CN114436271A - White carbon black production process utilizing sulfur circulation - Google Patents

White carbon black production process utilizing sulfur circulation Download PDF

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Publication number
CN114436271A
CN114436271A CN202111647800.9A CN202111647800A CN114436271A CN 114436271 A CN114436271 A CN 114436271A CN 202111647800 A CN202111647800 A CN 202111647800A CN 114436271 A CN114436271 A CN 114436271A
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carbon black
white carbon
sodium sulfate
sodium
production process
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王君如
周航
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Sichuan Mabian Longtai Phosphorus And Electricity Co ltd
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Sichuan Mabian Longtai Phosphorus And Electricity Co ltd
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00Silicon; Compounds thereof
    • C01B33/113Silicon oxides; Hydrates thereof
    • C01B33/12Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/18Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof

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  • Inorganic Chemistry (AREA)
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Abstract

The invention provides a white carbon black production process utilizing sulfur circulation, and aims to solve the problem of treatment of sulfur-containing wastewater in the white carbon black production process in the prior art. The white carbon black production process utilizing sulfur circulation comprises the following steps: s1: treating sodium sulfate, quartz powder and coal powder to obtain sodium silicate melt and SO-containing molten sodium silicate2And recovering and purifying the gas containing SO2The gas of (4); s2: preparing sodium silicate solution from sodium silicate melt, and adding SO-containing solution for recovery and purification2Reacting the gas to obtain precipitated white carbon black and sodium bisulfite suspension; s3: treating the precipitated white carbon black and sodium bisulfite suspension to obtain a white carbon black filter cake and sodium sulfate filtrate; s4: and treating the white carbon black filter cake to obtain a white carbon black finished product, and treating the sodium sulfate filtrate to obtain sodium sulfate, and circulating the sodium sulfate to the step S1. The invention reduces the wastewater discharge and the production cost of the white carbon black by a closed-loop production mode.

