CN104843721B - A kind of recovery method of abandoned catalyst in direct synthesis methylchlorosilane - Google Patents
A kind of recovery method of abandoned catalyst in direct synthesis methylchlorosilane Download PDFInfo
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Abstract
The present invention relates to a kind of recovery method of abandoned catalyst in direct synthesis methylchlorosilane, methods described comprises the steps：(1) calcine abandoned catalyst in direct synthesis methylchlorosilane, remove its area carbon；(2) abandoned catalyst in direct synthesis methylchlorosilane after leaching step (1) is processed in the ammonia ammonium salt mixed solution containing oxidant, leaching finishes, and filters, and washing is dried filtering residue, obtains silicon-containing solid residue；(3) in the silicon-containing solid residue obtaining to step (2) add acid solution soaked, soak terminate after, separate, washing, be dried after obtain silica flour；(4) silica flour obtaining step (3) is dispersed in water, and temperature control activates, and obtains suspension, adds catalyst afterwards, and heated and stirred is reacted, and after standing, sucking filtration obtains Ludox.The method low cost, simple to operate, material is easy to get it is easy to large-scale production.
Description
Technical field
The present invention relates to abandoned catalyst in direct synthesis methylchlorosilane reclaims field, more particularly, to a kind of recycling abandoned catalyst in direct synthesis methylchlorosilane prepares silicon
The method of colloidal sol.
Background technology
Methylchlorosilane is to prepare the most important monomer of organosilicon polymer.Wherein, with dimethyldichlorosilane [M2]
Consumption is maximum, accounts for the 90% of methylchlorosilane.Producing M2Fluidized-bed reactor in, silica flour and copper catalyst are mixed to form
Active contact, with the prolongation in response time, the deposit on contact surface can get more and more, and so that contact activity is reduced, lead to M2
Selectivity reduces, and now, the mixture of wherein unreacted silica flour and catalyst need to discharge reactor, is simultaneously introduced new contact
It is beneficial to reaction continuously and stably to carry out.In addition, with the continuous consumption of silica flour in reaction, silicon grain constantly diminishes, fluid bed
Gas solid separation system continuously discharge the serious fine powder of surface contamination, this two parts waste residue becomes waste catalyst.These waste catalysts
Main Ingredients and Appearance is：Silicon, copper, carbon, zinc etc., their weight contents in waste catalyst are respectively 65%～80%, 3%～20%,
1%～10%, 0.05%～2.0%.Waste catalyst is tiny due to granule, and the activity of copper powder is higher, meets air and is susceptible to oxygen
Change reaction so as in organic substance and carbon burning emerge pungent white cigarette, be difficult to store, environmental pollution is serious, gives simultaneously
Safety in production brings very big hidden danger.The external recycling just having carried out abandoned catalyst in direct synthesis methylchlorosilane early in last century the fifties
Research, current silicone industry in China enterprise sells to small business to the processing mode of waste catalyst generally by burial or low price.This
Not only cause serious environmental pollution, be also to waste to silicon, copper resource.The presence of heavy metal pollutes the environment；And costliness
The discarded of elemental silicon causes organosilicon product cost very high.
State of the art is concentrated mainly on the recovery of silica flour and copper powder (such as to the comprehensive utilizating research of waste catalyst
CN1083418A, CN1844422A and CN1618840A), and carried out recovery silica flour processing and utilization research (CN1760124A
And CN1465524A), be such as processed into qualified silica flour and return organic silicon monomer production line, or silico briquette is become by smelting processing and in addition
Using.But the complex process that prior art comprehensively utilizes to abandoned catalyst in direct synthesis methylchlorosilane, during generate harmful gass, and the utilization of silicon
Rate can not reach 100%, still has waste silicon powder to generate.
Solve " three wastes " problem of waste catalyst, carry out environment-friendly type and Eco-power waste catalyst harmless treatment process reclaims and grinds
Study carefully, be the technical barrier that current field of organic silicon must solve, it, to organosilicon Reducing Cost in Enterprises, reduction pollution, promotes me
The sound development of state's silicone industry is extremely important.
