CN102674371B - Method for preparing white carbon black by utilizing silicon resin industrial waste acid - Google Patents
Method for preparing white carbon black by utilizing silicon resin industrial waste acid Download PDFInfo
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- CN102674371B CN102674371B CN 201210116359 CN201210116359A CN102674371B CN 102674371 B CN102674371 B CN 102674371B CN 201210116359 CN201210116359 CN 201210116359 CN 201210116359 A CN201210116359 A CN 201210116359A CN 102674371 B CN102674371 B CN 102674371B
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Abstract
The invention relates to a technology for preparing white carbon black. In order to solve the problem that a large quantity of waste hydrochloric acid generated in the preparation process of organic silicon resin pollutes the environment, the invention provides a method for preparing white carbon black by utilizing silicon resin industrial waste acid, which comprises the following steps: adding the silicon resin industrial waste acid into a reaction kettle, and agitating, heating and raising the temperature to 50-60 DEG C; dropwise adding water glass with a mass percent concentration of 10-30 percent into the reaction kettle within 1-1.5 hours, adjusting the pH value of the industrial waste acid to 6.5-8 after dropwise adding and uniformly agitating; and raising the temperature of reaction liquid to 75-90 DEG C, aging for 2-4 hours, carrying out centrifugal filtering or plate and frame type filtering, pulping and washing for more times, and drying and crushing to obtain the white carbon black. The method has the advantages of environment friendliness, simple process and low production cost, and moreover, the environment pollution brought by waste acid can be better solved.
Description
Technical field
The present invention relates to a kind of technology for preparing white carbon black, relate to specifically a kind of method of utilizing the silicone resin industrial waste acid to prepare white carbon black.
Background technology
White carbon black has another name called and is that hydrated SiO 2, molecular formula are SiO
2NH
2O, relative density is 2.319～2.653,1750 ℃ of fusing points are a kind of white, nontoxic, amorphous micro mist, have porous, light weight, high dispersive, high temperature resistant, do not burn, chemically stable and the excellent properties such as electrical insulating property is good.White carbon black is a kind of multifunction additive, is widely used in the industries such as silicon rubber, coating, printing ink, medicine, papermaking, food, makeup, chemically machinery polished, can play the effects such as reinforcement, thickening, thixotroping, delustring.At present the main production method of white carbon black has two kinds: vapor phase process and the precipitator method, and the former mainly adopts the raw materials such as silicoorganic compound, chlorosilane and silicon chlorides to produce, and product is of fine quality and valency is high; The latter utilizes silicate and inorganic acid reaction to produce, and product price is cheap, thereby the huge market demand.Along with the demand growth in fields such as tire production, Rubber Industry, toothpaste industry, coatings industries, the white carbon black that adopts the precipitator method to produce will be with 10% speed increment within the coming years at present.
Silicone resin is mainly from chlorosilane, makes through several operations such as hydrolysis, washing, concentrated and polycondensations.And this process of preparation silicone resin can produce a large amount of waste hydrochloric acids.Along with China's silicone resin output increases year by year, the amount of spent acid is also increasing, and contains organic solvent, organosilicon small molecules and other auxiliary agent in these spent acid, be difficult to process, and be a great potential safety hazard, if directly discharging is also very large source of pollution.Therefore, need to find a kind ofly can take full advantage of spent acid, not only technique is simple, and facility investment is few, can transform the method for the high product of production added value, and can fully utilize spent acid again, to satisfy the Sustainable development of organosilicon industry, solves simultaneously problem of environmental pollution.
The Chinese patent of CN1031821A discloses a kind of sulfuric acid alkylation acid sludge that utilizes and has made the white carbon black technology, this invention utilizes in acid sludge isolated sulfuric acid to replace in the past the precipitator method to make the required market of white carbon black pure sulfuric acid or hydrochloric acid in short supply, greatly reduce production costs, eliminate simultaneously spent acid to the pollution of environment.At first acid sludge is mixed with water, obtain dilute sulphuric acid and oil after standing demix, oil can be made oil fuel.Then make method for white carbon black by the precipitator method, carry out neutralization reaction with the dilute sulphuric acid and the water glass that are separated to, more aging, filter, washing, dry, pulverizing namely get transparent white carbon black products.But the method can only be used for the acid sludge of sulfuric acid alkylation to be processed, and can contain Na in the product that it obtains
2S and Na
2SR is difficult to clean out fully, and acid discharges hydrogen sulfide and stench appears in mercaptan when use procedure is met, and use is restricted.
