CN103754905A - Process for combined production of alumina as well as active calcium silicate and cement from gangue - Google Patents

Process for combined production of alumina as well as active calcium silicate and cement from gangue Download PDF

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CN103754905A
CN103754905A CN201210263998.5A CN201210263998A CN103754905A CN 103754905 A CN103754905 A CN 103754905A CN 201210263998 A CN201210263998 A CN 201210263998A CN 103754905 A CN103754905 A CN 103754905A
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coal gangue
calcium silicate
cement
active calcium
technique
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张宏
韓德民
雷菊花
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
    • Y02P40/18—Carbon capture and storage [CCS]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/20—Waste processing or separation

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  • Silicates, Zeolites, And Molecular Sieves (AREA)

Abstract

The invention provides a process for combined production of alumina as well as active calcium silicate and cement from gangue, and relates to the technology field of combined production of alumina and active calcium silicon. The invention carries out a desilicication reaction by calcinating gangue, and preparing a sodium hydroxide solution and sodium carbonate solution by reaction and processing, and calcining aluminium hydroxide for preparing alumina product. The invention has the advantages of simple process, low production cost, low energy consumption and little material consumption, and simultaneously three products with silicon containing products are prepared without waste generation.

Description

Coal gangue for producing alumina coproduction active calcium silicate and cement and technique thereof
Technical field
The present invention relates to the technical field of aluminum and coproducing active calcium silicate and manufacture of cement, particularly from coal gangue, extract aluminum and coproducing active calcium silicate and cement and technique.
Background technology
Coal gangue is China's discharge at present and piles high-volume maximum solid waste, causes larger environmental pollution and the wasting of resources.The mineral composition of coal gangue is mainly kaolinite, and wherein aluminum oxide and dioxide-containing silica are higher, is a kind of potential mineral wealth.Along with the continuous increase of country to metallurgical-grade aluminum oxide demand, and the day by day minimizing of China's bauxite reserves, utilize the aluminum-containing mineral resource of industrial production generation as flyash, coal gangue etc., replace natural bauxite to produce the industry such as aluminum oxide, and form the industry chain of circular economy of coal-electric power-metallurgy, day by day cause people's attention.
The method that the coal gangue of take is at present raw material extraction aluminum oxide has acid system, alkaline process, soda acid (salt) integrated process.Because acid system is in the industrial shortcomings such as etching apparatus, acid are difficult for reclaiming, the difficult removal of metallic impurity, environmental pollution that exist, Industry Promotion is restricted.Adopt in addition soda acid (salt) integrated process, exist technical process long, manufacturing cost is high, the problem of the low and environmental pollution of product purity.Alkali process is to add coal gangue to calcine soda ash or lime mostly, finally leaches aluminum oxide.Due to the interference of silicon-dioxide, there is the problem that alkaline consumption is large, energy consumption is high, less economical.
Chinese invention patent application number is a kind of 200510048215.1 " method with coal gangue for producing alumina ", discloses first and has pulverized coal gangue, and adds Na 2cO 3after ℃ roasting of D700～900, with the leaching of NaOH solution, filtration residue, filtrate is led to CO 2generate AI (OH) 3it is fixed to sink, and filters, and dries to sink to determine through high temperature dehydration, to obtain AI again 2o 3product.Chinese invention patent Shen number is " extracting the method for aluminium hydroxide or aluminum oxide and producing cement from fag end thereof in coal gangue " of 200710017303.4, disclose first by calcined coal gangue, the metakaolinite producing after calcining adds lime or calcium carbide mixing and water adding carries out steam pressure reaction, then steam pressure material is calcined at 800～1000 ℃, calcination of chamotte leaches with sodium carbonate solution, leaching liquid makes aluminium hydroxide through desiliconization, carbonization again, and aluminium hydroxide calcining is aluminum oxide." utilizing coal gangue aluminium hydroxide and silicic acid processing method " of Chinese invention patent application numbers 200710133214.6, disclose and first coal gangue has been added to soda ash alkali and melt, grog shrend, wet-milling, after slurry separated and dissolved, filter cake is used caustic soda alkali fusion again, the heating