CN105271254A - Method for preparing white carbon black through waste silicon slag - Google Patents
Method for preparing white carbon black through waste silicon slag Download PDFInfo
- Publication number
- CN105271254A CN105271254A CN201510769962.8A CN201510769962A CN105271254A CN 105271254 A CN105271254 A CN 105271254A CN 201510769962 A CN201510769962 A CN 201510769962A CN 105271254 A CN105271254 A CN 105271254A
- Authority
- CN
- China
- Prior art keywords
- silica
- white
- residue
- preparation
- carbon black
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Silicon Compounds (AREA)
Abstract
The invention relates to a preparing method for white carbon black, and belongs to the field of inorganic chemistries. The preparing method is a method in which waste silicon slag serves as raw materials and is subjected to a series of chemical reactions to extract the white carbon black. The preparing method includes the steps that firstly, the waste silicon slag with silicon dioxide and ammonium fluoride is chemically reacted to generate ammonium fluosilicate and ammonia gas; secondly, the obtained ammonium fluosilicate and ammonium hydroxide are chemically reacted to generate silicon dioxide and ammonium fluoride; finally, the obtained silicon dioxide is aged, washed and dried, and the white carbon black is prepared. According to the preparing method for the white carbon black, the technological process is short, and the number of required devices is small; raw material sources are wide and cheap, and high-energy-consumption products such as water glass are not used; the method is low in investment and cost, high in product added value and free of environmental pollution.
Description
Technical field
The present invention relates to a kind of preparation method of white carbon black, be react for raw material the method extracting white carbon black with useless white residue through sequence of chemical, belong to domain of inorganic chemistry.
Background technology
White carbon black is the general designation of fine powder or ultrafine particle shape anhydrous and aqueous silicon dioxide or silicates, is a kind of white, nontoxic, amorphous fine meal.Its SiO
2content comparatively large (being greater than 90%), initial size is generally 10-40nm, because comparatively poly-hydroxy is contained on surface, easily water suction and become the particulate of gathering.The relative density of white carbon black is 2.319-2.653g/cm
3.Fusing point is 1750 DEG C.Insoluble with water and acid, be dissolved in highly basic and hydrofluoric acid.Have porousness, internal surface area is large, polymolecularity, light weight, and chemical stability is good, high temperature resistant, do not burn, the excellent specific property such as nonpoisonous and tasteless and electrical insulating property is good.
At industrial circle, white carbon black is the important reinforcing filler of rubber item, and it significantly can improve the physicals of sizing material, reduces sizing material delayed, reduces the rolling resistance of tire, does not lose its anti-slippery simultaneously.In addition, white carbon black has a wide range of applications in plastics, papermaking, coating, makeup and ink etc., and exploitation prospect is very wide.
In view of the wide application of white carbon black, researchist wishes to utilize useless Preparation of White Silica by Silica Residue, realizes the object of achieving many things at one stroke.At home, researchist has done large quantifier elimination utilizing to prepare in white carbon black product containing the waste material of silicofluoric acid.Such as, Ning Ting makes profits and uses Phosphate Fertilizer Industry by product---and the waste material containing fluorine silica gel prepares high-reinforcement white carbon black.Wei Xiaoming has invented a kind of method utilizing industrial residue production of silica white, with the silicic acid sol waste residue produced in phosphate fertilizer, phosphamidon or other industrial production for raw material, produces the white carbon black that indices all meets plastics, rubber item needs.Abroad, the utilization overwhelming majority of fluorine and silicon is from silicofluoric acid, produces fluorochemical or silicon-dioxide, then produces other fluorochemical further.As US Patent No. 2945745, US3338673, US3501268, US4026997, US4915705 etc. adopt gas ammonia or ammonia soln and silicofluoric acid to react to produce Neutral ammonium fluoride and silicon-dioxide.