Ludox is the colloid solution that nanosized silica particles are dispersed in water, also known as silica sol, or titanium dioxide
The silicon hydrosol.Ludox has many advantageous properties, has very promising in inorganic silicon compound, due to its corrosion resistant
Erosion, the high temperature resistant, performance such as antioxidation, bigger serface, high adsorption, high degree of dispersion, high-insulativity, and raw material sources are wide
General, be easy to produce, cheap, to the advantages of the mankind and environment nonhazardouss, since twentieth century forties, Ludox is in machine
It is used widely in the industrial departments such as tool manufacture, petrochemical industry, light textile, electronics, particularly Inorganic Macromolecules Building Coatings
Rise and electronics industry develops rapidly, the demand of Ludox quickly increases.
This area have exploitation a kind of from abandoned catalyst in direct synthesis methylchlorosilane reclaim silica flour prepare Ludox method needs, described side
Method should have that process is simple, and raw material is easy to get, easy to operate characteristic.
Content of the invention
For the deficiencies in the prior art, an object of the present invention is to provide a kind of utilization abandoned catalyst in direct synthesis methylchlorosilane to reclaim
The method that Ludox prepared by silica flour, has significant economic benefit and environmental benefit.
The present invention realizes especially by following scheme：
A kind of recovery method of abandoned catalyst in direct synthesis methylchlorosilane, methods described comprises the steps：
(1) calcine abandoned catalyst in direct synthesis methylchlorosilane, remove its area carbon；
(2) abandoned catalyst in direct synthesis methylchlorosilane after leaching step (1) is processed in the ammonia containing oxidant-ammonium salt mixed solution, leaching
Finish, filter, washing, filtering residue is dried, obtains silicon-containing solid residue；
(3) add acid solution to be soaked in the silicon-containing solid residue obtaining to step (2), soak after terminating, separate, wash
Wash, be dried after obtain silica flour；
(4) silica flour obtaining step (3) is dispersed in water, and temperature control activates, and obtains suspension, adds catalyst afterwards,
Heated and stirred is reacted, and after standing, sucking filtration obtains Ludox.
Abandoned catalyst in direct synthesis methylchlorosilane is based on silicon, copper, carbon, and containing metal ingredients such as a small amount of stannum, zinc, provides through the present invention
Calcining, the leaching of ammonia-ammonium salt, acid soak, pure silica flour can be obtained；And silicon in the basic conditions can be with water generating silicic acid
Monomer and hydrogen, silicic acid monomer can form Ludox by the polymerization of itself.Specifically, silica flour is in the presence of catalyst and water
Hydrolysis are occurred to give birth to silicic acid molecule, as shown in formula (1)：
Si+2OH-+H2O→SiO3 2-+2H2↑ (1)
The active silicic acid generating have strong from agglomeration tendency, therefore active silicic acid soft-agglomerated after form polysilicon acid.When molten
After the concentration of silicic acid reaches supersaturation in liquid, undergo phase transition reaction, amount of activated silicic acid voluntarily occurs dehydration condensation to analyse
Go out nucleus, reaction is as shown in formula (2)：
mH2SiO3+nH2SiO3→(n+m)SiO2+(n+m)H2O (2)
After nucleus is formed, active silicic acid will adsorb in nucleating surface, so that nucleus is constantly grown up, thus it is molten to form silicon
Glue, reaction is as shown in formula (3)：
nSiO2+H2SiO3→(n+1)SiO2+H2O (3).
The described calcining heat of step (1) of the present invention is 300～800 DEG C, such as 320 DEG C, 350 DEG C, 370 DEG C, 450 DEG C, 480
DEG C, 562 DEG C, 650 DEG C, 730 DEG C, 775 DEG C etc.；Calcination time be 0.5～4h, such as 0.8h, 1.2h, 1.6h, 2.3h, 2.8h,
3.3h, 3.8h etc..
Preferably, the described calcining heat of step (1) is 500～600 DEG C；Calcination time is 0.5～2h.
Preferably, the described calcining of step (1) is carried out in Muffle furnace, tube furnace or batch-type furnace.
In organic silicon monomer building-up process, silicon powder surface meeting deposited carbon layer, form carbon distribution, affect follow-up reaction and live
Property, waste catalyst is carried out calcination processing, can remove the carbon distribution on waste catalyst surface by the therefore present invention.
Oxidant in the described ammonia-ammonium salt mixed solution containing oxidant of step (2) of the present invention is air, oxygen or dioxygen
Any a kind in water or at least 2 kinds of combination.
