CN101323453B

CN101323453B - Circulation novel process for preparing white carbon black

Info

Publication number: CN101323453B
Application number: CN2008100482954A
Authority: CN
Inventors: 徐旺生; 郭嘉; 刘芳; 赵彬; 王慧; 龙文露; 舒琼
Original assignee: Wuhan Institute of Technology
Current assignee: Wuhan Institute of Technology
Priority date: 2008-07-04
Filing date: 2008-07-04
Publication date: 2012-05-23
Anticipated expiration: 2028-07-04
Also published as: CN101323453A

Abstract

The invention relates to a new cycle technique for preparing white carbon black, comprising the following steps: 1) a water glass solution reacts with an ammonium hydrogen carbonate solution or solid ammonium hydrogen carbonate in the condition of the temperature of 30 to 50 DEG C, the white carbon black is obtained and ammonia escapes simultaneously; 2) the ammonia escaped from the step 1) is mixed with CO2 gas produced in the process of the preparation of the water glass solution and the obtained mixture is absorbed by water to obtain the ammonium hydrogen carbonate; 3) the white carbon black produced by reaction is filtered under the condition of vacuum to obtain a mother liquid A and a filter cake A, the mother liquid A is recovered and the filter cake A is washed, dried and crushed so as to obtain the white carbon black. The invention 1) solves the effective recovery of by-products in the production process, is used for self-production, improves the utilization value of materials, without three wastes discharge in the production process, and has high material utilization rate, good effect of discharge reduction and stable and reliable quality of products; 2) recovery of sodium bicarbonate is carried out after the mass concentration is increased by the evaporation in vacuum at low temperature, thus reducing the usage of organic solvent.

Description

A kind of circulation technology for preparing WHITE CARBON BLACK

Technical field

Of the present inventionly relate to a kind of circulation technology for preparing WHITE CARBON BLACK.

Background technology

WHITE CARBON BLACK is a kind of broad-spectrum inorganic fine chemical product, and traditional working method is to adopt the precipitator method, is raw material with water glass; Carry out replacement(metathesis)reaction with sulfuric acid or hydrochloric acid and process; Can produce sodium sulfate or the sodium chloride aqueous solution that concentration is low, liquid measure is big in this technological process, reclaim the low material of this type concentration, consume a large amount of energy; As do not recycle and outwards discharging, be certain to environment is caused severe contamination or is unfavorable for the protection of ecotope.This traditional working method is all to have great technological deficiency to enterprise or to country and society.

Summary of the invention

Problem to be solved by this invention is to propose a kind of circulation technology for preparing WHITE CARBON BLACK to above-mentioned prior art; This technology can save energy consumption, reduce to produce the pollution that waste causes environment and water body; Reduce production costs basic demands such as realization is energy-saving and cost-reducing, reduction of discharging to a great extent.

The present invention by the problem of the above-mentioned proposition of solution the employing solution be: a kind of circulation technology for preparing WHITE CARBON BLACK includes following steps:

1) makes water glass solution through existing technology; Under 30-50 ℃ of condition with the water glass solution of 9-10 ° of Be ' with ammonium bicarbonate soln or solid ammonium bicarbonate with and add mode carry out stirring reaction; Water glass solution and bicarbonate of ammonia mole proportioning are 1: 2.0～1: 2.2; The throw out WHITE CARBON BLACK that obtains loosening, the ammonia of overflowing simultaneously;

2) with above-mentioned steps 1) ammonia of overflowing prepares the CO that produces in the process with water glass solution ₂Gas is mixed together and water absorbs, and makes the bicarbonate of ammonia that is used for carrying out with water glass solution replacement(metathesis)reaction;

3) the throw out WHITE CARBON BLACK of the step 1) reaction being processed filters under vacuum condition, obtains mother liquor first and filter cake first, and the mother liquor first reclaims, and the filter cake first promptly obtains the WHITE CARBON BLACK of polymolecularity through washing, drying, pulverizing.

