CN104843721A - Organic silicon waste contact recovery method - Google Patents
Organic silicon waste contact recovery method Download PDFInfo
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- CN104843721A CN104843721A CN201510218038.0A CN201510218038A CN104843721A CN 104843721 A CN104843721 A CN 104843721A CN 201510218038 A CN201510218038 A CN 201510218038A CN 104843721 A CN104843721 A CN 104843721A
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Abstract
The invention relates to an organic silicon waste contact recovery method which includes the steps: (1) calcining an organic silicon waste contact and removing surface carbon deposits; (2) leaching, filtering and washing the organic silicon waste contact treated in the step (1) in ammonia-ammonium salt mixed solution containing oxidizing agents, and drying filter residues to obtain silicon containing solid residues; (3) adding acid liquor into the silicon containing solid residues obtained in the step (2), and soaking, separating, washing and drying the silicon containing solid residues to obtain silicon powder; (4) dispersing the silicon powder obtained in the step (3) in water, controlling temperature and activating the silicon powder to obtain suspending liquid, adding a catalyst into the suspending liquid, heating and stirring the suspending liquid, performing reaction, and performing suction filtration after standing to obtain silica solution. The method is low in cost and simple to operate, materials are easily obtained, and large-scale popularization is easily performed.
Description
Technical field
The present invention relates to abandoned catalyst in direct synthesis methylchlorosilane and reclaim field, particularly relate to a kind of method recycling abandoned catalyst in direct synthesis methylchlorosilane and prepare silicon sol.
Background technology
Methyl chlorosilane prepares the most important monomer of organosilicon polymer.Wherein, with dimethyldichlorosilane(DMCS) [M
2] consumption maximum, account for 90% of methyl chlorosilane.At production M
2fluidized-bed reactor in, silica flour and copper catalyst are mixed to form active contact, and along with the prolongation in reaction times, the settling on contact surface can get more and more, make contact activity reduce, cause M
2selectivity reduce, now, wherein the mixture of unreacted silica flour and catalyzer need discharge reactor, add simultaneously new contact be beneficial to reaction carry out continuously and stably.In addition, along with the continuous consumption of silica flour in reaction, silicon grain constantly diminishes, and the gas solid separation system of fluidized-bed discharges the serious fine powder of surface contamination continuously, and this two portions waste residue becomes waste catalyst.The major ingredient of these waste catalysts is: silicon, copper, carbon, zinc etc., and their weight contents in waste catalyst are respectively 65% ~ 80%, 3% ~ 20%, 1% ~ 10%, 0.05% ~ 2.0%.Waste catalyst due to particle tiny, and the activity of copper powder is higher, meets air and easily oxidizing reaction occurs, and organic substance wherein and carbon burning are emerged pungent white cigarette, and not easily store, environmental pollution is serious, brings very large hidden danger to safety in production simultaneously.Abroad as far back as last century the fifties just carried out the recycling research of abandoned catalyst in direct synthesis methylchlorosilane, current silicone industry in China enterprise is generally by burying or selling to small business at a low price to the processing mode of waste catalyst.This not only causes serious environmental pollution, is also waste to silicon, copper resource.The existence of heavy metal pollutes the environment; And the discarded organosilicon product cost that causes of the elemental silicon of costliness is very high.
State of the art mainly concentrates on the recovery (as CN1083418A, CN1844422A and CN1618840A) of silica flour and copper powder to the comprehensive utilizating research of waste catalyst, and carry out recovery silica flour processing and utilization research (CN1760124A and CN1465524A), return organosilane monomer production line as being processed into qualified silica flour, or become silico briquette by smelting processing and be used.But the complex process that prior art fully utilizes abandoned catalyst in direct synthesis methylchlorosilane, generates obnoxious flavour in process, and the utilization ratio of silicon 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 recovery research, it is the technical barrier that current field of organic silicon must solve, it pollutes organosilicon Reducing Cost in Enterprises, reduction, and the sound development promoting China's silicone industry is extremely important.
