CN110270328A - Three-phase copper-based catalysts and the preparation method and application thereof - Google Patents
Three-phase copper-based catalysts and the preparation method and application thereof Download PDFInfo
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- CN110270328A CN110270328A CN201810222432.5A CN201810222432A CN110270328A CN 110270328 A CN110270328 A CN 110270328A CN 201810222432 A CN201810222432 A CN 201810222432A CN 110270328 A CN110270328 A CN 110270328A
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- 239000010949 copper Substances 0.000 title claims abstract description 115
- 239000003054 catalyst Substances 0.000 title claims abstract description 75
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 56
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000002245 particle Substances 0.000 claims abstract description 101
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 19
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 19
- 238000003786 synthesis reaction Methods 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 18
- 230000015572 biosynthetic process Effects 0.000 claims description 17
- 239000007767 bonding agent Substances 0.000 claims description 12
- 238000000498 ball milling Methods 0.000 claims description 10
- 238000005516 engineering process Methods 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000011258 core-shell material Substances 0.000 claims description 8
- 238000009826 distribution Methods 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- 238000003701 mechanical milling Methods 0.000 claims description 7
- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- 229910018292 Cu2In Inorganic materials 0.000 claims description 3
- 239000002356 single layer Substances 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- 230000001788 irregular Effects 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- 239000003921 oil Substances 0.000 claims description 2
- 239000012188 paraffin wax Substances 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920000193 polymethacrylate Polymers 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 21
- 230000000694 effects Effects 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 abstract description 4
- 230000009471 action Effects 0.000 abstract description 3
- 239000000376 reactant Substances 0.000 abstract description 3
- 230000009257 reactivity Effects 0.000 abstract description 3
- 239000011863 silicon-based powder Substances 0.000 abstract description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 26
- 238000000034 method Methods 0.000 description 13
- 229910052710 silicon Inorganic materials 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 239000010703 silicon Substances 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 239000000178 monomer Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- YGZSVWMBUCGDCV-UHFFFAOYSA-N chloro(methyl)silane Chemical compound C[SiH2]Cl YGZSVWMBUCGDCV-UHFFFAOYSA-N 0.000 description 3
- 230000007812 deficiency Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000005046 Chlorosilane Substances 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000005474 detonation Methods 0.000 description 1
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/12—Organo silicon halides
- C07F7/16—Preparation thereof from silicon and halogenated hydrocarbons direct synthesis
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of three-phase copper-based catalysts and the preparation method and application thereof.The three-phase copper-based catalysts include mainly by Cu2The aggregate that O particle and CuO particle, Cu particle are formed, wherein CuO particle and Cu particle surround Cu2The setting of O particle.In three-phase copper-based catalysts of the invention, the highest superfine nano Cu particle of activity is exposed to the outer layer of aggregate, it is most fast and most directly with reactant Si powder and CH3Cl contact, and trigger action, CuO, Cu of aggregate internal layer are played to reaction2O particle gradually converts Cu phase and participates in reacting, it ensure that the continuity of entire reaction process, simultaneously three-phase copper catalyst of the invention have higher reactivity and, it is able to maintain that stable dimethyldichlorosilane selectivity, and the reaction rate and production efficiency of dimethyldichlorosilane synthetic reaction are promoted, reduce cost.
Description
Technical field
The catalyst and preparation method thereof that the present invention relates to a kind of for synthesizing methyl-chloro-silane, in particular to a kind of three-phase
Copper-based catalysts and the preparation method and application thereof belong to catalyst technical field.
Background technique
Organosilicon material is a major class using Si-O key as main chain, and high score of the organic group as side chain is introduced on Si atom
Sub- compound has the function of much excellent performances and special since it has half inorganic, half organic structure.Have
Machine silicon monomer is the base stock for manufacturing organosilicon material, and is wherein accounted for by the dimethyldichlorosilane that direct synthesis technique reaches
To 90% or more of the total dosage of organic silicon monomer.
In the industrial production, methylchlorosilane is all made of direct method and is closed under catalytic condition by metallic silicon and gas phase chloromethanes
At specific catalytic reaction process are as follows:
Industrial organosilicon product is the mixture of a variety of degrees of functionality, can use formula M enHmSiCl4-(n+m)It indicates, formula
In, n is 0~4；M is that 0~4, n+m is 0~4.Wherein with dimethyldichlorosilane Me2SiCl2Dosage it is maximum, account for about methyl
90% (mass percent) of chlorosilane.
The maximum difficult point of organosilicon production is the synthesis of monomer, and improving the efficiency of synthesis and reducing cost is the field
Eternal project.The yield and diformazan selectivity for influencing organic silicon monomer synthesis, in addition to process units, material quality and synthesis work
Outside skill, catalyst is its key factor.