Press such scheme; It is under vacuum condition, to filter in the mother liquor first that obtains to contain the sodium hydrogencarbonate that mass concentration is 10%-12% that step 3) mother liquor first reclaims; Being evaporated to mass concentration through vacuum and low temperature is 25%-30%, reduces to room temperature, adds organic solvent; Stirring and evenly mixing can therefrom be separated out a large amount of NaHCO ₃Crystal filters, and obtains mother liquor second and filter cake second, and filter cake second is carried out pyroreaction in horseshoe flame furnace after mixing with quartz mine in molar ratio 2: 3.1-3.4 after the drying, make solid water glass; Mother liquor second then in distillation tower with LP steam heating, under 78-80 ℃ of temperature condition, reclaim and obtain organic solvent, the hot water that steams after surplus then is used for dissolved solids water glass and processes water glass solution.

Press such scheme, described LP steam is to adopt water glass solution to prepare recovery waste heat in the process and the LP steam that produces.

Press such scheme, described organic solvent is absolute ethyl alcohol, anhydrous methanol or anhydrous propyl alcohol.

The main raw material of whole process of preparation is natural crystal-silica sand, and all the other raw materials then recycle in system, suitably adds because the loss part that evaporating, emitting, dripping or leaking of liquid or gas caused.Principal reaction equation of the present invention is Na ₂OmSiO ₂+ 2NH ₄HCO ₃→ 2NaHCO ₃+ mSiO ₂NH ₂O ↓+2NH ₃The H of ↑+(1-mn) ₂O.

Advantage of the present invention:

1) the present invention has reasonably solved the efficient recovery of by product in the production process, and is used for self production, has improved the starting material recycle greatly and has been worth, and the sodium hydrogencarbonate that promptly reclaims is used to prepare water glass, and the ammonia of effusion contains CO with calcining workshop section ₂The high temperature kiln after the waste heat boiler recovery waste heat produces LP steam, get into absorption unit together, water absorbs processes ammonium bicarbonate aqueous solution, organic solvent is through also recycling in system after the underpressure distillation; The surplus water of heat then is used to dissolve water glass; Make and accomplish three-waste free discharge in the whole process of production, utilization rate of raw materials is high, and its emission reduction effect is good; The white carbon black production cost can reduce more than 50%, stable and reliable product quality.

2) sodium hydrogencarbonate in the mother liquor first is reclaimed after the vacuum and low temperature evaporation raises mass concentration again, significantly reduced the usage quantity of organic solvent.

Description of drawings

Fig. 1 is the circulation technology schematic flow sheet that the present invention prepares WHITE CARBON BLACK.

Embodiment

Below in conjunction with embodiment the present invention is described further.

Embodiment 1:

Like Fig. 1, be that 3.2 water glass is configured to 10 ° of Be ' after purifying treatment dilute solution 300ml joins in the stirred reactor of 1000ml with modulus, keep reaction mass 45 ℃ of scopes, add 20g while stirring through purified NH ₄HCO ₃, make it to carry out reactions: Na ₂OmSiO ₂+ 2NH ₄HCO ₃=2NaHCO ₃+ mSiO ₂NH ₂O ↓+2NH ₃The H of ↑+(1-mn) ₂O, wherein water glass solution and NH ₄HCO ₃Mol ratio be controlled at 1: 2.0～1: 2.2 (wherein 3.1＜m＜3.4), behind the reaction 45-60min, can't smell ammonia flavor (available moistening test paper check) from the reactor head evolving gas and then be reaction end, the throw out WHITE CARBON BLACK that obtains loosening.

The throw out that above-mentioned reaction is processed filters under vacuum condition, obtains filter cake first and mother liquor first, initial mother liquor first is removed 1/3 moisture through vacuum and low temperature evaporation after; Making the mass concentration of sodium hydrogencarbonate in the mother liquor first is 25%-30%; Be cooled to room temperature, add the 150ml absolute ethyl alcohol, and carry out vigorous stirring; Leave standstill 5min, separate out NaHCO ₃Crystal obtains NaHCO through filtration, drying ₃Be 20.81g, reclaiming transformation efficiency is 97.88%, and obtains mother liquor second; Mother liquor second then heats with LP steam in distillation tower, under 80 ℃ of conditions, carries out vacuum distilling, reclaims absolute ethyl alcohol 145.1ml, and the recovery is 96.7%.NaHCO ₃Then through existing routine techniques prepared water glass solution.