Preferably, the described ammonia-ammonium salt of step (2) is to contain ammonia and ammonium salt simultaneously, and described ammonium salt is ammonium chloride, ammonium carbonate
Or any a kind in ammonium hydrogen carbonate or at least 2 kinds of combination.
Preferably, in the described ammonia-ammonium salt mixed solution containing oxidant of step (2), ammonia and the mol ratio of ammonium salt are 1:
1.5～5, such as 1:1.6、1:1.9、1:2.3、1:2.6、1:3.5、1:4.2、1:4.8 waiting.
Preferably, in the described ammonia-ammonium salt mixed solution containing oxidant of step (2), ammonia-ammonium salt is given up with the organosilicon of leaching
The mass ratio of contact is 0.2～1:1, such as 0.2:1、0.5:1、0.6:1、0.8:1 etc..
The described leaching temperature of step (2) of the present invention is 20～100 DEG C, such as 25 DEG C, 32 DEG C, 38 DEG C, 46 DEG C, 55 DEG C, 68
DEG C, 75 DEG C, 88 DEG C, 95 DEG C etc., leaching time is 1～8h.
Preferably, the described leaching temperature of step (2) is 20～70 DEG C, and leaching time is 3～5h.
The described acid solution of step (3) of the present invention is selected from any a kind or at least 2 kinds in nitric acid, sulphuric acid, hydrochloric acid or phosphoric acid of group
Close；
Preferably, H in described acid solution+Concentration be 2～10mol/L, such as 3mol/L, 5mol/L, 9mol/L etc.；
Preferably, the addition of described acid solution and the mass ratio of silicon-containing solid residue are 0.5～1:1.
The described soaking temperature of step (3) of the present invention is 20～60 DEG C, such as 23 DEG C, 25 DEG C, 36 DEG C, 42 DEG C, 48 DEG C, 55 DEG C
It is 1～10h Deng, soak time；Preferably described soaking temperature is 20～60 DEG C, and soak time is 3～5h.
The described silica flour of step (4) of the present invention is 1 with the mass ratio of water:1～20, such as 1:2、1:6、1:12、1:15、1:
18、1:19 etc..
The described catalyst of step (4) of the present invention is selected from sodium hydroxide, potassium hydroxide, Lithium hydrate, ammonia, sodium silicate or silicon
Any a kind in sour potassium or at least 2 kinds of combination.
Preferably, the mass ratio of the described catalyst of step (4) and silica flour is 0.02～0.1:1, such as 0.04:1、0.06:
1、0.12:1、0.15:1、0.18:1 etc..
The temperature of the described heated and stirred of step (4) of the present invention is 30～100 DEG C, such as 40 DEG C, 50 DEG C, 68 DEG C, 85 DEG C, 92
DEG C etc., the time is 3～10h；
Preferably, the temperature of the described heated and stirred of step (4) is 80～90 DEG C, and the time is 8～10h；
Preferably, the described time of repose of step (4) is more than 5h, and such as 6h, 8h, 11h, 16h, 20h, 23h, 25h etc. are excellent
Select more than 10h.
Silicon powder surface contains one layer of inert coating, predominantly silicon dioxide film, and inner material can be passivated by it, stops reaction
Occur.The present invention carry out with catalyst reaction before activated, can remove the oxide layer of silicon powder surface, increase reaction and live
Property, make reaction be more easy to occur, the silica flour being otherwise in passive state will extend reaction required time.
As optimal technical scheme, the recovery method of abandoned catalyst in direct synthesis methylchlorosilane of the present invention, comprise the steps：
(1) at 300～800 DEG C, abandoned catalyst in direct synthesis methylchlorosilane is calcined, calcination time is 0.5～4h, by waste catalyst table
The carbon distribution in face removes；
(2) ammonia-ammonium salt mixed solution containing oxidant is added to be leached in the sample obtaining to step (1), leaching temperature
20～100 DEG C of degree, leaching time is 1～8h, obtains silicon-containing solid residue after filtering, wash, being dried；
(3) add acid solution in the silicon-containing solid residue of step (2) gained, at 20～60 DEG C of temperature, soak 1～10h,
Silica flour is obtained after separating, washing, drying；
(4) silica flour obtaining step (3) is sufficiently mixed with water, obtains mixing suspension, then in 30～100 DEG C of temperature
Under the conditions of priming reaction 10～60min；Add catalyst, reacting by heating in gained mixing suspension, wherein added catalysis
The amount of agent is 0.02 with the mass ratio of step (3) gained silica flour:1～0.1:1, carry out solid-liquid separation after reaction, remove unreacted
Silica flour, the solution obtaining is Ludox.