But in actual industrial production process, there is a large amount of waste material containing silicon-dioxide needs to process.Such as, after phosphatic fertilizer company waste gas containing fluoride ammonification (ammonia solution) or alkalization, obtain waste material, in detail can referenced patent (a kind of ammonia solution of fluorosilicone compound and the separation method of fluorine element silicon, application number: 2006100511407); Insoluble potassium bearing rock is after acidic fluoride process, and the white residue obtained after producing silicon tetrafluoride ammonification, in detail can referenced patent (a kind of method utilizing insoluble potassium bearing rock to produce potassium sulfate, application number: 2013105098514).But the not favourable preparation research realizing white carbon black with above-mentioned waste material as raw material.
Summary of the invention
For the limitation of existing preparation method, the object of the present invention is to provide the preparation method of a kind of economy, simple and feasible, prepare approach with what increase white carbon black.
The present invention adopts following technical scheme: a kind of method utilizing useless Preparation of White Silica by Silica Residue, and it comprises the following steps:
A, useless white residue and Neutral ammonium fluoride are carried out chemical reaction, generate ammonium silicofluoride and ammonia;
B, step a gained ammonium silicofluoride and ammoniacal liquor are carried out chemical reaction, generate silicon-dioxide and Neutral ammonium fluoride;
C, step b gained silicon-dioxide can obtain white carbon black through ageing, washing, drying;
Wherein, described useless white residue contains silicon-dioxide.
In preparation process:
Preferably: in the chemical reaction described in step a, the actual charged material weight of Neutral ammonium fluoride is the theoretical amount of 140 ~ 180%, and it is 7.8 ~ 21.6% that Neutral ammonium fluoride initial mass concentration controls.
Further, useless white residue remaining in step a can reclaim, and recycle, can also make ammoniacal liquor by the ammonia of step a gained, and obtained ammoniacal liquor can participate in the chemical reaction described in step b further.
Preferably, in chemical reaction described in step b:
It is 7.94 ~ 8.8 that terminal pH controls, and temperature of reaction is 20 ~ 40 DEG C;
Actual the feeding intake of ammoniacal liquor is 105 ~ 110% theoretical ammonia volume;
Ammonium silicofluoride initial mass concentration is 14.6 ~ 20.1%.
Further, step b gained Neutral ammonium fluoride all can reclaim, recycle.
In addition, the chemical reaction described in step b can be carried out under the existence having properties-correcting agent.
Preferably, described properties-correcting agent is propyl carbinol or Sodium dodecylbenzene sulfonate.
The thick white residue of raw material of the present invention dissolves through ammonium fluoride solution in a heated condition, and obtain ammonium fluosilicate solution and ammonia, reaction principle is as follows:
6NH
4F+SiO
2→(NH
4)
2SiF
6+4NH
3 ↑+2H
2O
Be transported to next reaction workshop section after ammonium fluosilicate solution filtering and impurity removing and carry out next chemical reaction, the filter cake after filtration is unreacted SiO mainly
2residue, is returned to initial reaction workshop section and is continued solubilizing reaction.Ammonia enters next reaction workshop section after absorbing cooling, recycle.
Obtain certain density ammonium fluosilicate solution after filter station, squeeze in synthesis reaction vessel through product pump, add ammoniacal liquor, properties-correcting agent in proportion simultaneously, obtain ammonium fluoride solution and silicon-dioxide.Its reaction principle is:
4NH
3+(NH
4)
2SiF
6+mH
2O→6NH
4F+SiO
2·nH
2O
In synthesis reaction vessel, material overflows to ageing at a certain temperature in subsider, uses pressure filter press filtration after ageing 1 ~ 2h, obtains white carbon black product after the silicon-dioxide washing of gained.Isolated ammonium fluoride solution returns first reaction workshop section as the raw material dissolving white residue.Then the reuse of Phosphoric Acid Concentration workshop can be returned to containing ammonia washing lotion.Utilize above-mentioned two mutual reversible chemical reactions, what make reactive material obtains sufficient recycle, greatly reduces preparation cost.