Silicon sol is the colloidal solution that nanosized silica particles is scattered in water, has another name called silicic acid sol, or silica hydrosol.Silicon sol has many advantageous properties, in inorganic silicon compound, tool is very promising, corrosion-resistant due to it, high temperature resistant, anti-oxidant, bigger serface, high absorbability, high degree of dispersion, the performances such as high-insulativity, and raw material sources are extensive, be convenient to produce, cheap, to advantages such as the mankind and environment toxicological harmlesss, since twentieth century forties, silicon sol is in machinofacture, petrochemical complex, light textile, be used widely in the industrial sectors such as electronics, particularly the rise of Inorganic Macromolecules Building Coatings and electronic industry develop rapidly, the demand of silicon sol increases fast.
There are a kind of needs reclaiming silica flour and prepare the method for silicon sol from abandoned catalyst in direct synthesis methylchlorosilane of exploitation this area, and it is simple that described method should have process, and raw material is easy to get, easy to operate characteristic.
Summary of the invention
For the deficiencies in the prior art, an object of the present invention is to provide a kind of silica flour utilizing abandoned catalyst in direct synthesis methylchlorosilane to reclaim to prepare the method for silicon sol, has significant economic benefit and environmental benefit.
The present invention realizes especially by following scheme:
A recovery method for abandoned catalyst in direct synthesis methylchlorosilane, described method comprises the steps:
(1) calcine abandoned catalyst in direct synthesis methylchlorosilane, remove its area carbon;
(2) abandoned catalyst in direct synthesis methylchlorosilane in the ammonia-ammonium salt mixing solutions containing oxygenant after leaching step (1) process, leaches complete, filters, washing, and dry filter residue, obtains silicon-containing solid residue;
(3) add acid solution in the silicon-containing solid residue obtained to step (2) to soak, soak after terminating, be separated, washing, obtain silica flour after drying;
(4) be dispersed in water by the silica flour that step (3) obtains, temperature control activates, and obtain suspension, add catalyzer afterwards, heated and stirred is reacted, and after leaving standstill, suction filtration obtains silicon sol.
Abandoned catalyst in direct synthesis methylchlorosilane based on silicon, copper, carbon, and containing a small amount of metal ingredient such as tin, zinc, through calcining provided by the invention, ammonia-ammonium salt leaching, acid soak, can obtain pure silica flour; And silicon can generate silicic acid monomer and hydrogen with water in the basic conditions, silicic acid monomer can form silicon sol by the polymerization of self.Particularly, silica flour gives birth to silicic acid molecule, shown in (1) with water generation hydrolysis reaction under the effect of catalyzer:
Si+2OH
-+H
2O→SiO
3 2-+2H
2↑ (1)
The active silicic acid generated has strong in agglomeration tendency, thus active silicic acid soft-agglomerated after form polysilicon acid.After the concentration of solution mesosilicic acid reaches supersaturation, undergo phase transition reaction, there is dehydration condensation and separate out nucleus in amount of activated silicic acid, reacts such as formula shown in (2) voluntarily:
mH
2SiO
3+nH
2SiO
3→(n+m)SiO
2+(n+m)H
2O (2)
After nucleus is formed, active silicic acid will adsorb at nucleating surface, and nucleus is constantly grown up, thus forms silicon sol, reacts such as formula shown in (3):
nSiO
2+H
2SiO
3→(n+1)SiO
2+H
2O (3)。
Step of the present invention (1) described calcining temperature 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 is 0.5 ~ 4h, such as 0.8h, 1.2h, 1.6h, 2.3h, 2.8h, 3.3h, 3.8h etc.
Preferably, step (1) described calcining temperature is 500 ~ 600 DEG C; Calcination time is 0.5 ~ 2h.
Preferably, step (1) described calcining is carried out in retort furnace, tube furnace or box-type furnace.
In organosilane monomer building-up process, silicon powder surface meeting deposited carbon layer, form carbon distribution, affect follow-up reactive behavior, therefore waste catalyst is carried out calcination processing by the present invention, can remove the carbon distribution on waste catalyst surface.