of gained underflow material obtains dry powder and dissolves, after filtering separation, filter cake is again through caustic soda stripping, above three technology process slurry is dissolved, dry powder dissolves, caustic soda stripping obtains filtrate and produces aluminium hydroxide through dilution hydrolysis, dilution water solution obtains filtrate and divides three carbonizations, and product is respectively aluminium hydroxide, silicic acid and sodium carbonate.Above three technology patent is alkaline process, because dioxide-containing silica in coal gangue is high, directly extracts aluminum oxide very large to the need consumption of alkali, although the patent of application number 200710133214.6 is produced byproduct silicic acid, technique is very loaded down with trivial details, less economical.Chinese invention patent application number is 200410062965.X " a kind of technique of producing aluminum oxide ", discloses and in advance kaolinite, fire pot coal ash etc. has been carried out to active pre-desiliconizing, then baking mixed from pulverizing sintering process with Wingdale.The leaching of sodium carbonate sig water, leaching liquid complex reaction are purified, carbonization makes aluminium hydroxide, high-temperature roasting is aluminum oxide again, pre-desiliconizing has first been carried out in this invention, alkali has lacked alkali consumption, but the silicon-dioxide removing is not utilized, and has caused the wasting of resources, in this invention, the Wingdale of kaolinite calcination activation is all higher from the temperature of pulverizing sintering in addition, and energy consumption is larger.
Summary of the invention
The deficiency existing in order to overcome above-mentioned prior art, the object of this invention is to provide a kind of extract aluminum and coproducing active calcium silicate and cement from coal gangue and technique.The method technique is simple, production cost is low, energy consumption is low, material consumption amount is few, makes three kinds of silicon-containing products byproducts simultaneously, and without generation of waste materials.
In order to reach foregoing invention object, technical scheme of the present invention realizes as follows; Will
From coal gangue, extract aluminum and coproducing active calcium silicate and cement and a technique thereof, its key step is:
1. after pulverizing coal gangue, carry out high-temperature roasting activation;
2. the coal gangue grog after roasting adds sodium hydroxide solution to carry out alkali solution-off pasc reaction, and then filtering separation, obtains desiliconization coal gangue and sodium silicate solution;
3. milk of lime is added in sodium silicate solution, carry out causticizing reaction, then filtering separation obtains containing water gaging Calucium Silicate powder and sodium hydroxide solution, and moisture Calucium Silicate powder is dried and made active calcium silicate micro mist, can return to step and 2. recycle after sodium hydroxide solution is concentrated;
4. in the desiliconization coal gangue that 2. step obtains, add levigate Wingdale and sodium carbonate solution, send into ball mill endosphere and grind into charge pulp;
5. charge pulp is sent into rotary kiln baking, and the CO in recovered flue gas 2, for step 8. the refine carbon of liquid of sodium aluminate divide;
6. the grog water stripping after raw material roasting, filtering separation, obtains crude liquor of sodium aluminate and calcium silicate slag, calcium silicate slag after dealkalize is processed as cement raw material;
7. use two sections of desiliconization methods to crude liquor of sodium aluminate deep desilication, obtain sodium aluminate essence;
8. in sodium aluminate essence, pass into CO 2carbon divides, and filtering separation obtains aluminium hydroxide and sodium carbonate solution, returns to step and 4. recycle after sodium carbonate solution is concentrated.
9. aluminium hydroxide high-temperature calcination makes alumina product.
In aforesaid method, AI in described coal gangue 2o 3content>=50%, SiO 2content>=60%.
In aforesaid method, described coal gangue grinding particle size is 100～200 orders.
In aforesaid method, described coal gangue maturing temperature is 600～900 ℃, and roasting time table is 0.5～1.5h.
In aforesaid method, the simmer down to 10～20% of sodium hydroxide solution for described coal gangue desiliconization, the mass ratio of sodium hydroxide and coal gangue is 0.4～0.6, and desilication reaction temperature is 80～110 ℃, and the reaction times is 1.5～2 hours.
In aforesaid method, described milk of lime add-on is pressed CaO and SiO 2mol ratio is 1.0～1.3, and causticizing reaction temperature is 80～100 ℃, and the reaction times is 1～1.5 hour.
In aforesaid method, the bake out temperature of described moisture Calucium Silicate powder is 200～300 ℃, and drying time is 0.5～2 hour.
In aforesaid method, described charge pulp water ratio is 30～35%, and calcium ratio is 1.8～2, and alkali ratio is 0.8～1.