Summary of the invention
For solving the problem that produces a large amount of waste hydrochloric acid contaminate environment in the silicone resin preparation process, the invention provides a kind of method of utilizing the silicone resin industrial waste acid to prepare white carbon black, the method is environmentally friendly, technique is simple, and production cost is low, and can well solve the environmental pollution that spent acid brings.
The present invention is achieved by the following technical solutions: a kind of method of utilizing the silicone resin industrial waste acid to prepare white carbon black, described preparation method are following steps:
(1), add silicone resin industrial waste acid, stirring heating to be warming up to 50～60 ℃ in reactor;
(2), to add mass percent concentration in 1～1.5 hour in the reactor be 15～30% water glass, dropwise to stir after with the silicone resin industrial waste acid, the pH value of reaction solution being adjusted to 6.5～8 afterwards; Under regular situation, churning time was to the maximum about 0.5 hour.
(3), reaction solution is warming up to 75～90 ℃, ageing 2～4 hours is adopted centrifugal or plate and frame filters, and carries out drying after making beating washing several times, pulverizes and obtains white carbon black;
Wherein, the mass ratio of silicone resin industrial waste acid and water glass is 1:1.075～3.15.
Silicone resin industrial waste acid described in step (1) is selected from the chlorosilane monomer or organosilicon high-boiling product is produced the spent acid that silicone resin produces, as preferably, the silicone resin industrial waste acid is selected from and produces organic group and Siliciumatom mol ratio (R/Si) is the spent acid that 0.95～1.3 chlorosilane monomer or organosilicon high-boiling product production silicone resin produce, the mass percent concentration of silicone resin industrial waste acid is 8～20%, as being preferably 10～20%.
Can contain organic solvent in silicone resin Industry Waste hydrochloric acid, the machine solvent that contains in silicone resin Industry Waste hydrochloric acid is the mixture of one or more arbitrary proportions in methyl alcohol, ethanol, propyl carbinol or Virahol.
The modulus of the water glass described in step (2) is 2.0～3.2, and as preferably, modulus is 2.5～3.0.
The present invention adopts and produces by chlorosilane monomer or organosilicon high-boiling product the spent acid that silicone resin produces, owing to having a small amount of organosilicon performed polymer and strong solvent in spent acid, need not separately to add relevant auxiliary agent and namely can overcome because gel produces the problem that strong aggregation produces bad dispersibility, thereby obtain the better white carbon black of performance.Whole technique is simple, and the environmental pollution that can fine minimizing spent acid brings.Product can be used for the fields such as rubber item, jointing compound and coating.
Compared with prior art, the invention has the beneficial effects as follows:
(1) preparation method of the present invention is environmentally friendly, technique is simple, and production cost is low, and facility investment is few, can transform the high product of production added value.
(2) can fully utilize spent acid, to satisfy the Sustainable development of organosilicon industry, solve simultaneously problem of environmental pollution.
Specific implementation method
Below in conjunction with embodiment, the present invention is described in further detail, desired raw material is all commercially available.
Embodiment 1:
Add in the reactor of 5L that to use R/Si be the industrial waste acid 2000g that 0.95 silicone resin produces, it is mixed with mass percent concentration is 20%, be heated with stirring to 50 ℃, 1.5 in individual hour with modulus be 3 and mass percent concentration be that 30% water glass 2150g drops in reactor, after dropwising, stir again after with pH regulator to 7.5 with 20% industrial waste acid.Reaction solution is warming up to 75 ℃, ageing 2 hours.Obtain white carbon black after centrifuging, making beating washing 2 times, drying, pulverizing.
The dioxide-containing silica 96.4% of this white carbon black, specific surface area 125m
2/ g, particle diameter 195nm.