Step of the present invention (2) is described is the combination of any a kind or at least 2 kinds in air, oxygen or hydrogen peroxide containing the oxygenant in the ammonia-ammonium salt mixing solutions of oxygenant.
Preferably, the described ammonia-ammonium salt of step (2) is simultaneously containing ammoniacal liquor and ammonium salt, and described ammonium salt is the combination of any a kind or at least 2 kinds in ammonium chloride, volatile salt or bicarbonate of ammonia.
Preferably, step (2) is described is 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 etc. containing the mol ratio of ammoniacal liquor and ammonium salt in the ammonia-ammonium salt mixing solutions of oxygenant.
Preferably, step (2) is described containing in the ammonia-ammonium salt mixing solutions of oxygenant, and the mass ratio of the abandoned catalyst in direct synthesis methylchlorosilane of ammonia-ammonium salt and leaching is 0.2 ~ 1:1, such as 0.2:1,0.5:1,0.6:1,0.8:1 etc.
Step of the present invention (2) described leaching temperature is 20 ~ 100 DEG C, and 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, step (2) described leaching temperature is 20 ~ 70 DEG C, and leaching time is 3 ~ 5h.
Step of the present invention (3) described acid solution is selected from the combination of any a kind or at least 2 kinds in nitric acid, sulfuric acid, hydrochloric acid or phosphoric acid;
Preferably, H in described acid solution
+concentration be 2 ~ 10mol/L, such as 3mol/L, 5mol/L, 9mol/L etc.;
Preferably, the add-on of described acid solution and the mass ratio of silicon-containing solid residue are 0.5 ~ 1:1.
Step of the present invention (3) described soaking temperature is 20 ~ 60 DEG C, and such as 23 DEG C, 25 DEG C, 36 DEG C, 42 DEG C, 48 DEG C, 55 DEG C etc., soak time is 1 ~ 10h; Preferred described soaking temperature is 20 ~ 60 DEG C, and soak time is 3 ~ 5h.
The mass ratio of step of the present invention (4) described silica flour and water is 1:1 ~ 20, such as 1:2,1:6,1:12,1:15,1:18,1:19 etc.
Step of the present invention (4) described catalyzer is selected from the combination of any a kind or at least 2 kinds in sodium hydroxide, potassium hydroxide, lithium hydroxide, ammoniacal liquor, water glass or potassium silicate.
Preferably, the mass ratio of step (4) described catalyzer 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 step of the present invention (4) described heated and stirred is 30 ~ 100 DEG C, and 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 step (4) described heated and stirred is 80 ~ 90 DEG C, and the time is 8 ~ 10h;
Preferably, step (4) described time of repose is more than 5h, such as 6h, 8h, 11h, 16h, 20h, 23h, 25h etc., preferred more than 10h.
Silicon powder surface contains one deck inert coating, is mainly silicon dioxide film, and it can, by inner material passivation, stop reaction to occur.The present invention carry out with catalyst reaction before activate, the zone of oxidation of silicon powder surface can be removed, increase reactive behavior, reaction is more easily occurred, otherwise the silica flour being 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, comprises the steps:
(1) at 300 ~ 800 DEG C, calcine abandoned catalyst in direct synthesis methylchlorosilane, calcination time is 0.5 ~ 4h, is removed by the carbon distribution on waste catalyst surface;
(2) in the sample obtained to step (1), the ammonia-ammonium salt mixing solutions added containing oxygenant leaches, leaching temperature 20 ~ 100 DEG C, and leaching time is 1 ~ 8h, after filtration, washing, obtains silicon-containing solid residue after drying;
(3) in the silicon-containing solid residue of step (2) gained, add acid solution, at temperature 20 ~ 60 DEG C, soak 1 ~ 10h, after separation, washing, drying, obtain silica flour;
(4) silica flour that step (3) obtains fully is mixed with water, obtain mixing suspension, then priming reaction 10 ~ 60min under 30 ~ 100 DEG C of temperature condition; Catalyzer is added in gained mixing suspension, reacting by heating, wherein the amount of added catalyzer and the mass ratio of step (3) gained silica flour are 0.02:1 ~ 0.1:1, carry out solid-liquid separation after reaction, remove unreacted silica flour, the solution obtained is silicon sol.