The utilization provided by the invention method that white residue prepares silicon-dioxide of giving up has following characteristics:
1, the white carbon black technical indicator obtained by the present invention reaches precipitated silica standard (HG/T3061-2009) requirement, and quality product meets the requirement of rubber-like matrix material reinforcing function.
2, the preparation method of white carbon black provided by the present invention, its technical process is short, and required equipment quantity is few; Raw material sources are extensively cheap, do not use water glass high energy consumption product; Invest little, cost is low, added value of product is high, non-environmental-pollution.
Embodiment
Further describe technical scheme of the present invention below, but described in claimed scope is not limited to.Below in conjunction with specific embodiment, elaboration detailed is further done to the present invention, but embodiments of the present invention are not limited to the scope that embodiment represents.These embodiments only for illustration of the present invention, but not for limiting the scope of the invention.In addition, after reading content of the present invention, those skilled in the art can do various amendment to the present invention, and these equivalent variations fall within appended claims limited range of the present invention equally.
Embodiment 1
Useless white residue 30g containing 90% silicon-dioxide is placed in 1000mL reaction vessel.Get 139.86g Neutral ammonium fluoride reagent (140% theoretical value weight) and be made into 1.793kg distilled water the ammonium fluoride solution that mass concentration is 7.8%, the ammonium fluoride solution prepared is poured in reactor, 90 DEG C of stirring in water bath backflows, keep slip to boil to silicon-dioxide to dissolve, be cooled to room temperature, filter, wash.Filter cake after filtration is unreacted useless white residue mainly, collects and as most initial reactant, makes it to be able to recycle.The ammonia that bubble absorption volatilizes, ammonia obtains the raw material that ammoniacal liquor can be used as next chemical reaction system after absorbing, cooling.In addition, controlling to be 14.6% by filtering the ammonium fluosilicate solution mass concentration obtained, then squeezing in reactor through product pump, adding the ammoniacal liquor (105% theoretical value weight) containing 32.13g ammonia simultaneously.Control reaction and be 20 DEG C and ensure that reaction end pH controls to be 7.94.Be obtained by reacting ammonium fluoride solution and silicon-dioxide.In reactor, material overflows to ageing at a certain temperature in subsider, uses pressure filter press filtration after ageing 2h.The silicon-dioxide of gained is washed, wash after white carbon black filter cake, add clear water, dispersion forms the SiO of massfraction 20%
2suspension, enters spray-dryer.Time dry, inlet temperature controls 180 DEG C of scopes, and it is 90 DEG C that temperature out controls.Just can carry out sampling Detection after drying step completes, finally pack, warehouse-in.Isolated ammonium fluoride solution returns first reaction workshop section as the raw material dissolving white residue.
Embodiment 2
Useless white residue 30g containing 90% silicon-dioxide is placed in 1000mL reaction vessel.Get 149.85g Neutral ammonium fluoride reagent (150% theoretical value weight) and be made into 1.4985kg distilled water the ammonium fluoride solution that mass concentration is 10%, the ammonium fluoride solution prepared is poured in reactor, 110 DEG C of stirring in water bath backflows, keep slip to boil to silicon-dioxide to dissolve, be cooled to room temperature, filter, wash.Filter cake after filtration is unreacted useless white residue mainly, collects and as most initial reactant, makes it to be able to recycle.The ammonia that bubble absorption volatilizes, ammonia obtains the raw material that ammoniacal liquor can be used as next chemical reaction system after absorbing, cooling.In addition, control to be 15% by filtering the ammonium fluosilicate solution mass concentration obtained, then squeeze in reactor through product pump, add the ammoniacal liquor (108% theoretical value weight) containing 33.048g ammonia simultaneously, add the propyl carbinol of 0.5% reaction soln weight, control reaction and be 30 DEG C and ensure that reaction end pH controls to be 8.Be obtained by reacting ammonium fluoride solution and silicon-dioxide.In reactor, material overflows to ageing at a certain temperature in subsider, uses pressure filter press filtration after ageing 2h.The silicon-dioxide of gained is washed, wash after white carbon black filter cake, add clear water, dispersion forms the SiO of massfraction 20%
2suspension, enters spray-dryer.Time dry, inlet temperature controls 160 DEG C of scopes, and it is 80 DEG C that temperature out controls.Just can carry out sampling Detection after drying step completes, finally pack, warehouse-in.Isolated ammonium fluoride solution returns first reaction workshop section as the raw material dissolving white residue.