Compared with prior art, the present invention has the advantages that：
(1) the invention provides (ammonia-ammonium is soaked through calcining, ammonia using the solid residue waste catalyst of organosilicon compound probability
Salt soaks), acidleach obtain the higher silica flour of purity, be then dispersed in the aqueous solution containing base catalyst, obtaining the side of Ludox
Method, this method saves production cost, has obvious economic benefit；Reduce the pollution to environment for the waste catalyst, have substantially
Environmental benefit；
(2) method that the present invention provides can prepare the higher silica flour of purity, both avoided heavy metals emission and caused ring
Border is polluted, and enables recycling of material again；
(3) method that the present invention provides is easy and simple to handle, with low cost；The reagent market using is common, and Material Cost is invested
Low, it is easy to accomplish large-scale production.
Brief description
The XRD spectra of the silica flour that Fig. 1 obtains for embodiment 1 step (3)；
Fig. 2 is obtained the SEM figure of Ludox for embodiment 1；
The SEM figure of the Ludox that Fig. 3 provides for comparative example.
Specific embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that described enforcement
Example is only to aid in understanding the present invention, is not construed as the concrete restriction to the present invention.
Embodiment 1
A kind of recovery method of abandoned catalyst in direct synthesis methylchlorosilane, comprises the steps：
(1) weigh 100g waste catalyst, put into 500 DEG C of calcining 1h in Muffle furnace, to remove the carbon distribution of particle surface；
(2) 17g ammonium carbonate, 36g (25.0wt%) ammonia are added in the solid that step (1) is obtained, 200mL water, 20
At DEG C, blowing air stirring leaching 3h, leaching finishes, and sucking filtration, washing are dried to obtain silicon-containing solid residue；
(3) add the hydrochloric acid of 100mL 20wt% in the silicon-containing solid residue obtaining to step (2), 20 DEG C are soaked 3h, molten
Solve various metallic element therein, then reduce pressure sucking filtration, and filtering residue water cleans to pH ≈ 7, afterwards 90 DEG C in vacuum drying oven
Vacuum drying 2h obtains silica flour；Acid solution (hydrochloric acid) can be reused and be neutralized to pH ≈ 7 to when can not reuse with sodium hydroxide
Discharge；The silica flour purity preparing is 97.3%；
(4) take the silica flour that 15g step (3) obtains, add 200mL moisture to dissipate, activate 30min at 80 DEG C, suspended
Liquid；It is subsequently adding 0.5g sodium hydroxide, stirring reaction 8h at 80 DEG C；Stand overnight afterwards, then sucking filtration, remove wherein unreacted
Silicon grain, that is, obtain Ludox.
Performance test：
Embodiment 1 is reclaimed, from waste catalyst, the X ' that the silica flour obtaining produces in Dutch Panalytical company (PANalytical)
Carry out XRD test on Pert PRO MPD type Multi-functional X ray diffractometer；Result is as shown in figure 1, Fig. 1 is embodiment 1 step
(3) XRD spectra of the silica flour obtaining, diffraction maximum therein is the characteristic diffraction peak of silicon, does not have other miscellaneous peaks, shows to adopt
This method achieves the purification of silicon；
The JSM6700 model field emission scanning electron microscope that Ludox prepared by embodiment 1 produces in NEC company is seen
Survey surface topography；Fig. 2 is obtained the SEM figure of Ludox for embodiment 1.