Compared with prior art, the present invention has following beneficial effect:
(1) the invention provides and adopt the solid residue waste catalyst of organosilicon compound probability to obtain the higher silica flour of purity through calcining, ammonia leaching (ammonia-ammonium salt leaching), acidleach, then the method obtaining silicon sol in the aqueous solution containing basic catalyst is dispersed in, this method save production cost, there is obvious economic benefit; Reduce the pollution of waste catalyst to environment, there is obvious environmental benefit;
(2) method provided by the invention can prepare the higher silica flour of purity, has both avoided heavy metals emission and has caused environmental pollution, and can realize again the recycle of material;
(3) method provided by the invention is easy and simple to handle, with low cost; The reagent market used is common, and Material Cost investment is low, is easy to realize scale operation.
Accompanying drawing explanation
Fig. 1 is the XRD spectra of the silica flour that embodiment 1 step (3) obtains;
Fig. 2 is the SEM figure that embodiment 1 obtains silicon sol;
The SEM figure of the silicon sol that Fig. 3 provides for comparative example.
Embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art should understand, described embodiment is only help to understand the present invention, should not be considered as concrete restriction of the present invention.
Embodiment 1
A recovery method for abandoned catalyst in direct synthesis methylchlorosilane, comprises the steps:
(1) take 100g waste catalyst, put into 500 DEG C of calcining 1h in retort furnace, to remove the carbon distribution of particle surface;
(2) add 17g volatile salt in solid step (1) obtained, 36g (25.0wt%) ammoniacal liquor, 200mL water, at 20 DEG C, blowing air stirs leaching 3h, and leach complete, suction filtration, washing, drying obtains silicon-containing solid residue;
(3) hydrochloric acid of 100mL 20wt% is added in the silicon-containing solid residue obtained to step (2), 20 DEG C are soaked 3h, dissolve wherein each kind of metallic element, then decompress filter, the cleaning of filter residue use water is to pH ≈ 7, and in vacuum drying oven, 90 DEG C of vacuum-drying 2h obtain silica flour afterwards; Acid solution (hydrochloric acid) can be reused and discharge to being neutralized to pH ≈ 7 with sodium hydroxide when can not re-use; The silica flour purity prepared is 97.3%;
(4) get the silica flour that 15g step (3) obtains, add 200mL water-dispersion, at 80 DEG C, activate 30min, obtain suspension; Then 0.5g sodium hydroxide is added, stirring reaction 8h at 80 DEG C; Hold over night afterwards, then suction filtration, remove wherein unreacted silicon grain, namely obtain silicon sol.
Performance test:
Embodiment 1 is reclaimed from waste catalyst X ' Pert PRO MPD type Multi-functional X ray diffractometer that the silica flour that obtains produces Dutch Panalytical company (PANalytical) and carries out XRD test; As shown in Figure 1, Fig. 1 is the XRD spectra of the silica flour that embodiment 1 step (3) obtains to result, and diffraction peak is wherein the characteristic diffraction peak of silicon, does not have other assorted peak, shows to adopt this method to achieve the purification of silicon;
The JSM6700 model field emission scanning electron microscope observation surface topography that silicon sol embodiment 1 prepared is produced in NEC company; Fig. 2 is the SEM figure that embodiment 1 obtains silicon sol.