Embodiment 2:
Add in the reactor of 5L that to use R/Si be the industrial waste acid 1000g that 1.3 silicone resin produces, it is mixed with mass percent concentration is 10%, be heated with stirring to 60 ℃, in 1 hour with modulus be 2 and concentration be that 15% water glass 3150g drops in reactor, after dropwising, the industrial waste acid with 10% stirs after with pH regulator to 8 again.Be warming up to 90 ℃, ageing 4 hours.Obtain white carbon black after centrifuging, making beating washing 2 times, drying, pulverizing.
The dioxide-containing silica 97.6% of this white carbon black, specific surface area 185m
2/ g, particle diameter 135nm.
Embodiment 3:
Add in the reactor of 5L that to use R/Si be the industrial waste acid 1300g that 1.1 silicone resin produces, it is mixed with mass percent concentration is 15%, be heated with stirring to 55 ℃, in 1 hour with modulus be 2.6 and concentration be that 20% water glass 2950g drops in reactor, after dropwising, the industrial waste acid with 15% stirs after with pH regulator to 6.5 again.Be warming up to 90 ℃, ageing 4 hours.Obtain white carbon black after centrifuging, making beating washing 2 times, drying, pulverizing.
The dioxide-containing silica 97.3% of this white carbon black, specific surface area 225m
2/ g, particle diameter 85nm.
Embodiment 4:
Add in the reactor of 100L that to use R/Si be the industrial waste acid 26Kg that 1.2 silicone resin produces, it is mixed with mass percent concentration is 8%, be heated with stirring to 55 ℃, 1.5 in individual hour with modulus be 2.5 and concentration be that 10% water glass 60.4Kg drops in reactor, after dropwising, the industrial waste acid with 8% continues to stir after pH is controlled at 7.Be warming up to 85 ℃, ageing 3 hours.After filtering, pull an oar washing 3 times, drying, pulverizing, plate and frame obtains white carbon black.
The dioxide-containing silica 97.7% of this white carbon black, specific surface area 245m
2/ g, particle diameter 80nm.
Claims (3)
1. a method of utilizing the silicone resin industrial waste acid to prepare white carbon black, is characterized in that, described method is following steps:
(1), add the silicone resin industrial waste acid in reactor, be heated to 50～60 ℃ under agitation condition, described silicone resin industrial waste acid is selected from the chlorosilane monomer or organosilicon high-boiling product is produced the spent acid that silicone resin produces, and wherein in the chlorosilane monomer, organic group and Siliciumatom mol ratio are 0.95～1.3;
(2), to drip mass percent concentration in 1～1.5 hour in the reactor be 10～30% water glass, dropwise to stir after with the silicone resin industrial waste acid, the pH value of reaction solution being adjusted to 6.5～8 afterwards;
(3), reaction solution is warming up to 75～90 ℃, ageing 2～4 hours is adopted centrifugal or plate and frame filters, and carries out drying after making beating washing several times, pulverizes and obtain white carbon black;
Wherein, the mass ratio of silicone resin industrial waste acid and water glass is 1:1.075～3.15.
2. a kind of method of utilizing the silicone resin industrial waste acid to prepare white carbon black according to claim 1, it is characterized in that: the mass percent concentration of silicone resin industrial waste acid is 8～20%.
3. a kind of method of utilizing the silicone resin industrial waste acid to prepare white carbon black according to claim 1 and 2, it is characterized in that: the modulus of the water glass described in step (2) is 2.0～3.2.
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| CN 201210116359 CN102674371B (en) | 2012-04-20 | 2012-04-20 | Method for preparing white carbon black by utilizing silicon resin industrial waste acid |
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| CN 201210116359 CN102674371B (en) | 2012-04-20 | 2012-04-20 | Method for preparing white carbon black by utilizing silicon resin industrial waste acid |
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| CN102674371B true CN102674371B (en) | 2013-11-06 |
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| CN105540926B (en) * | 2016-01-07 | 2018-02-16 | 江苏盛吉化工有限公司 | A kind of method using acid waste water co-producing white carbon black and inorganic salts |
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