The prior art and report have proven to the most effective catalyst that copper is direct synthesis methylchlorosilane, as master
The Cu-Cu of fluid catalyst system2O-CuO (abbreviation three-phase copper) three-phase mixed catalyst powder has length reaction time, dimethyl
The advantages such as dichlorosilane yield is high, activity is good are catalyzed the effect of reaction other than related with three Phase Proportions, also with the spy of powder
Property, such as three-phase distribution mode, pattern, granularity are related to specific surface area.
Existing three-phase Copper catalyst system is Cu, Cu2O and CuO be crushed-is mixed (such as Fig. 1) by ball-milling technology, and three
Kind object phase particle size distribution range shows as disordered uniform distribution, powder shape between 1~50 micron, on both macro and micro
Looks are sheet or graininess, and this disorder distribution leads to the unstable of reaction process and is difficult to continue, the activity of such catalyst
Selectively have with diformazan to be hoisted, it is more difficult to the synthetic reaction process of dimethyldichlorosilane be made steadily to carry out and maintain higher
Production efficiency.Such as during the reaction, Cu phase preferentially participates in reaction, at this time Cu2O and CuO and copper oxide also have not enough time to join
It is separated and takes out of by cyclone system with reaction, the Cu of preferential reaction is placed in reunion volume surrounding, subsequent aggregate internal layer by the present invention
Cu2O gradually participates in reacting, and ensure that the continuity and duration of reaction, can obtain preferably catalytic effect.
Summary of the invention
The main purpose of the present invention is to provide a kind of three-phase copper-based catalysts and the preparation method and application thereof, existing to overcome
There is the deficiency of technology.
For realization aforementioned invention purpose, the technical solution adopted by the present invention includes:
On the one hand the embodiment of the present invention discloses a kind of three-phase copper-based catalysts, including mainly by Cu2O particle and CuO particle,
The aggregate that Cu particle is formed, wherein CuO particle and Cu particle surround Cu2The setting of O particle.
On the other hand the embodiment of the present invention additionally provides the preparation method of the three-phase copper-based catalysts, comprising: will
Cu2In O particle, CuO particle and Cu particle merging vibration ball-grinding machine, and bonding agent is put into vibration mechanical milling process, and control
The additive amount of bonding agent processed shakes ball milling 10min~30min within 1wt%, by mixed material, obtains that the three-phase is copper-based to urge
Agent.
The embodiment of the invention also provides three-phase copper-based catalysts the answering in dimethyldichlorosilane synthesis technology
With.
Compared with prior art, in three-phase copper-based catalysts of the invention, the highest superfine nano Cu particle exposure of activity
In the outer layer of aggregate, it is most fast and most directly with reactant Si powder and CH3Cl contact, and trigger action is played to reaction, reunite
CuO, Cu of internal layer2O particle gradually converts Cu phase and participates in reacting, and ensure that the continuity of entire reaction process, while this hair
Bright three-phase copper catalyst has higher reactivity and is able to maintain that stable dimethyldichlorosilane selectivity, and is promoted
The reaction rate and production efficiency of dimethyldichlorosilane synthetic reaction, reduce cost.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of three-phase Copper catalyst system in the prior art；
Fig. 2 is the structural schematic diagram of three-phase copper catalyst in an exemplary embodiments of the invention.
Specific embodiment
In view of deficiency in the prior art, inventor is studied for a long period of time and is largely practiced, and is able to propose of the invention
Technical solution.The technical solution, its implementation process and principle etc. will be further explained as follows.
On the one hand the embodiment of the present invention discloses a kind of three-phase copper-based catalysts, including mainly by Cu2O particle and CuO particle,
The aggregate that Cu particle is formed, wherein CuO particle and Cu particle surround Cu2The setting of O particle.
Further, the aggregate has core-shell structure, wherein Cu2O distribution of particles is in stratum nucleare, CuO particle and Cu
Distribution of particles is in shell.
Further, in the aggregate, CuO particle surrounds Cu2The setting of O particle, Cu particle are set around CuO particle
It sets.
Further, it is 50%~85%:0%~45%:5%~35% Cu that the aggregate, which includes mass ratio,2O
Particle, CuO particle and Cu particle.
It is more preferred, the Cu2The partial size of O particle is 1~50 μm.
More preferred, the partial size of the CuO particle is 0.01~0.5 μm.
More preferred, the partial size of the Cu particle is 0.01~0.5 μm.
It is more preferred, the Cu2O particle, CuO particle, Cu particle are spherical, spherical or irregular pattern particle
Shape.
More preferably, the Cu2O particle, CuO particle, the partial size of Cu particle three are different.
Further, the three-phase copper-based catalysts further include binder.
Preferably, the bonding agent includes bobbin oil, paraffin powder, stearic acid, polymethacrylate, polyethylene glycol
In any one or two or more combinations, but not limited to this.