Embodiment 2
A recovery method for abandoned catalyst in direct synthesis methylchlorosilane, comprises the steps:
(1) take 100g waste catalyst, put into 500 DEG C of calcining 30min in retort furnace, to remove the carbon distribution of particle surface;
(2) 22.5g volatile salt is added in solid step (1) obtained, 40g (25.0wt%) ammoniacal liquor, 200mL water, at 40 DEG C, blowing air stirs leaching reaction 3h, leaches complete, suction filtration, washing, drying obtains silicon-containing solid residue;
(3) add the hydrochloric acid of 100mL 20wt% in the silicon-containing solid residue obtained to step (2), 30 DEG C are soaked 3h, dissolve wherein each kind of metallic element, then decompress filter; The cleaning of filter residue use water is to pH ≈ 7, and in vacuum drying oven, 90 DEG C of vacuum-drying 2h obtain silica flour afterwards; Acid solution (hydrochloric acid) can be reused and discharge to being neutralized to pH ≈ 7 with sodium hydroxide when can not re-use; The silica flour purity prepared is 96.8%;
(4) get the silica flour that 15g step (3) obtains, add 200mL water-dispersion, at 80 DEG C, activate 30min, obtain suspension; Then 0.5g sodium hydroxide is added, stirring reaction 8h at 90 DEG C; By liquid hold over night, then suction filtration, remove wherein unreacted silicon grain, namely obtain silicon sol.
Embodiment 3
A recovery method for abandoned catalyst in direct synthesis methylchlorosilane, comprises the steps:
(1) take 100g waste catalyst, put into 550 DEG C of calcining 1h in retort furnace, to remove the carbon distribution of particle surface;
(2) add 20g volatile salt in solid step (1) obtained, 45.5g (25.0wt%) ammoniacal liquor, 200mL water, at 60 DEG C, blowing air stirs leaching 3h, and leach complete, suction filtration, washing, drying obtains silicon-containing solid residue;
(3) hydrochloric acid of 100mL 20wt% is added in the silicon-containing solid residue obtained to step (2), 40 DEG C are soaked 3h, dissolve wherein each kind of metallic element, then decompress filter, the cleaning of filter residue use water is to pH ≈ 7, and in vacuum drying oven, 90 DEG C of vacuum-drying 2h obtain silica flour afterwards; Acid solution (hydrochloric acid) can be reused and discharge to being neutralized to pH ≈ 7 with sodium hydroxide when can not re-use; The silica flour purity prepared is 97.2%;
(4) get the silica flour that 25g step (3) obtains, add 200mL water-dispersion, at 80 DEG C, activate 30min, obtain suspension; Then 1.0g sodium hydroxide is added, stirring reaction 8h at 80 DEG C; Hold over night afterwards, then suction filtration, remove wherein unreacted silicon grain, namely obtain silicon sol.
Embodiment 4
A recovery method for abandoned catalyst in direct synthesis methylchlorosilane, comprises the steps:
(1) take 100g waste catalyst, put into 550 DEG C of calcining 2h in retort furnace, to remove the carbon distribution of particle surface;
(2) 25g bicarbonate of ammonia is added in solid step (1) obtained, 53.5g (25.0wt%) ammoniacal liquor, 200mL water, at 40 DEG C, blowing air stirs leaching 5h, leaches complete, suction filtration, washing, drying obtains silicon-containing solid residue;
(3) nitric acid of 100mL 20wt% is added in the silicon-containing solid residue obtained to step (2), 25 DEG C are soaked 3h, dissolve wherein each kind of metallic element, then decompress filter, the cleaning of filter residue use water is to pH ≈ 7, and in vacuum drying oven, 90 DEG C of vacuum-drying 2h obtain silica flour afterwards; Acid solution (nitric acid) can be reused and discharge to being neutralized to pH ≈ 7 with sodium hydroxide when can not re-use; The silica flour purity prepared is 96.8%;
(4) get the silica flour that 25g step (3) obtains, add 200mL water-dispersion, at 80 DEG C, activate 30min, obtain suspension; Then 1.0g sodium hydroxide is added, stirring reaction 8h at 90 DEG C; Hold over night afterwards, then suction filtration, remove wherein unreacted silicon grain, namely obtain silicon sol.