Embodiment 2
A kind of recovery method of abandoned catalyst in direct synthesis methylchlorosilane, comprises the steps：
(1) weigh 100g waste catalyst, put into 500 DEG C of calcining 30min in Muffle furnace, to remove the carbon distribution of particle surface；
(2) addition 22.5g ammonium carbonate in the solid that step (1) is obtained, 40g (25.0wt%) ammonia, 200mL water,
At 40 DEG C, blowing air stirring leaching reaction 3h, leaching finishes, and sucking filtration, washing are dried to obtain silicon-containing solid residue；
(3) add the hydrochloric acid of 100mL 20wt% in the silicon-containing solid residue obtaining to step (2), 30 DEG C are soaked 3h, molten
Solve various metallic element therein, then reduce pressure sucking filtration；Filtering residue water cleans to pH ≈ 7, afterwards 90 DEG C in vacuum drying oven
Vacuum drying 2h obtains silica flour；Acid solution (hydrochloric acid) can be reused and be neutralized to pH ≈ 7 to when can not reuse with sodium hydroxide
Discharge；The silica flour purity preparing is 96.8%；
(4) take the silica flour that 15g step (3) obtains, add 200mL moisture to dissipate, activate 30min at 80 DEG C, suspended
Liquid；It is subsequently adding 0.5g sodium hydroxide, stirring reaction 8h at 90 DEG C；Liquid is stood overnight, then sucking filtration, remove wherein not anti-
The silicon grain answered, that is, obtain Ludox.
Embodiment 3
A kind of recovery method of abandoned catalyst in direct synthesis methylchlorosilane, comprises the steps：
(1) weigh 100g waste catalyst, put into 550 DEG C of calcining 1h in Muffle furnace, to remove the carbon distribution of particle surface；
(2) addition 20g ammonium carbonate in the solid that step (1) is obtained, 45.5g (25.0wt%) ammonia, 200mL water,
At 60 DEG C, blowing air stirring leaching 3h, leaching finishes, and sucking filtration, washing are dried to obtain silicon-containing solid residue；
(3) add the hydrochloric acid of 100mL 20wt% in the silicon-containing solid residue obtaining to step (2), 40 DEG C are soaked 3h, molten
Solve various metallic element therein, then reduce pressure sucking filtration, and filtering residue water cleans to pH ≈ 7, afterwards 90 DEG C in vacuum drying oven
Vacuum drying 2h obtains silica flour；Acid solution (hydrochloric acid) can be reused and be neutralized to pH ≈ 7 to when can not reuse with sodium hydroxide
Discharge；The silica flour purity preparing is 97.2%；
(4) take the silica flour that 25g step (3) obtains, add 200mL moisture to dissipate, activate 30min at 80 DEG C, suspended
Liquid；It is subsequently adding 1.0g sodium hydroxide, stirring reaction 8h at 80 DEG C；Stand overnight afterwards, then sucking filtration, remove wherein unreacted
Silicon grain, that is, obtain Ludox.
Embodiment 4
A kind of recovery method of abandoned catalyst in direct synthesis methylchlorosilane, comprises the steps：
(1) weigh 100g waste catalyst, put into 550 DEG C of calcining 2h in Muffle furnace, to remove the carbon distribution of particle surface；
(2) addition 25g ammonium hydrogen carbonate in the solid that step (1) is obtained, 53.5g (25.0wt%) ammonia, 200mL water,
At 40 DEG C, blowing air stirring leaching 5h, leaching finishes, and sucking filtration, washing are dried to obtain silicon-containing solid residue；
(3) add the nitric acid of 100mL 20wt% in the silicon-containing solid residue obtaining to step (2), 25 DEG C are soaked 3h, molten
Solve various metallic element therein, then reduce pressure sucking filtration, and filtering residue water cleans to pH ≈ 7, afterwards 90 DEG C in vacuum drying oven
Vacuum drying 2h obtains silica flour；Acid solution (nitric acid) can be reused and be neutralized to pH ≈ 7 to when can not reuse with sodium hydroxide
Discharge；The silica flour purity preparing is 96.8%；
(4) take the silica flour that 25g step (3) obtains, add 200mL moisture to dissipate, activate 30min at 80 DEG C, suspended
Liquid；It is subsequently adding 1.0g sodium hydroxide, stirring reaction 8h at 90 DEG C；Stand overnight afterwards, then sucking filtration, remove wherein unreacted
Silicon grain, that is, obtain Ludox.