Preferably, in the three-phase copper-based catalysts content of binder in 1wt% or less.
On the other hand the embodiment of the present invention additionally provides the preparation method of the three-phase copper-based catalysts, comprising: will
Cu2In O particle, CuO particle and Cu particle merging vibration ball-grinding machine, and bonding agent is put into vibration mechanical milling process, and control
The additive amount of bonding agent processed shakes ball milling 10min~30min within 1wt%, by mixed material, obtains that the three-phase is copper-based to urge
Agent.
In some more specific embodiments, the preparation method includes: by Cu2O particle, CuO particle and Cu
In particle merging vibration ball-grinding machine, wherein CuO particle and Cu particle are to put into simultaneously, and investment is viscous in vibration mechanical milling process
Agent is connect, mixed material is shaken into ball milling 10min~30min and obtains three-phase copper-based catalysts, the three-phase copper-based catalysts packet
Containing the aggregate with single layer core-shell structure.
In some more specific embodiments, the preparation method includes: by Cu2O particle, CuO particle and Cu
In particle merging vibration ball-grinding machine, wherein Cu particle is to put into after CuO particle feeds intake 10min~30min, and shaking
Bonding agent is put into mechanical milling process, and mixed material is shaken into ball milling 10min~30min and obtains three-phase copper-based catalysts, it is described
Three-phase copper-based catalysts include the aggregate with the double-deck core-shell structure.
The embodiment of the invention also provides three-phase copper-based catalysts the answering in dimethyldichlorosilane synthesis technology
With.
The technical solution, its implementation process and principle etc. will be further explained in conjunction with specific embodiments as follows
It is bright.
Specifically, a kind of method for preparing the three-phase copper-based catalysts, may include steps of:
1) Cu is prepared by oxidizing process2The O or high-purity Cu of purchase2O powder, partial size is in 150um hereinafter, carrying out at ball milling again
Reason, stops ball milling when partial size reaches 50 microns or less, obtains required Cu2O raw material.
2) according to the above Particle size requirements, CuO or Cu superfines is prepared using electric detonation, plasma discharge or extraction.
3) according to ratio, first by Cu2Tri- kinds of raw material powders of O are placed in vibration ball mill, investment bonding during vibration
Agent, the additive amount of bonding agent are to shake 10 minutes to 30 minutes within 1%
4) for the aggregate of single layer core-shell structure, Cu and CuO powder is added simultaneously in proportion and shakes 10 minutes~30 points
Clock.
5) CuO powder is first added in proportion and shakes 10~30 minutes, then presses for the aggregate of the core-shell structure double-deck for formation
Ratio is added Cu powder and continues vibration 10~30 minutes
6) mixed-powder is put into batch mixer and is further uniformly mixed, weighed, packaging.
Each batch three-phase copper-based catalysts made from the above method are carried out in fluidized-bed using (three-phase cupper-based catalyst
Agent uses bibliography " organosilicon synthesis technology and products application " Chemical Industry Press, good fortune Song Min in fluidized-bed),
(the three-phase copper of CN103127936A, CN103599782A, CN106140160A preparation is catalyzed with conventional commercial catalyst for assessment
Agent) difference, and assess performance under the conditions of different material and reaction temperature (following test data be multiple batches of sample
Carry out the average value of repeatedly test data acquired).
Embodiment 1
Three-phase copper-based catalysts are prepared refering to each component content in Tables 1 and 2, are calculated separately as catalyst A and catalyst
C,
Table 1 is the part material proportion of three-phase copper-based catalysts in embodiment 1
Table 2 is the part material proportion of three-phase copper-based catalysts in embodiment 1
By the catalyst reference provided in catalyst A, catalyst C and CN103127936A " organosilicon synthesis technology and
Products application " Chemical Industry Press, good fortune Song Min, the method for record catalyzes and synthesizes dimethyldichlorosilane, synthesis reaction temperature
285~293 DEG C, using 421 silicon as synthesis material；It tests and records it and catalyze and synthesize performance, the results are shown in Table 3；
Table 3 is the catalytic performance of catalyst A, the catalyst provided in catalyst C and CN103127936A
Embodiment 2
Three-phase copper-based catalysts are prepared refering to each component content in table 4, are calculated separately as catalyst B,
Table 4 is the part material proportion of three-phase copper-based catalysts in embodiment 2
The catalyst reference " organosilicon synthesis technology and products application " that will be provided in catalyst B and CN103599782A
Chemical Industry Press, good fortune Song Min, the method for record catalyze and synthesize dimethyldichlorosilane, synthesis reaction temperature 295~300
DEG C, using 411 silicon as synthesis material；It tests and records it and catalyze and synthesize performance, the results are shown in Table 5；
Table 5 is the catalytic performance of the catalyst provided in catalyst B and CN103599782A
Embodiment 3
Three-phase copper-based catalysts are prepared refering to each component content in table 6, are calculated separately as catalyst D,
Table 6 is the part material proportion of three-phase copper-based catalysts in embodiment 3
The catalyst reference " organosilicon synthesis technology and products application " that will be provided in catalyst D and CN106140160A
Chemical Industry Press, good fortune Song Min, the method for record catalyze and synthesize dimethyldichlorosilane, synthesis reaction temperature 285~290
DEG C, using 321 silicon as synthesis material；It tests and records it and catalyze and synthesize performance, the results are shown in Table 7；
Table 7 is the catalytic performance of the catalyst provided in catalyst D and CN106140160A
In three-phase copper-based catalysts of the invention, the highest ultra-fine sub-micron Cu particle of activity is exposed to the outer of aggregate
Layer, it is most fast and most directly with reactant Si powder and CH3Cl contact, and trigger action played to reaction, the CuO of aggregate internal layer,
Cu2O particle gradually converts Cu phase and participates in reacting, and ensure that the continuity of entire reaction process, while three-phase copper of the invention is urged
Agent has higher reactivity and is able to maintain that stable dimethyldichlorosilane selectivity, and promote dimethyl dichloro
The reaction rate and production efficiency of silane synthetic reaction, reduce cost.