Embodiment 5
A recovery method for abandoned catalyst in direct synthesis methylchlorosilane, comprises the steps:
(1) take 100g waste catalyst, put into 500 DEG C of 30min in tube furnace, to remove the carbon distribution of particle surface;
(2) 22.7g bicarbonate of ammonia is added in solid step (1) obtained, 58.5g (25.0wt%) ammoniacal liquor, 200mL water, at 50 DEG C, blowing air stirs leaching 5h, leaches complete, suction filtration, washing, drying obtains silicon-containing solid residue;
(3) add the nitric acid of 100mL 20wt% in the silicon-containing solid residue obtained to step (2), 30 DEG C are soaked 3h, dissolve wherein each kind of metallic element, then decompress filter; The cleaning of filter residue use water is to pH ≈ 7, and in vacuum drying oven, 90 DEG C of vacuum-drying 2h obtain silica flour afterwards; Acid solution (nitric acid) can be reused and discharge to being neutralized to pH ≈ 7 with sodium hydroxide when can not re-use; The silica flour purity prepared is 97.4%;
(4) get the silica flour that 30g step (3) obtains, add 200mL water-dispersion, at 80 DEG C, activate 30min, obtain suspension; Then 1.0g sodium hydroxide is added, stirring reaction 8h at 90 DEG C; By liquid hold over night, then suction filtration, remove wherein unreacted silicon grain, namely obtain silicon sol.
Embodiment 6
A recovery method for abandoned catalyst in direct synthesis methylchlorosilane, comprises the steps:
(1) take 100g waste catalyst, put into 500 DEG C of calcining 1h in tube furnace, to remove the carbon distribution of particle surface;
(2) add 25g volatile salt in solid step (1) obtained, 35.5g (25.0wt%) ammoniacal liquor, 200mL water, at 60 DEG C, blowing air stirs leaching 5h, and leach complete, suction filtration, washing, drying obtains silicon-containing solid residue;
(3) hydrochloric acid of 100mL 20wt% is added in the silicon-containing solid residue obtained to step (2), 50 DEG C are soaked 5h, dissolve wherein each kind of metallic element, then decompress filter, the cleaning of filter residue use water is to pH ≈ 7, and in vacuum drying oven, 90 DEG C of vacuum-drying 2h obtain silica flour afterwards; Acid solution (hydrochloric acid) can be reused and discharge to being neutralized to pH ≈ 7 with sodium hydroxide when can not re-use; The silica flour purity prepared is 96.9%;
(4) get the silica flour of the above-mentioned acquisition of 20g, add 200mL water, at 80 DEG C, activate 30min, obtain suspension; Then 0.5g sodium hydroxide is added, stirring reaction 10h at 80 DEG C; Hold over night afterwards, then suction filtration, remove wherein unreacted silicon grain, namely obtain silicon sol.
Embodiment 7
A recovery method for abandoned catalyst in direct synthesis methylchlorosilane, comprises the steps:
(1) take 100g waste catalyst, put into 550 DEG C of calcining 1h in tube furnace, to remove the carbon distribution of particle surface;
(2) 30g volatile salt is added in solid step (1) obtained, 42.6g (25.0wt%) ammoniacal liquor, 200mL water, at 60 DEG C, blowing air stirs leaching reaction 5h, leaches complete, suction filtration, washing, drying obtains silicon-containing solid residue;
(3) hydrochloric acid of 100mL 20wt% is added in the silicon-containing solid residue obtained to step (2), 50 DEG C are soaked 7h, dissolve wherein each kind of metallic element, then decompress filter, the cleaning of filter residue use water is to pH ≈ 7, and in vacuum drying oven, 90 DEG C of vacuum-drying 2h obtain silica flour afterwards; Acid solution (hydrochloric acid) can be reused and discharge to being neutralized to pH ≈ 7 with sodium hydroxide when can not re-use; The silica flour purity prepared is 97.3%;
(4) get the silica flour of the above-mentioned acquisition of 30g, add 200mL water, at 80 DEG C, activate 30min, obtain suspension; Then 1.0g sodium hydroxide is added, stirring reaction 10h at 80 DEG C; Hold over night afterwards, then suction filtration, remove wherein unreacted silicon grain, namely obtain silicon sol.