Embodiment 3
Useless white residue 30g containing 90% silicon-dioxide is placed in 1000mL reaction vessel.Get 179.82g Neutral ammonium fluoride reagent (180% theoretical value weight) and be made into 0.8325kg distilled water the ammonium fluoride solution that mass concentration is 21.6%, the ammonium fluoride solution prepared is poured in reactor, 120 DEG C of stirring in water bath backflows, keep slip to boil to silicon-dioxide to dissolve, be cooled to room temperature, filter, wash.Filter cake after filtration is unreacted useless white residue mainly, collects and as most initial reactant, makes it to be able to recycle.The ammonia that bubble absorption volatilizes, ammonia obtains the raw material that ammoniacal liquor can be used as next chemical reaction system after absorbing, cooling.In addition, control to be 20.1% by filtering the ammonium fluosilicate solution mass concentration obtained, then squeeze in reactor through product pump, add the ammoniacal liquor (110% theoretical value weight) containing 33.66g ammonia simultaneously, add the Sodium dodecylbenzene sulfonate of 0.5% reaction soln weight, control reaction and be 40 DEG C and ensure that reaction end pH controls to be 8.8.Be obtained by reacting ammonium fluoride solution and silicon-dioxide.In reactor, material overflows to ageing at a certain temperature in subsider, uses pressure filter press filtration after ageing 1h.The silicon-dioxide of gained is washed, wash after white carbon black filter cake, add clear water, dispersion forms the SiO of massfraction 20%
2suspension, enters spray-dryer.Time dry, inlet temperature controls 150 DEG C of scopes, and it is 70 DEG C that temperature out controls.Just can carry out sampling Detection after drying step completes, finally pack, warehouse-in.Isolated ammonium fluoride solution returns first reaction workshop section as the raw material dissolving white residue.
Embodiment 1 gained white carbon black product physics, chemical property detected result are respectively as shown in table 1, table 2.
Table 1 white carbon black product chemical property index
| Sequence number | Project | Standard | Detect data |
| 1 | Dioxide-containing silica/% | ≥90 | 91 |
| 2 | Mensuration/the % of 45 μm of screeningss | ≤0.5 | 0.1 |
| 3 | Weight loss on heating/% | 4.0～8.0 | 4.2 |
| 4 | Burning decrement/% | ≤7.0 | 6.6 |
| 5 | PH value | 5.0～8.0 | 6.6 |
| 6 | Total copper/mg/kg | ≤10 | 2.0 |
| 7 | Total manganese/mg/kg | ≤40 | 6.0 |
| 8 | Total iron/mg/kg | ≤600 | 216 |
| 9 | Dibutyl phthalate absorption/cm3/g | 2.00～3.50 | 2.95 |
| 10 | Water-soluble substance/% | ≤2.5 | 2.0 |
| 11 | F-/ppm | / | 696 |
| 12 | Specific surface area/m2/g | / | 146.8 |
The mechanical performance index of table 2 white carbon black sulfuration test piece
| Sequence number | Project | Standard | Detect data |
| 1 | 300% stress at definite elongation/MPa | ≥5.5 | 7.2 |
| 2 | 500% stress at definite elongation/MPa | ≥13.0 | 16.8 |
| 3 | Tensile strength/MPa | ≥19.0 | 24.8 |
| 4 | Tensile yield/% | ≥550 | 617 |
From above-mentioned detection data, active silica product quality indicator meets " HG/T3061-2009 rubber ingredients-precipitated hydrated silica technical qualification ", and quality product meets the requirement of rubber-like matrix material reinforcing function.