Description

White carbon black production process utilizing sulfur circulation
Technical Field
The invention relates to the technical field of white carbon black production, in particular to a white carbon black production process utilizing sulfur circulation.
Background
The precipitated white carbon black (SiO 2. nH2O) is white powder in appearance, insoluble in water and acid, soluble in strong base and hydrofluoric acid, porous, large in inner surface area, high in dispersibility, light in weight, good in chemical stability, high in temperature resistance, non-combustible, non-toxic, tasteless, good in electrical insulation property and the like. It is used as reinforcing filler in rubber industry, mainly for shoes, tyres and other light-colored rubber products. Can be used as a carrier or a flowing agent in the industries of pesticide, feed and the like, can be used as a rubbing agent in toothpaste, and can be used as a dispersing agent, an anti-settling agent or a delustering agent in the coating industry.
In the production process, about 30-35m3 m sodium sulfate (or sodium chloride) containing wastewater of each ton of precipitated silica white is discharged by simple treatment because the sodium sulfate (or sodium chloride) has low value and high recovery cost.
A large amount of untreated sulfate-containing wastewater is discharged into water, so that a water body is acidified and aquatic organisms are damaged; when the fertilizer is discharged into farmland, the soil structure can be damaged, the soil is hardened, and the yield and the quality of crops are influenced; in drinking water, when the sulfate is more than 750mg/L, a person can have a laxative symptom; when the sulfate in the drinking water is as high as 1000mg/L, the drinking water can inhibit and weaken gastric secretion, reduce gastric acidity and activity of pepsin, hinder digestion and further damage human health. Therefore, enterprises need to invest a large amount of capital to treat the sulfate-containing wastewater, and the production cost of the enterprises is increased.
Disclosure of Invention
The invention aims to solve the problem of sulfur-containing wastewater treatment in the white carbon black production process in the prior art, provides a white carbon black production process utilizing sulfur circulation, and reduces wastewater discharge and production cost of white carbon black by a closed-loop production mode.
The technical scheme adopted by the invention is as follows:
a white carbon black production process utilizing sulfur circulation comprises the following steps:
s1: treating sodium sulfate, quartz powder and coal powder to obtain sodium silicate melt and SO-containing molten sodium silicate2And recovering and purifying the gas containing SO2The gas of (4);
s2: preparing sodium silicate solution from sodium silicate melt, and adding SO-containing solution for recovery and purification2The gas reacts with the carbon dioxide to obtain precipitated white carbon black and sodium bisulfite suspension;
s3: treating the precipitated white carbon black and sodium bisulfite suspension to obtain a white carbon black filter cake and sodium sulfate filtrate;
s4: and treating the white carbon black filter cake to obtain a white carbon black finished product, and treating the sodium sulfate filtrate to obtain sodium sulfate, and circulating the sodium sulfate to the step S1.
Alternatively, in step S1: introducing the sodium sulfate filtrate obtained in the step S3 to the reaction kettle containing SO2The gas is washed by dynamic wave and purified by an electric demister.
Optionally, the step S2 further includes the following steps:
s21: cooling the sodium silicate melt to obtain solid sodium silicate;
s22: hydrolyzing solid sodium silicate to obtain sodium silicate solution;
s23: adding the SO-containing liquid into the recovery and purification treatment2The gas is reacted in sodium silicate solution to obtain precipitated white carbon black and sodium bisulfite suspension.
Alternatively, in step S22: the mass ratio of the solid sodium silicate to the hydrolytic agent is 1: 2; pressurizing to 0.5Mpa, heating to 130-.
Optionally, the hydrolyzing agent is the sodium sulfate solution in step S3.
Optionally, in the step S23, the sodium silicate solution is diluted 1:1 by using condensed water, and then the condensed water is introduced into the recovery and purification treatment to contain SO2The reaction temperature is 65-85 ℃, and the precipitated white carbon black and sodium bisulfite suspension is obtained. Optionally, in step S3, oxygen is introduced into the suspension of precipitated silica and sodium bisulfite, the sodium bisulfite is oxidized into sodium sulfate and SO2 is removed, the precipitated silica is aged, and then solid-liquid separation and washing are performed to obtain a precipitated silica filter cake and a sodium sulfate filtrate.
Optionally, the pH of the sodium sulfate filtrate is between 4 and 6.
Optionally, in step S2, SO is contained2SO in the flue gas discharged in the reaction process of the gas and the sodium silicate solution2≤200ppm。
Optionally, in step S4, the sodium sulfate filtrate is subjected to desiliconization, membrane filtration concentration, MVR evaporation concentration, vapor multiple-effect evaporation concentration, cooling, crystallization, separation and drying to obtain sodium sulfate and condensed water, wherein the sodium sulfate is returned to step S1 for the next cycle, and the condensed water is introduced to step S3 to be used as washing water for precipitating the silica cake for the next cycle.
Compared with the prior art, the invention has the beneficial effects that:
realizes the closed cyclic utilization of sodium sulfate-sodium silicate-SO 2-white carbon black sulfur, cancels the consumption of sodium carbonate and sulfuric acid and realizes the zero discharge of wastewater compared with the domestic mainstream process of sodium carbonate-sodium silicate-sulfuric acid-white carbon black.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings used in the embodiments or the prior art descriptions will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present application, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a schematic view of a process structure of a white carbon black production process using sulfur cycle.
FIG. 2 is a flow chart of a process for producing white carbon black by using the existing process.
Detailed Description
In the following, only certain exemplary embodiments are briefly described. As those skilled in the art will recognize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention. Accordingly, the drawings and description are to be regarded as illustrative in nature, and not as restrictive.
The following disclosure provides many different embodiments or examples for implementing different features of the invention. To simplify the disclosure of the present invention, the components and arrangements of specific examples are described below. Of course, they are merely examples and are not intended to limit the present invention. Furthermore, the present invention may repeat reference numerals and/or letters in the various examples, such repetition is for the purpose of simplicity and clarity and does not in itself dictate a relationship between the various embodiments and/or configurations discussed. In addition, the present invention provides examples of various specific processes and materials, but one of ordinary skill in the art may recognize applications of other processes and/or uses of other materials.
Embodiments of the present invention will be described in detail below with reference to the accompanying drawings.
The embodiment of the invention provides a white carbon black production process by utilizing sulfur circulation, which comprises the following steps of:
s1: sodium sulfate, quartz powder and coal powder are melted and reacted at high temperature to obtain sodium silicate melt and SO-containing solution2And recovering and purifying the gas containing SO2Is introduced into the sodium sulfate filtrate generated in step S3 to contain SO during the treatment2The gas is washed by dynamic wave and purified by an electric demister;
s2: cooling the sodium silicate melt to prepare solid sodium silicate, hydrolyzing the solid sodium silicate to prepare a sodium silicate solution, and adding the sodium silicate solution for recycling and purifying SO2The gas reacts with the white carbon black to obtain precipitated white carbon black and sodium bisulfite suspension, and the reacted waste flue gas contains SO22≤200ppm;
S3: introducing oxygen into the precipitated white carbon black and sodium bisulfite suspension, oxidizing ammonium bisulfite to obtain sodium sulfate and removing SO2, aging the precipitated white carbon black, carrying out oxidation aging reaction, keeping the pH value of the precipitated white carbon black and the sodium sulfate suspension at 4-6, and carrying out solid-liquid washing separation on the precipitated white carbon black and the sodium sulfate suspension to obtain a precipitated white carbon black filter cake and a sodium sulfate filtrate;
s4: and treating the white carbon black filter cake to obtain a finished white carbon black product, and subjecting the sodium sulfate filtrate to desiliconization, membrane filtration and concentration, MVR evaporation and concentration, vapor multiple-effect evaporation and concentration, cooling, crystallization, separation and drying to obtain sodium sulfate and condensed water, wherein the sodium sulfate is returned to the step S1 for the next cycle, and the condensed water is introduced to the step S3 for the next cycle.
In another embodiment, the mass ratio of the solid sodium silicate to the hydrolytic agent (in this embodiment, sodium sulfate solution is used as the hydrolytic agent, and the sodium sulfate solution is generated in step S3 in the method) is 1: 2; pressurizing to 0.5Mpa, heating to 150 ℃ for dissolution to obtain a solution, and filtering the solution to remove impurities to obtain the sodium silicate solution.
In another embodiment, the condensed water generated in step S4 is recycled to step S2, and the condensed water is used to perform 1:1 treatment on the sodium silicate solutionIs then introduced with SO2The reaction temperature is 70 ℃, and the white carbon black semi-finished product and the sodium bisulfite suspension are obtained. Realizing zero discharge of waste water.
The specific working principle is as follows:
sodium sulfate, quartz powder and coal powder are subjected to high-temperature melting reaction to obtain sodium silicate melt and 2-3% SO2(volume ratio) flue gas containing 2-3% SO2Washing and purifying the gas, then directly reacting the gas with sodium silicate solution which is dissolved and refined to obtain 5-20% (calculated by the sodium silicate) of sodium silicate solution to prepare precipitated white carbon black and sodium bisulfite suspension, then introducing oxygen to convert the sodium bisulfite into sodium sulfate, removing SO2, filtering, washing and separating the precipitated white carbon black and the sodium sulfate suspension to obtain white carbon black filter cake and sodium sulfate filtrate; the white carbon black filter cake is further processed into a white carbon black finished product, sodium sulfate is obtained by desiliconizing, refining, concentrating, crystallizing and drying the sodium sulfate-containing filtrate, the sodium sulfate is returned to the first step for recycling, and the condensed water is returned for recycling and is mainly used for washing the precipitated white carbon black filter cake and diluting the sodium silicate solution. The reaction formula is as follows:
2Na2SO4+2mSiO2+C→2Na2O·mSiO2+2SO2↑+CO2
Na2O·mSiO2+2SO2+nH2O→2NaHSO3+mSiO2·nH2O↓
2NaHSO3+O2→Na2SO+SO2↑+H2O
and (3) sulfur cycle verification:
the process only needs 1 ton of quartz sand and 0.05 ton of reduced carbon powder for producing 1 ton of precipitated white carbon black, and compared with the modes of soda ash-sodium silicate-sulfuric acid-white carbon black of the existing mainstream enterprises, the process consumes 0.6 ton of sodium carbonate and 0.5 ton of sulfuric acid less, discharges 30-35m3 less sodium sulfate wastewater, reduces 0.12 ton of emission of CO2 in process reaction, and has obvious effects of consumption reduction and emission reduction.
Compared with the production data of the production process of the existing mainstream enterprises, the method comprises the following specific processes:
the production process is shown in figure 1
The existing mainstream enterprise production process is shown in figure 2
The main parameter pairs are as follows:
Figure BDA0003442017060000051
Figure BDA0003442017060000061
finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A white carbon black production process utilizing sulfur circulation is characterized by comprising the following steps:
s1: treating the sodium sulfate, the quartz powder and the coal powder to obtain a sodium silicate melt and SO2And recovering and purifying the gas containing SO2The gas of (4);
s2: preparing sodium silicate solution from sodium silicate melt, and adding SO-containing solution for recovery and purification2The gas reacts with the carbon dioxide to obtain precipitated white carbon black and sodium bisulfite suspension;
s3: treating the precipitated white carbon black and sodium bisulfite suspension to obtain a white carbon black filter cake and sodium sulfate filtrate;
s4: and treating the white carbon black filter cake to obtain a white carbon black finished product, and treating the sodium sulfate filtrate to obtain sodium sulfate, and circulating the sodium sulfate to the step S1.
2. The white carbon black production process utilizing sulfur cycle according to claim 1,in step S1: introducing the sodium sulfate filtrate obtained in the step S3 to the reaction kettle containing SO2The gas is washed by dynamic wave and purified by an electric demister.
3. The white carbon black production process utilizing sulfur cycle as claimed in claim 1, wherein said step S2 further comprises the steps of:
s21: cooling the sodium silicate melt to obtain solid sodium silicate;
s22: hydrolyzing solid sodium silicate to obtain sodium silicate solution;
s23: adding the SO-containing liquid into the recovery and purification treatment2The gas is reacted in sodium silicate solution to obtain precipitated white carbon black and sodium bisulfite suspension.
4. The white carbon black production process using sulfur cycle as claimed in claim 3, wherein in step S22: the mass ratio of the solid sodium silicate to the hydrolytic agent is 1: 2; pressurizing to 0.5Mpa, heating to 130-.
5. The white carbon black production process utilizing sulfur cycle as claimed in claim 4, wherein the hydrolyzing agent is the sodium sulfate solution in step S3.
6. The white carbon black production process utilizing sulfur cycle as claimed in claim 3, wherein in the step S23, the sodium silicate solution is diluted 1:1 by using condensed water, and then the SO-containing solution is recycled and purified2The reaction temperature is 65-85 ℃, and the precipitated white carbon black and sodium bisulfite suspension is obtained.
7. The silica production process using sulfur cycle as recited in claim 1, wherein in step S3, oxygen is introduced into the precipitated silica and the suspension of sodium bisulfite to oxidize the sodium bisulfite into sodium sulfate and remove SO2, the precipitated silica is aged, and then the precipitated silica is washed by solid-liquid separation to obtain a precipitated silica cake and a sodium sulfate filtrate.
8. The white carbon black production process utilizing sulfur cycle as claimed in claim 7, wherein the pH value of the sodium sulfate filtrate is 4-6.
9. The silica production process using sulfur cycle as claimed in claim 7, wherein in step S2, SO is contained2In the flue gas discharged from the reaction process of the gas and sodium silicate solution2≤200ppm。
10. The silica production process using sulfur cycle as claimed in claim 1, wherein the sodium sulfate filtrate is subjected to desiliconization, membrane filtration concentration, MVR evaporation concentration, vapor multi-effect evaporation concentration, cooling, crystallization, separation and drying in step S4 to obtain sodium sulfate and condensed water, wherein the sodium sulfate is returned to step S1 for the next cycle, and the condensed water is introduced into S3 to be used as washing water for precipitating silica cake for the next cycle.
CN202111647800.9A 2021-12-29 2021-12-29 White carbon black production process utilizing sulfur circulation Pending CN114436271A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1699163A (en) * 2005-06-08 2005-11-23 卢元健 Process for producing white carbon black and sodium sulphite by sodium sulfate method
CN111153412A (en) * 2020-01-15 2020-05-15 河南省睿博环境工程技术有限公司 White carbon black production flow based on filtering washing liquid and sodium sulfate cyclic utilization
CN112010417A (en) * 2019-05-29 2020-12-01 云南民族大学 Oxidation method of sulfite or bisulfite or mixture thereof
CN113213685A (en) * 2021-04-26 2021-08-06 萍乡市华星环保工程技术有限公司 Desulfurization product sulfur recycling treatment process

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1699163A (en) * 2005-06-08 2005-11-23 卢元健 Process for producing white carbon black and sodium sulphite by sodium sulfate method
CN112010417A (en) * 2019-05-29 2020-12-01 云南民族大学 Oxidation method of sulfite or bisulfite or mixture thereof
CN111153412A (en) * 2020-01-15 2020-05-15 河南省睿博环境工程技术有限公司 White carbon black production flow based on filtering washing liquid and sodium sulfate cyclic utilization
CN113213685A (en) * 2021-04-26 2021-08-06 萍乡市华星环保工程技术有限公司 Desulfurization product sulfur recycling treatment process

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Application publication date: 20220506