Embodiment 8
A recovery method for abandoned catalyst in direct synthesis methylchlorosilane, comprises the steps:
(1) take 100g waste catalyst, put into 600 DEG C of calcining 1h in tube furnace, to remove the carbon distribution of particle surface;
(2) add 30g bicarbonate of ammonia in solid step 1 obtained, 68.3g (25.0wt%) ammoniacal liquor, 200mL water, at 70 DEG C, blowing air stirs leaching reaction 5h, and leach complete, suction filtration, washing, drying obtains silicon-containing solid residue;
(3) hydrochloric acid of 100mL 20wt% is added in the silicon-containing solid residue obtained to step (2), 60 DEG C are soaked 5h, dissolve wherein each kind of metallic element, then decompress filter, the cleaning of filter residue use water is to pH ≈ 7, and in vacuum drying oven, 90 DEG C of vacuum-drying 2h obtain silica flour afterwards; Acid solution (hydrochloric acid) can be reused and discharge to being neutralized to pH ≈ 7 with sodium hydroxide when can not re-use; The silica flour purity prepared is 97.5%;
(4) get the silica flour of the above-mentioned acquisition of 30g, add 200mL water, at 80 DEG C, activate 30min, obtain suspension; Then 1.0g sodium hydroxide is added, stirring reaction 10h at 90 DEG C; Hold over night afterwards, then suction filtration, remove wherein unreacted silicon grain, namely obtain silicon sol.
Comparative example
Be purchased silicon sol, purchased from the hx model silicon sol of Beijing Red Star spacious mansion chemical building material company limited.
The SEM figure of the silicon sol that Fig. 3 provides for comparative example; Silicon sol given by Fig. 2 and Fig. 3 is all spherical in shape.
The performance test results of embodiment and comparative example is in table 1:
The performance test results of the silicon sol that table 1 embodiment and comparative example provide
Performance test methods is: SiO
2content: Method of burning of high temperature; Na
2o content and median size: volumetry; PH:PHS-3C type pH meter; Density: Beaumé scale.
Industry standard is:
SiO
2content:>=20wt%; Na
2o content :≤0.4wt%; PH:9.0 ~ 10.0; 25 DEG C of density: 1.12-1.21g/cm
3; Median size ,≤100nm.
Applicant states, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, namely do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of ancillary component, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.
Claims (9)
1. a recovery method for abandoned catalyst in direct synthesis methylchlorosilane, is characterized in that, described method comprises the steps:
(1) calcine abandoned catalyst in direct synthesis methylchlorosilane, remove its area carbon;
(2) abandoned catalyst in direct synthesis methylchlorosilane in the ammonia-ammonium salt mixing solutions containing oxygenant after leaching step (1) process, leaches complete, filters, washing, and dry filter residue, obtains silicon-containing solid residue;
(3) add acid solution in the silicon-containing solid residue obtained to step (2) to soak, soak after terminating, be separated, washing, obtain silica flour after drying;
(4) be dispersed in water by the silica flour that step (3) obtains, temperature control activates, and obtain suspension, add catalyzer afterwards, heated and stirred is reacted, and after leaving standstill, suction filtration obtains silicon sol.
2. method as claimed in claim 1, it is characterized in that, step (1) described calcining temperature is 300 ~ 800 DEG C; Calcination time is 0.5 ~ 4h;
Preferably, step (1) described calcining temperature is 500 ~ 600 DEG C; Calcination time is 0.5 ~ 2h;
Preferably, step (1) described calcining is carried out in retort furnace, tube furnace or box-type furnace.