Embodiment 5
A kind of recovery method of abandoned catalyst in direct synthesis methylchlorosilane, comprises the steps：
(1) weigh 100g waste catalyst, put into 500 DEG C of 30min in tube furnace, to remove the carbon distribution of particle surface；
(2) 22.7g ammonium hydrogen carbonate, 58.5g (25.0wt%) ammonia, 200mL are added in the solid that step (1) is obtained
Water, at 50 DEG C, blowing air stirring leaching 5h, leaching finishes, and sucking filtration, washing are dried to obtain silicon-containing solid residue；
(3) add the nitric acid of 100mL 20wt% in the silicon-containing solid residue obtaining to step (2), 30 DEG C are soaked 3h, molten
Solve various metallic element therein, then reduce pressure sucking filtration；Filtering residue water cleans to pH ≈ 7, afterwards 90 DEG C in vacuum drying oven
Vacuum drying 2h obtains silica flour；Acid solution (nitric acid) can be reused and be neutralized to pH ≈ 7 to when can not reuse with sodium hydroxide
Discharge；The silica flour purity preparing is 97.4%；
(4) take the silica flour that 30g step (3) obtains, add 200mL moisture to dissipate, activate 30min at 80 DEG C, suspended
Liquid；It is subsequently adding 1.0g sodium hydroxide, stirring reaction 8h at 90 DEG C；Liquid is stood overnight, then sucking filtration, remove wherein not anti-
The silicon grain answered, that is, obtain Ludox.
Embodiment 6
A kind of recovery method of abandoned catalyst in direct synthesis methylchlorosilane, comprises the steps：
(1) weigh 100g waste catalyst, put into 500 DEG C of calcining 1h in tube furnace, to remove the carbon distribution of particle surface；
(2) addition 25g ammonium carbonate in the solid that step (1) is obtained, 35.5g (25.0wt%) ammonia, 200mL water,
At 60 DEG C, blowing air stirring leaching 5h, leaching finishes, and sucking filtration, washing are dried to obtain silicon-containing solid residue；
(3) add the hydrochloric acid of 100mL 20wt% in the silicon-containing solid residue obtaining to step (2), 50 DEG C are soaked 5h, molten
Solve various metallic element therein, then reduce pressure sucking filtration, and filtering residue water cleans to pH ≈ 7, afterwards 90 DEG C in vacuum drying oven
Vacuum drying 2h obtains silica flour；Acid solution (hydrochloric acid) can be reused and be neutralized to pH ≈ 7 to when can not reuse with sodium hydroxide
Discharge；The silica flour purity preparing is 96.9%；
(4) take the silica flour of the above-mentioned acquisition of 20g, add 200mL water, activate 30min at 80 DEG C, obtain suspension；Then
Add 0.5g sodium hydroxide, stirring reaction 10h at 80 DEG C；Stand overnight afterwards, then sucking filtration, remove wherein unreacted silicon
Grain, that is, obtain Ludox.
Embodiment 7
A kind of recovery method of abandoned catalyst in direct synthesis methylchlorosilane, comprises the steps：
(1) weigh 100g waste catalyst, put into 550 DEG C of calcining 1h in tube furnace, to remove the carbon distribution of particle surface；
(2) addition 30g ammonium carbonate in the solid that step (1) is obtained, 42.6g (25.0wt%) ammonia, 200mL water,
At 60 DEG C, blowing air stirring leaching reaction 5h, leaching finishes, and sucking filtration, washing are dried to obtain silicon-containing solid residue；
(3) add the hydrochloric acid of 100mL 20wt% in the silicon-containing solid residue obtaining to step (2), 50 DEG C are soaked 7h, molten
Solve various metallic element therein, then reduce pressure sucking filtration, and filtering residue water cleans to pH ≈ 7, afterwards 90 DEG C in vacuum drying oven
Vacuum drying 2h obtains silica flour；Acid solution (hydrochloric acid) can be reused and be neutralized to pH ≈ 7 to when can not reuse with sodium hydroxide
Discharge；The silica flour purity preparing is 97.3%；
(4) take the silica flour of the above-mentioned acquisition of 30g, add 200mL water, activate 30min at 80 DEG C, obtain suspension；Then
Add 1.0g sodium hydroxide, stirring reaction 10h at 80 DEG C；Stand overnight afterwards, then sucking filtration, remove wherein unreacted silicon
Grain, that is, obtain Ludox.