According to the technology of the present invention, produce through extension, built 300t/a active carbon white pilot plant, industrial benefit has clear superiority.
Claims (10)
1. utilize the method for useless Preparation of White Silica by Silica Residue, comprise the following steps:
A, useless white residue and Neutral ammonium fluoride are carried out chemical reaction, generate ammonium silicofluoride and ammonia;
B, step a gained ammonium silicofluoride and ammoniacal liquor are carried out chemical reaction, generate silicon-dioxide and Neutral ammonium fluoride;
C, the ageing of step b gained silicon-dioxide, washing, drying can be obtained white carbon black;
Wherein, described useless white residue contains silicon-dioxide.
2. utilization according to claim 1 is given up the method for Preparation of White Silica by Silica Residue, and its characteristic is: in the chemical reaction described in step a, and the actual charged material weight of Neutral ammonium fluoride is the theoretical amount of 140 ~ 180%, and Neutral ammonium fluoride initial mass concentration is 7.8 ~ 21.6%.
3. the method for Preparation of White Silica by Silica Residue of giving up according to the arbitrary described utilization of claim 1 or 2, is characterized in that: it comprises the step of the ammonia recycle generated.
4. the method for Preparation of White Silica by Silica Residue of giving up according to the arbitrary described utilization of claim 1 or 2, is characterized in that: it comprises the step of the useless white residue circulation of remnants.
5. utilization according to claim 1 is given up the method for Preparation of White Silica by Silica Residue, and its characteristic is: the terminal pH of chemical reaction described in step b is 7.94 ~ 8.8, and temperature of reaction is 20 ~ 40 DEG C.
6. utilization according to claim 1 is given up the method for Preparation of White Silica by Silica Residue, and its characteristic is: in the chemical reaction described in step b, and actual the feeding intake of ammoniacal liquor is 105 ~ 110% theoretical ammonia volume.
7. utilization according to claim 1 is given up the method for Preparation of White Silica by Silica Residue, and its characteristic is: in the chemical reaction described in step b, and ammonium silicofluoride initial mass concentration is 14.6 ~ 20.1%.
8. the method for Preparation of White Silica by Silica Residue of giving up according to described utilization arbitrary in claim 1 or 5-7, its characteristic is: can carry out the chemical reaction described in step b under the existence having properties-correcting agent.
9. utilization according to claim 8 is given up the method for Preparation of White Silica by Silica Residue, and its characteristic is: described properties-correcting agent is propyl carbinol or Sodium dodecylbenzene sulfonate.
10. utilization according to claim 1 is given up the method for Preparation of White Silica by Silica Residue, it is characterized in that: it comprises the step of the Neutral ammonium fluoride circulation generated.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510769962.8A CN105271254A (en) | 2015-11-11 | 2015-11-11 | Method for preparing white carbon black through waste silicon slag |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510769962.8A CN105271254A (en) | 2015-11-11 | 2015-11-11 | Method for preparing white carbon black through waste silicon slag |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105271254A true CN105271254A (en) | 2016-01-27 |
Family
ID=55141194
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510769962.8A Pending CN105271254A (en) | 2015-11-11 | 2015-11-11 | Method for preparing white carbon black through waste silicon slag |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105271254A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110844911A (en) * | 2019-12-20 | 2020-02-28 | 黄冈师范学院 | Method for directly preparing high-purity white carbon black by using fluorine-containing silicon slag |
| CN111841548A (en) * | 2020-08-01 | 2020-10-30 | 山东科技大学 | Method for preparing basic nickel silicate catalyst from silicon-containing industrial solid waste |