3. method as claimed in claim 1 or 2, is characterized in that, step (2) is described is the combination of any a kind or at least 2 kinds in air, oxygen or hydrogen peroxide containing the oxygenant in the ammonia-ammonium salt mixing solutions of oxygenant;
Preferably, the described ammonia-ammonium salt of step (2) is simultaneously containing ammoniacal liquor and ammonium salt, and described ammonium salt is the combination of any a kind or at least 2 kinds in ammonium chloride, volatile salt or bicarbonate of ammonia;
Preferably, step (2) is described is 1:1.5 ~ 5 containing the mol ratio of ammoniacal liquor and ammonium salt in the ammonia-ammonium salt mixing solutions of oxygenant;
Preferably, step (2) is described containing in the ammonia-ammonium salt mixing solutions of oxygenant, and the mass ratio of the abandoned catalyst in direct synthesis methylchlorosilane of ammonia-ammonium salt and leaching is 0.2 ~ 1:1.
4. method as described in one of claims 1 to 3, is characterized in that, step (2) described leaching temperature is 20 ~ 100 DEG C, and leaching time is 1 ~ 8h;
Preferably, step (2) described leaching temperature is 20 ~ 70 DEG C, and leaching time is 3 ~ 5h.
5. method as described in one of Claims 1 to 4, is characterized in that, step (3) described acid solution is selected from the combination of any a kind or at least 2 kinds in nitric acid, sulfuric acid, hydrochloric acid or phosphoric acid;
Preferably, H in described acid solution
+concentration be 2 ~ 10mol/L;
Preferably, the add-on of described acid solution and the mass ratio of silicon-containing solid residue are 0.5 ~ 1:1.
6. method as described in one of Claims 1 to 5, is characterized in that, step (3) described soaking temperature is 20 ~ 60 DEG C, and soak time is 1 ~ 10h; Preferred described soaking temperature is 20 ~ 60 DEG C, and soak time is 3 ~ 5h.
7. method as described in one of claim 1 ~ 6, is characterized in that, the mass ratio of step (4) described silica flour and water is 1:1 ~ 20.
8. method as described in one of claim 1 ~ 7, is characterized in that, step (4) described catalyzer is selected from the combination of any a kind or at least 2 kinds in sodium hydroxide, potassium hydroxide, lithium hydroxide, ammoniacal liquor, water glass or potassium silicate;
Preferably, the mass ratio of step (4) described catalyzer and silica flour is 0.02 ~ 0.1:1.
9. method as described in one of claim 1 ~ 8, is characterized in that, the temperature of step (4) described heated and stirred is 30 ~ 100 DEG C, and the time is 3 ~ 10h;
Preferably, the temperature of step (4) described heated and stirred is 80 ~ 90 DEG C, and the time is 8 ~ 10h;
Preferably, step (4) described time of repose is more than 5h, preferred more than 10h.
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| CN105152174A (en) * | 2015-09-22 | 2015-12-16 | 中橡集团炭黑工业研究设计院 | Preparing method for high-purity white carbon black |
| CN106744996A (en) * | 2016-11-28 | 2017-05-31 | 济南汇川硅溶胶厂 | A kind of Ludox and preparation method thereof |
| CN109319795A (en) * | 2018-10-18 | 2019-02-12 | 江西星火狮达科技有限公司 | The method of recycling purification silicon powder production silica solution from organosilicon slag |
| CN114349010A (en) * | 2022-02-23 | 2022-04-15 | 新疆大全绿创环保科技有限公司 | Method for removing carbon from waste silicon powder after copper extraction |
| CN115058586A (en) * | 2022-06-30 | 2022-09-16 | 武汉理工大学 | Method for recovering 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 |
| CN116462199B (en) * | 2023-05-08 | 2024-10-22 | 昆明理工大学 | Method for removing carbon in organosilicon waste contact and waste slurry slag |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105152174A (en) * | 2015-09-22 | 2015-12-16 | 中橡集团炭黑工业研究设计院 | Preparing method for high-purity white carbon black |
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| 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 |
| CN116462199B (en) * | 2023-05-08 | 2024-10-22 | 昆明理工大学 | Method for removing carbon in organosilicon waste contact and waste slurry slag |
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