It should be appreciated that the technical concepts and features of above-described embodiment only to illustrate the invention, its object is to allow be familiar with this
The personage of item technology cans understand the content of the present invention and implement it accordingly, and it is not intended to limit the scope of the present invention.It is all
Equivalent change or modification made by Spirit Essence according to the present invention, should be covered by the protection scope of the present invention.
Claims (10)
1. a kind of three-phase copper-based catalysts, it is characterised in that including mainly by Cu2The group that O particle and CuO particle, Cu particle are formed
Aggressiveness, wherein CuO particle and Cu particle surround Cu2The setting of O particle.
2. three-phase copper-based catalysts according to claim 1, it is characterised in that: the aggregate has core-shell structure,
Middle Cu2O distribution of particles is in stratum nucleare, and CuO particle and Cu distribution of particles are in shell.
3. three-phase copper-based catalysts according to claim 2, it is characterised in that: in the aggregate, CuO particle is surrounded
Cu2The setting of O particle, Cu particle are arranged around CuO particle.
4. three-phase copper-based catalysts according to any one of claim 1-3, it is characterised in that: the aggregate includes matter
Amount is than being 50%~85%:0%~45%:5%~35% Cu2O particle, CuO particle and Cu particle.
5. three-phase copper-based catalysts according to any one of claim 1-3, it is characterised in that: the Cu2The grain of O particle
Diameter is 1~50 μm；And/or the partial size of the CuO particle is 0.01~0.5 μm；And/or the partial size of the Cu particle is 0.01
~0.5 μm；And/or the Cu2O particle, CuO particle, Cu particle are spherical, spherical or irregular pattern graininess；With/
Or, the Cu2O particle, CuO particle, the partial size of Cu particle three are different.
6. three-phase copper-based catalysts according to any one of claim 1-3, it is characterised in that further include binder；It is preferred that
, the bonding agent includes bobbin oil, paraffin powder, stearic acid, polymethacrylate, any one in polyethylene glycol
Or two or more combination；Preferably, in the three-phase copper-based catalysts content of binder in 1wt% or less.
7. such as the preparation method of three-phase copper-based catalysts of any of claims 1-6, characterized by comprising: will
Cu2In O particle, CuO particle and Cu particle merging vibration ball-grinding machine, and bonding agent is put into vibration mechanical milling process, and control
The additive amount of bonding agent processed shakes ball milling 10min~30min within 1wt%, by mixed material, obtains that the three-phase is copper-based to urge
Agent.
8. preparation method according to claim 7, characterized by comprising: by Cu2O particle, CuO particle and Cu particle are set
Enter to shake in ball-grinding machine, wherein CuO particle and Cu particle are to put into simultaneously, and put into bonding agent in vibration mechanical milling process,
Mixed material is shaken into ball milling 10min~30min and obtains three-phase copper-based catalysts, the three-phase copper-based catalysts include to have
The aggregate of single layer core-shell structure.
9. preparation method according to claim 7, characterized by comprising: by Cu2O particle, CuO particle and Cu particle are set
Enter to shake in ball-grinding machine, wherein CuO particle and Cu particle are in Cu2O particle feeds intake and puts into after 10min~30min, and
Bonding agent is put into vibration mechanical milling process, mixed material is shaken into ball milling 10min~30min and obtains three-phase copper-based catalysts,
The three-phase copper-based catalysts include the aggregate with the double-deck core-shell structure.
10. application of the three-phase copper-based catalysts in dimethyldichlorosilane synthesis technology described in any one of claim 1-6.
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