In aforesaid method, described charge pulp maturing temperature in rotary kiln is 1000～1200 ℃, and roasting time is 0.5～1.5h.
In aforesaid method, described grog stripping temperature is 60～80%, and dissolution time table is 9～15min;
In aforesaid method, described sodium aluminate essence carbon minute temperature of reaction is 80～100% ℃, and it is 9～9.5 that carbon divides terminal to control PH.
Compared with the prior art, the invention has the advantages that:
(1) the present invention of pre-activated desilication process adopts coal gangue roasting sensitization, control rational maturing temperature and time, make aluminum oxide separated in the molten process of alkali with silicon-dioxide, 60% above silicon-dioxide enters into solution and is removed, greatly improve the alumina silica ratio in coal gangue, can reach more than 3.9.
(2) Energy Intensity Reduction coal gangue adopts preroasting activation, and maturing temperature, lower than prior art, improves its activity one, also be conducive to the roasting of raw material in alumina extraction technique, adopt soda-lime sintering process to reduce the maturing temperature of raw material simultaneously, shorten raw material roasting time, reduce energy consumption.
(3) Energy Intensity Reduction coal gangue takes active desiliconization to process, and greatly reduces the content of silicon-dioxide, reduces the alkali consumption of raw material roasting in alumina extraction technique, reduces the silico-calcium quantity of slag, has improved whole explained hereafter efficiency.
(4) this technique Raw that saves production cost adopts waste coal gangue, and sodium hydroxide and sodium carbonate all can recycle, and in raw material roasting process, produce CO 2recycle, reduced production cost.
(5) CO of refuse zero release chamotte kiln discharge 2gas, reclaims for carbon operation break-down; Sodium hydroxide and sodium carbonate Recycling Mother Solution are used; Calcium silicate slag is as cement raw material after dealkalize is processed, and whole technique has realized refuse zero release.
(6) Product Activity calcium silicate powder whiteness is high, foreign matter content is low, can be widely used in the industries such as rubber, plastics, coating, papermaking, and valuable resource is fully utilized, and increases economic efficiency.
Below in conjunction with the drawings and specific embodiments mode, invention is described in further detail.
Accompanying drawing explanation
Embodiment
Referring to accompanying drawing, production stage of the present invention is:
1. raw material choose is containing AI 2o 342.93%/SiO 251.92% coal gangue, is milled down to after 200 orders, and high-temperature roasting is active, and maturing temperature is 650 ℃, soaking time table 2h.
2. after roasting grog naturally cooling, by coal gangue and NaOH mass ratio, add 15% sodium hydroxide solution at 1: 1.5, at 110 ℃, carry out desilication reaction, reaction times table 2h.After reaction finishes, carry out filtering separation, the filtrate sodium silicate solution obtaining and filter cake desiliconization coal gangue.
3. milk of lime is joined in filtrate sodium silicate solution and carry out causticizing reaction, milk of lime add-on is pressed CaO and SiO 2mol ratio is 1.1,90 ℃ of temperature of reaction, and filtering separation after reaction Ih, filtrate is sodium hydroxide solution, by returning to step after evaporation concentration, 2. recycles.Filter cake is moisture Calucium Silicate powder, makes active calcium silicate micro mist after drying Ih at 350 ℃.
4. by the coal gangue after desiliconization, levigate Wingdale, circulation carbon mother liquid are that sodium carbonate solution is mixed in proportion, and ball milling is prepared charge pulp, and charge pulp proportioning calcium ratio is 2.02, and alkali ratio is 0.96, and the water ratio of charge pulp is 38%.
5. the charge pulp making is sent into rotary kiln baking, sintering Ih under 1200 ℃ of high temperature, and reclaim with the solvent method of industrial maturation the CO that roasting produces 2for the refine carbon of liquid of sodium aluminate, divide.
6. the grog water stripping after raw material roasting, stripping temperature 70 C 15min, liquid-solid ratio 2: 1, it is crude liquor of sodium aluminate that filtering separation obtains filtrate, filter cake is calcium silicate slag, calcium silicate slag after dealkalize is processed as cement raw material.
7. by two sections of desiliconization methods of existing mature technology, crude liquor of sodium aluminate is carried out to deep desilication, obtain the sodium aluminate liquid of refining.
8. the liquid of refining of the sodium aluminate after desiliconization divides in tower at carbon, CO used 2come from CO in rotary kiln flue gas 2recovery purify, carbon minute temperature is 80 ℃, terminal pH value is 10, filtering separation obtains aluminium hydroxide and sodium carbonate solution, returns to step and 4. recycle after sodium carbonate solution is concentrated.
9. aluminium hydroxide makes alumina product by existing mature technology high-temperature calcination.