The filter cake first is washed till pH=6.5～7.5 scopes through UW, dewaters, dry 2h under 120 ℃ pulverizes 5min through Universalpulverizer, obtains the WHITE CARBON BLACK 14.37g of ultrafine powder powder, and ult rec reached for 95% (various losses add up to 5%).

Embodiment 2

Like Fig. 1, be that 3.2 water glass is configured to 9 ° of Be ' after purifying treatment dilute solution 300ml joins in the stirred reactor of 1000ml with modulus, keep reaction mass 30 ℃ of scopes, add 19g while stirring through purified NH ₄HCO ₃, make it to carry out reactions: Na ₂OmSiO ₂+ 2NH ₄HCO ₃=2NaHCO ₃+ mSiO ₂NH ₂O ↓+2NH ₃The H of ↑+(1-mn) ₂O, wherein water glass solution and NH ₄HCO ₃Mol ratio be controlled at 1: 2.0～1: 2.2 (wherein 3.1＜m＜3.4), behind the reaction 45-60min, can't smell ammonia flavor (available moistening test paper check) from the reactor head evolving gas and then be reaction end, the throw out WHITE CARBON BLACK that obtains loosening.

The throw out that above-mentioned reaction is processed filters under vacuum condition, obtains filter cake first and mother liquor first, initial mother liquor first is removed 1/3 moisture through vacuum and low temperature evaporation after; Making the mass concentration of sodium hydrogencarbonate in the mother liquor first is 25%-30%; Be cooled to room temperature, add the 150ml anhydrous methanol, and carry out vigorous stirring; Leave standstill 5min, separate out NaHCO ₃Crystal obtains NaHCO through filtration, drying ₃Be 19.76g, reclaiming transformation efficiency is 97.56%, and obtains mother liquor second; Mother liquor second then heats with LP steam in distillation tower, under 78 ℃ of conditions, carries out vacuum distilling, reclaims anhydrous methanol 145.5ml, and the recovery is 96.30%.NaHCO ₃Then through existing routine techniques prepared water glass solution.

The filter cake first is washed till pH=6.5～7.5 scopes through UW, dewaters, dry 2h under 120 ℃ pulverizes 5min through Universalpulverizer, obtains the WHITE CARBON BLACK 13.86g of ultrafine powder powder, and ult rec reached for 95.46% (various losses add up to 4.54%).

Claims

1. circulation technology for preparing WHITE CARBON BLACK is characterized in that including following steps:

3) the throw out WHITE CARBON BLACK of the step 1) reaction being processed filters under vacuum condition; Obtain mother liquor first and filter cake first, the mother liquor first reclaims, and the filter cake first promptly obtains the WHITE CARBON BLACK of polymolecularity through washing, drying, pulverizing; Wherein the mother liquor first being reclaimed is under vacuum condition, to filter in the mother liquor first that obtains to contain the sodium hydrogencarbonate that mass concentration is 10%-12%; Being evaporated to mass concentration through vacuum and low temperature is 25%-30%, reduces to room temperature, adds organic solvent absolute ethyl alcohol, anhydrous methanol or anhydrous propyl alcohol; Stirring and evenly mixing can therefrom be separated out a large amount of NaHCO ₃Crystal filters, and obtains mother liquor second and filter cake second, and filter cake second is carried out pyroreaction in horseshoe flame furnace after mixing with quartz mine in molar ratio 2: 3.1-3.4 after the drying, make solid water glass; Mother liquor second then in distillation tower with LP steam heating, under 78-80 ℃ of temperature condition, reclaim and obtain organic solvent, the hot water that steams after surplus then is used for dissolved solids water glass and processes water glass solution.

2. by the described a kind of circulation technology for preparing WHITE CARBON BLACK of claim 1, it is characterized in that described LP steam is to adopt water glass solution to prepare recovery waste heat in the process and the LP steam that produces.