Embodiment 8
A kind of recovery method of abandoned catalyst in direct synthesis methylchlorosilane, comprises the steps：
(1) weigh 100g waste catalyst, put into 600 DEG C of calcining 1h in tube furnace, to remove the carbon distribution of particle surface；
(2) addition 30g ammonium hydrogen carbonate in the solid that step 1 is obtained, 68.3g (25.0wt%) ammonia, 200mL water,
At 70 DEG C, blowing air stirring leaching reaction 5h, leaching finishes, and sucking filtration, washing are dried to obtain silicon-containing solid residue；
(3) add the hydrochloric acid of 100mL 20wt% in the silicon-containing solid residue obtaining to step (2), 60 DEG C are soaked 5h, molten
Solve various metallic element therein, then reduce pressure sucking filtration, and filtering residue water cleans to pH ≈ 7, afterwards 90 DEG C in vacuum drying oven
Vacuum drying 2h obtains silica flour；Acid solution (hydrochloric acid) can be reused and be neutralized to pH ≈ 7 to when can not reuse with sodium hydroxide
Discharge；The silica flour purity preparing is 97.5%；
(4) take the silica flour of the above-mentioned acquisition of 30g, add 200mL water, activate 30min at 80 DEG C, obtain suspension；Then
Add 1.0g sodium hydroxide, stirring reaction 10h at 90 DEG C；Stand overnight afterwards, then sucking filtration, remove wherein unreacted silicon
Grain, that is, obtain Ludox.
Comparative example
Commercially available Ludox, purchased from the hx model Ludox of Beijing Red Star spacious mansion chemical building material company limited.
The SEM figure of the Ludox that Fig. 3 provides for comparative example；Ludox given by Fig. 2 and Fig. 3 is all spherical in shape.
The performance test results of embodiment and comparative example are shown in Table 1：
The performance test results of the Ludox of table 1 embodiment and comparative example offer
Performance test methods are：SiO2Content：Method of burning of high temperature；Na2O content and mean diameter：Titrimetry；pH：PHS-3C
Type pH meter；Density：Baume hydrometer.
Industry standard is：
SiO2Content：>=20wt%；Na2O content：≤ 0.4wt%；pH：9.0～10.0；25 DEG C of density：1.12-1.21g/
cm3；Mean diameter ,≤100nm.
Applicant states, the present invention illustrates detailed process equipment and the technological process of the present invention by above-described embodiment,
But the invention is not limited in above-mentioned detailed process equipment and technological process, that is, do not mean that the present invention has to rely on above-mentioned detailed
Process equipment and technological process could be implemented.Person of ordinary skill in the field it will be clearly understood that any improvement in the present invention,
The interpolation of the equivalence replacement to each raw material of product of the present invention and auxiliary element, selection of concrete mode etc., all fall within the present invention's
Within the scope of protection domain and disclosure.
Claims (22)
1. a kind of recovery method of abandoned catalyst in direct synthesis methylchlorosilane is it is characterised in that methods described comprises the steps：
(1) calcine abandoned catalyst in direct synthesis methylchlorosilane, remove its area carbon；
(2) abandoned catalyst in direct synthesis methylchlorosilane after leaching step (1) is processed in the ammonia containing oxidant-ammonium salt mixed solution, leaching finishes,
Filter, washing, filtering residue is dried, obtains silicon-containing solid residue；
(3) add acid solution to be soaked in the silicon-containing solid residue obtaining to step (2), soak after terminating, separate, wash, do
Silica flour is obtained after dry；
(4) silica flour obtaining step (3) is dispersed in water, and temperature control activates, and obtains suspension, adds catalyst, heating afterwards
Stirring is reacted, and after standing, sucking filtration obtains Ludox.
2. method as claimed in claim 1 is it is characterised in that the described calcining heat of step (1) is 300～800 DEG C；Calcination time
For 0.5～4h.
3. method as claimed in claim 1 is it is characterised in that the described calcining heat of step (1) is 500～600 DEG C；Calcination time
For 0.5～2h.
4. method as claimed in claim 1 is it is characterised in that the described calcining of step (1) is in Muffle furnace, tube furnace or batch-type furnace
Carry out.
5. method as claimed in claim 1 is it is characterised in that in the described ammonia-ammonium salt mixed solution containing oxidant of step (2)
Oxidant is the combination of any a kind or at least 2 kinds in air, oxygen or hydrogen peroxide.
6. method as claimed in claim 1 it is characterised in that the described ammonia-ammonium salt of step (2) be contain ammonia and ammonium salt simultaneously,
Described ammonium salt is the combination of any a kind or at least 2 kinds in ammonium chloride, ammonium carbonate or ammonium hydrogen carbonate.