Claims (10)

1. from coal gangue, extract aluminum and coproducing active calcium silicate and cement and a technique, its key step is:
1. pulverize coal gangue and carry out high-temperature roasting after 100-200 order:
2. the coal gangue grog after roasting adds sodium hydroxide solution to carry out alkali solution-off pasc reaction, and then filtering separation, obtains desiliconization coal gangue and sodium silicate solution;
3. milk of lime is added in sodium silicate solution, carry out causticizing reaction, then filtering separation obtains moisture Calucium Silicate powder and sodium hydroxide solution, and moisture Calucium Silicate powder is dried and made active calcium silicate micro mist, can return to step and 2. recycle after sodium hydroxide solution is concentrated;
4. in the desiliconization coal gangue that 2. step obtains, add levigate Wingdale and sodium carbonate solution, send into ball mill ball milling and make charge pulp;
5. charge pulp is sent into rotary kiln baking, and the CO in recovered flue gas 2for step 8. the refine carbon of liquid of sodium aluminate divide;
6. the grog water stripping after raw material roasting, filtering separation, obtains crude liquor of sodium aluminate and calcium silicate slag, calcium silicate slag after dealkalize is processed as cement raw material;
7. use two sections of desiliconization methods to sodium aluminate deep desilication, obtain the sodium aluminate liquid of refining;
8. sodium aluminate is refined in liquid and is passed into CO 2carbon divides, and filtering separation obtains aluminium hydroxide and sodium carbonate solution, returns to step and 4. recycle after sodium carbonate solution is concentrated;
9. aluminium hydroxide high-temperature calcination makes alumina product.
2. according to extract aluminum and coproducing active calcium silicate and cement from coal gangue and technique claimed in claim 1, it is characterized in that Al in described coal gangue 2o 3content>=50%SiO 2content>=60%.
3. according to extract aluminum and coproducing active calcium silicate and cement from coal gangue and technique claimed in claim 3, it is characterized in that, described coal gangue maturing temperature is 600～900 ℃, and roasting time is 0.5～1.5h.
4. according to extract aluminum and coproducing active calcium silicate and cement from coal gangue and technique claimed in claim 1, it is characterized in that, described bastard coal desiliconization is 10～20% by the concentration of sodium hydroxide solution, the mass ratio of sodium hydroxide and coal gangue is 0.4～0.6, desilication reaction temperature is 80～110 ℃, and the reaction times is 1.5～2 hours.
5. according to extract aluminum and coproducing active calcium silicate and cement from coal gangue and technique claimed in claim 1, it is characterized in that, described milk of lime add-on is pressed CaO and SiO 2mol ratio is 1.0～1.3, and causticizing reaction temperature is that 80～100 ℃ of reaction times are 1～1.5 hour.
6. according to extract aluminum and coproducing active calcium silicate and cement from coal gangue and technique claimed in claim 1, it is characterized in that, the bake out temperature of described moisture Calucium Silicate powder is 200～300 ℃, and drying time is 0.5～1.5 hour.
7. according to extract aluminum and coproducing active calcium silicate and cement from coal gangue and technique claimed in claim 7, it is characterized in that, described charge pulp water ratio is 30～35%, and calcium ratio is 1.8～2, and alkali ratio is 0.8～1.0.
8. according to its technique of using of extracting aluminum and coproducing active calcium silicate and cement from coal gangue claimed in claim 1, it is characterized in that, described charge pulp maturing temperature in rotary kiln is 100～1200 ℃, and roasting time table is 0.5～1.5h.
9. according to its technique of using of extracting aluminum and coproducing active calcium silicate and cement from coal gangue claimed in claim 1, it is characterized in that, described grog stripping temperature is that 60～80 ℃ of dissolution times are 9～15min.
10. according to extract aluminum and coproducing active calcium silicate and cement from coal gangue and technique claimed in claim 1, it is characterized in that, the described sodium aluminate liquid carbon temperature of reaction of refining is 80～100 ℃, and it is 9～9.5 that carbon divides terminal to control pH.
CN201210263998.5A 2012-07-27 2012-07-27 Process for combined production of alumina as well as active calcium silicate and cement from gangue Pending CN103754905A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016050332A1 (en) * 2014-09-29 2016-04-07 Karlsruher Institut für Technologie Method for separating aluminum during calcium silicate production
CN106542551A (en) * 2016-11-24 2017-03-29 中南大学 A kind of method of coproduction dawsonite and hydrated calcium silicate from flyash
CN108545781A (en) * 2018-07-03 2018-09-18 贵州大学 A kind of comprehensive utilization process of high-sulfur bauxite and ardealite

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016050332A1 (en) * 2014-09-29 2016-04-07 Karlsruher Institut für Technologie Method for separating aluminum during calcium silicate production
CN106542551A (en) * 2016-11-24 2017-03-29 中南大学 A kind of method of coproduction dawsonite and hydrated calcium silicate from flyash
CN106542551B (en) * 2016-11-24 2017-12-01 中南大学 A kind of method of coproduction dawsonite and hydrated calcium silicate from flyash
CN108545781A (en) * 2018-07-03 2018-09-18 贵州大学 A kind of comprehensive utilization process of high-sulfur bauxite and ardealite

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