoter:
(1) in carrier containing Si (mean containing Si lower than 100ppm time), or containing Si seldom time when (meaning containing Si lower than 1000ppm), described a kind of containing in tin promoter:
Cu (5～99.0%), Sn (0.05～90.0%), containing oxygen (0.05～20.0%), the plumbous objectionable impurities content that waits is lower, for example: Pb≤200ppm, Fe≤800ppm, other each metals content impurities individual event≤50ppm, other every nonmetallic inclusion individual event≤100ppm;
(2) while containing Si in carrier, described a kind of containing in tin promoter:
Cu (5～99.0%), Sn (0.05～90.0%), Si (1～99.0%), containing oxygen 0.05～19.8%, the plumbous objectionable impurities content that waits is lower, for example: Pb≤200ppm, Fe≤0.5%, other each metals content impurities individual event≤500ppm, other every nonmetallic inclusion individual event≤100ppm.
6. a kind of tin promoter that contains according to claim 1, is characterized in that the composition according to described carrier, the mass percent example of described a kind of thing phase containing main component in tin promoter:
(1) when carrier is metallic copper and/or Cu oxide powder, as Cu, CuO, Cu2O, Cu-CuO, Cu-Cu2O, CuO-Cu2O, during Cu-Cu2O-CuO, described a kind of containing in tin promoter:
Cu (5～99.0%), Cu
2o (0.05～90.0%), CuO (O.05～85.O%), simple substance Sn and/or containing the alloy of Sn and/or containing the compound 0.05～90.0% of Sn;
(2) when carrier is metallic silicon (Si) powder, described a kind of containing in tin promoter:
Si (1～99.0%), simple substance Sn and/or containing the alloy of Sn and/or containing the compound 0.05～90.0% of Sn;
(3) when carrier is the mixture of metallic copper and/or Cu oxide powder, metallic silicon (Si) powder, described a kind of containing in tin promoter:
Cu (5～95.0%), Cu
2o (0.05～85.0%), CuO (0.05～80.0%), Si (1～98.0%), simple substance Sn and/or containing the alloy of Sn and/or containing the compound O.05～90.0% of Sn.
7. according to claim 1 a kind of containing tin promoter, it is characterized in that described tin can derive from one or more any combination including but not limited in elemental metals tin, stanniferous alloy, stanniferous compound, wherein said stanniferous alloy includes but not limited to signal bronze (Cu-Sn), Zinc-tin alloy (Zn-Sn), the any combination of one or more in copper-zinc-ashbury metal (Cu-Zn-Sn), wherein said stanniferous compound includes but not limited to that the oxide of tin is as SnO and SnO
2, the hydroxide of tin, the carbonate of tin, the halide of tin, the nitrate of tin, any combination of one or more in the soap of tin and the organic compound of tin.
8. according to claim 1 a kind of containing tin promoter, it is characterized in that described a kind of granularity containing tin promoter, its D
50=-1～300 μ m, D
90=8～1500 μ m.
9. a kind of tin promoter that contains according to claim 1, is characterized in that a small amount of inorganic agent is contained on the surface of its particle, protects described particle not to be oxidized and peptizaiton, and its quality percentage composition is between 0.05～1.5%.
10. according to claim 1 a kind of containing tin promoter, it is characterized in that its granule-morphology includes but not limited to any combination of irregularly shaped, near-spherical, spherical, sheet, above-mentioned one or more granule-morphologies.
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| CN201410346117.5A CN104138760A (en) | 2014-07-10 | 2014-07-10 | Stanniferous catalyst promoter |
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|---|---|---|---|
| CN201410346117.5A CN104138760A (en) | 2014-07-10 | 2014-07-10 | Stanniferous catalyst promoter |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104941653A (en) * | 2015-05-29 | 2015-09-30 | 中国科学院过程工程研究所 | Copper-tin composite oxide catalyst, and preparation method and use thereof |
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|---|---|---|---|---|
| US4520130A (en) * | 1984-05-08 | 1985-05-28 | Scm Corporation | Halosilane catalyst and process for making same |
| CN1834098A (en) * | 2004-03-18 | 2006-09-20 | 信越化学工业株式会社 | Preparation of organohalosilanes |
| CN102773099A (en) * | 2011-05-13 | 2012-11-14 | 中国科学院过程工程研究所 | Cu-Cu2O-CuO ternary copper-based solid solution catalyst and its preparation method |
| CN102941101A (en) * | 2012-11-30 | 2013-02-27 | 湖南省天心博力科技有限公司 | Preparation process of sheet-shaped copper-tin alloy powder auxiliary catalyst |
-
2014
- 2014-07-10 CN CN201410346117.5A patent/CN104138760A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4520130A (en) * | 1984-05-08 | 1985-05-28 | Scm Corporation | Halosilane catalyst and process for making same |
| CN1834098A (en) * | 2004-03-18 | 2006-09-20 | 信越化学工业株式会社 | Preparation of organohalosilanes |
| CN102773099A (en) * | 2011-05-13 | 2012-11-14 | 中国科学院过程工程研究所 | Cu-Cu2O-CuO ternary copper-based solid solution catalyst and its preparation method |
| CN102941101A (en) * | 2012-11-30 | 2013-02-27 | 湖南省天心博力科技有限公司 | Preparation process of sheet-shaped copper-tin alloy powder auxiliary catalyst |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104941653A (en) * | 2015-05-29 | 2015-09-30 | 中国科学院过程工程研究所 | Copper-tin composite oxide catalyst, and preparation method and use thereof |
| CN104941653B (en) * | 2015-05-29 | 2018-04-03 | 中国科学院过程工程研究所 | A kind of copper and tin composite oxide catalysts and its production and use |
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Application publication date: 20141112 |
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