7. method as claimed in claim 1 is it is characterised in that ammonia in the described ammonia-ammonium salt mixed solution containing oxidant of step (2)
Water is 1 with the mol ratio of ammonium salt:1.5～5.
8. method as claimed in claim 1 is it is characterised in that in the described ammonia-ammonium salt mixed solution containing oxidant of step (2),
Ammonia-ammonium salt is 0.2～1 with the mass ratio of the abandoned catalyst in direct synthesis methylchlorosilane of leaching:1.
9. method as claimed in claim 1 it is characterised in that the described leaching temperature of step (2) be 20～100 DEG C, leaching time
For 1～8h.
10. method as claimed in claim 1 it is characterised in that the described leaching temperature of step (2) be 20～70 DEG C, leaching time
For 3～5h.
11. methods as claimed in claim 1 are it is characterised in that the described acid solution of step (3) is selected from nitric acid, sulphuric acid, hydrochloric acid or phosphoric acid
In any a kind or at least 2 kinds of combination.
12. methods as claimed in claim 1 are it is characterised in that H in described acid solution+Concentration be 2～10mol/L.
13. methods as claimed in claim 1 are it is characterised in that the mass ratio of the addition of described acid solution and silicon-containing solid residue
For 0.5～1:1.
14. methods as claimed in claim 1 it is characterised in that the described soaking temperature of step (3) be 20～60 DEG C, soak time
For 1～10h.
15. methods as claimed in claim 1 it is characterised in that the described soaking temperature of step (3) be 20～60 DEG C, soak time
For 3～5h.
16. methods as claimed in claim 1 are it is characterised in that the described silica flour of step (4) is 1 with the mass ratio of water:1～20.
17. methods as claimed in claim 1 it is characterised in that the described catalyst of step (4) be selected from sodium hydroxide, potassium hydroxide,
Any a kind in Lithium hydrate, ammonia, sodium silicate or potassium silicate or at least 2 kinds of combination.
18. methods as claimed in claim 1 it is characterised in that the described catalyst of step (4) and silica flour mass ratio be 0.02～
0.1:1.
19. methods as claimed in claim 1 it is characterised in that the described heated and stirred of step (4) temperature be 30～100 DEG C, when
Between be 3～10h.
20. methods as claimed in claim 1 it is characterised in that the described heated and stirred of step (4) temperature be 80～90 DEG C, when
Between be 8～10h.
21. methods as claimed in claim 1 are it is characterised in that the described time of repose of step (4) is more than 5h.
22. methods as claimed in claim 1 are it is characterised in that the described time of repose of step (4) is more than 10h.
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| CN106744996A (en) * | 2016-11-28 | 2017-05-31 | 济南汇川硅溶胶厂 | A kind of Ludox and preparation method thereof |
| CN109319795B (en) * | 2018-10-18 | 2020-07-31 | 江西星火狮达科技有限公司 | Method for producing silica sol by recovering and purifying silicon powder from organic silicon slag |
| CN114349010B (en) * | 2022-02-23 | 2023-07-14 | 新疆大全新能源股份有限公司 | Method for removing carbon from waste silicon powder after copper extraction |
| CN115058586B (en) * | 2022-06-30 | 2024-06-18 | 武汉理工大学 | Method for recycling copper and silicon powder from organic silicon waste contact |
| CN116462199A (en) * | 2023-05-08 | 2023-07-21 | 昆明理工大学 | Method for removing carbon in organosilicon waste contact and waste slurry slag |
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| CN1329292C (en) * | 2005-11-11 | 2007-08-01 | 山东大学 | Method for reactivating and regenerating waste silicon powder |
| CN102795653B (en) * | 2011-05-25 | 2014-09-24 | 中国科学院过程工程研究所 | Method for recycling copper oxide and zinc oxide from organosilicon spent contact mass |
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Effective date of registration: 20190507 Address after: 100190 Science and Technology Development Department, Institute of Process Engineering, Chinese Academy of Sciences, No. 1, North Second Article, Zhongguancun, Haidian District, Beijing Patentee after: Institute of Process Engineering, Chinese Academy of Sciences Address before: 100190 No. 1 north of Zhongguancun, Haidian District, Haidian District, Beijing Co-patentee before: Nanjing He Feng new chemical materials Science and Technology Ltd. Patentee before: Institute of Process Engineering, Chinese Academy of Sciences |