| CN112047347A (en) * | 2020-08-25 | 2020-12-08 | 凯里市鑫泰熔料有限公司 | Preparation of nano-silicon dioxide from waste residue in polyaluminium chloride production |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102491369A (en) * | 2011-12-02 | 2012-06-13 | 瓮福（集团）有限责任公司 | Method for producing ammonium fluoride by recovering fluorine resources |
| CN102942185A (en) * | 2012-12-13 | 2013-02-27 | 贵州瓮福蓝天氟化工股份有限公司 | Method for preparing nano-scale white carbon black product |
-
2015
- 2015-11-11 CN CN201510769962.8A patent/CN105271254A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102491369A (en) * | 2011-12-02 | 2012-06-13 | 瓮福（集团）有限责任公司 | Method for producing ammonium fluoride by recovering fluorine resources |
| CN102942185A (en) * | 2012-12-13 | 2013-02-27 | 贵州瓮福蓝天氟化工股份有限公司 | Method for preparing nano-scale white carbon black product |
Non-Patent Citations (1)
| Title |
|---|
| 何川等: "利用废弃物含氟硅渣制白炭黑实验研究", 《硫磷设计与粉体工程》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110844911A (en) * | 2019-12-20 | 2020-02-28 | 黄冈师范学院 | Method for directly preparing high-purity white carbon black by using fluorine-containing silicon slag |
| CN111841548A (en) * | 2020-08-01 | 2020-10-30 | 山东科技大学 | Method for preparing basic nickel silicate catalyst from silicon-containing industrial solid waste |
| CN112047347A (en) * | 2020-08-25 | 2020-12-08 | 凯里市鑫泰熔料有限公司 | Preparation of nano-silicon dioxide from waste residue in polyaluminium chloride production |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103663474B (en) | A kind of method of fluorine-containing Preparation of White Silica by Silica Residue | |
| CN105271254A (en) | Method for preparing white carbon black through waste silicon slag | |
| CN101913637A (en) | Process method for producing fluorine compounds and silicon compounds by cleanly utilizing fluosilicic acid | |
| CN102887532B (en) | Process for preparing potassium fluoride and co-producing white carbon black from fluosilicic acid | |
| CN101214960B (en) | Integrated utilization method for phosphorus chemical industry byproduct fluorosilicic acid | |
| CN104925817B (en) | The preparation method of nanometer grade silica | |
| CN102951649A (en) | Preparation method of modified precipitated white carbon black | |
| CN102942185B (en) | Method for preparing nano-scale white carbon black product | |
| CN104744175A (en) | Method for producing nitrogen-phosphorus-potassium mixed fertilizer by utilizing phosphorus-potassium associated ore | |
| CN101863482B (en) | Method for continuously preparing white carbon black and ammonium fluoride by carrying out fluosilicic acid ammoniation | |
| CN103803569B (en) | A kind of method that tourmaline powder hydrothermal method brightens | |
| CN106829983B (en) | Preparation method of sodium silicate | |
| CN102633269A (en) | Preparation method of aerogel | |
| CN103663499B (en) | The method of Potassium monofluoride co-production of ultrafine white carbon black is prepared with phosphate fertilizer by-product ammonium silicofluoride | |
| CN104692436A (en) | Method for preparing cryolite from coal ash | |
| CN101293655A (en) | Novel method for preparing high purity silicon dioxide | |
| CN104211104A (en) | Separation and recovery method of thermal coal power plant flue gas desulfurization gypsum waste residues | |
| CN101734667B (en) | Process for producing precipitated white carbon black by silicon tetrachloride | |
| CN103539130A (en) | Technological method for preparing white carbon black from potassium feldspar | |
| CN103922345B (en) | A kind of method utilizing the ultrapure silicofluoric acid of industrial fluorinated tail gas acid extraction and silicon-dioxide | |
| CN104445219A (en) | Preparation method of white carbon black | |
| CN105585032B (en) | The method that fluorine resource is reclaimed from low product bauxite waste gas decomposition | |
| CN103112873A (en) | Method for preparing high-purity potassium fluoride and co-producing white carbon black by adopting potassium fluosilicate | |
| CN102491342B (en) | Method for preparing white carbon black by using fluosilicic acid gas ammonification process | |
| CN104495803A (en) | Purification method of natural microcrystalline graphite |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20160127 |