CN101857253B - Process for producing aluminium hydroxide, silicic acid and sodium carbonate by utilizing fly ash - Google Patents
Process for producing aluminium hydroxide, silicic acid and sodium carbonate by utilizing fly ash Download PDFInfo
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Abstract
A process for producing aluminium hydroxide, silicic acid and sodium carbonate by utilizing fly ash belongs to the chemical development and utilization methods of aluminum-silicate minerals. Aiming at the following problems in the existing method: the alumina components in the fly ash are only utilized and the extraction ratio of the alumina components is only 60-85%; the main component silica is abandoned; the energy consumption and cost are high; washing is carried out multiple times and secondary pollution is caused because the washing liquid is not recycled, in the process of the invention, simultaneous extraction of 95% of alumina and 90% of silica is realized through sodium carbonate fusion, sodium hydroxide fusion, carbonization and hydrolysis by utilizing the principle of sodium carbonate circulation and adopting the sintering process to produce the aluminium hydroxide, the silicic acid and the sodium carbonate. The process flow is simple and the production cycle of the products is short. The carbon dioxide, the waste heat and the washing liquid in the sodium carbonate and the flue gas are recycled, thus greatly lowering the production cost. The products are applicable to the industries such as papermaking, printing ink, printing and dyeing, medicines, detergents and the like, and the extended products can be used in the industries such as petrochemicals, rubber and plastics and the like.
Description
Utilize flyash to produce white lake and silicic acid and soda ash process method.
Technical field: the method that the present invention relates to utilize the chemical development of aluminium silicate mineral to utilize, particularly a kind of process method of utilizing flyash to produce white lake and silicic acid and soda ash.
Background technology: according to the limit bright prosperous, separate strong, Zhao Youcai and in " coal solid changing waste into resources technology " (Chemical Industry Press's in May, 2005 first version) book, claim: national flyash output was 1.6 hundred million tons in 2000; Take up an area of 500,000 mu; Add 1,100,000,000 tons of flyash of stock over the years, national flyash in 2000 accumulates total amount and reaches 12.5 hundred million tons.Since the increase of thermal power output, by the end of the end of the year 2006, nearly 2,000,000,000 tons in the flyash that whole nation accumulative total is accumulated.The essentially consist of flyash is an aluminosilicate, mainly is aluminum oxide and silicon-dioxide, and two components total accounts for 75-92%; Wherein aluminum oxide accounts for 23-38%; Silicon-dioxide generally accounts for more than 50%, and other contains the oxide compound of elements such as small amounts of iron, calcium, magnesium, and each components contents is different because of the place of production of coal.From trade waste flyash, extracting Chemicals, turn waste into wealth, improve environment, is countries in the world, the important industry policy of China especially.
People such as Sun Yazhen CN1095689.1994 and Chen Jianlin the 14th page of 1994 the 4th phase " environment Leader " publish the article (documents 1) propose with the sulfuric acid immersion flyash of 50-60% 12-14 hour; 100 ℃ of heating 2-4 hour; Filtered while hot, the repetitive scrubbing filter cake discards filter cake to neutral; The heating of will filtrating is concentrated into 15-20 degree Beaume crystallisation by cooling again, and suction filtration obtains the Tai-Ace S 150 crystal.This documents 1 adopts acidleach flyash technology to obtain the Tai-Ace S 150 product, and the extraction yield of aluminum oxide has only 60-65%, and the main components silica of the another kind in the flyash is not utilized, and the economic worth of technology is not high.
Xie Ying the 54th page of 1992 the 3rd phase " total utilization of PCA " publish the article (documents 2) propose flyash is mixed stirring and is heated to boiling with caustic soda soln; Insulated and stirred for some time again; Filter, discard filter cake, filtrating is added water or feeds carbonic acid gas, adds volatile salt; Obtain aluminum hydroxide precipitation, again through filtering, the filter cake oven dry being obtained white lake.The wet processing that this documents 2 adopts, the extraction yield of aluminum oxide also has only about 70%, and another main components silica is not utilized yet in the flyash.
Han Huaiqiang, Jiang Tingda propose to use lime sinter process at " utilization of fly ash technology " (Chemical Industry Press's first version in January calendar year 2001) (documents 3) 177-179 page or leaf; Flyash is mixed the back to be burnt till at 1320-1400 ℃ with limestone powder; Make aluminum oxide change into sodium aluminate and calcium aluminate, from efflorescence, yellow soda ash stripping, milk of lime desiliconization waste, dioxide gas carbonization, extract white lake through grog; Again with white lake 1200 ℃ of calcinings, obtain aluminum oxide.The waste residue that discards during desiliconization is used to produce cement.It is 80-85% that Liu Xiaobo proposes the rational alumina extraction ratio of lime sinter process technology at 1999 the 2nd phases " ACTA Scientiae Circumstantiae " 210-213 page or leaf.This documents 3 adopts lime sinter process, and the extraction yield of aluminum oxide is greatly improved in the powdered coal ash, but also can only reach 85%; Simultaneously, in the flyash another more main ingredient silicon-dioxide just be used to produce cement still not by high value added utilization as waste residue, the economic worth of silica component is underutilized.
In sum, there is following deficiency in documents 1,2,3:
1, all only the alumina component in the flyash is utilized, also can only reach 60-85% to the extraction yield of aluminum oxide, so the utilization ratio of resource is all lower, only has been equivalent to utilize about the 20-30% of powdered coal ash total amount; When alumina content in the raw material powder coal ash is low, the raw material powder coal ash can not utilize.
2, to another the main components silica in the flyash, abandon in the documents 1,2, just be used for the cement of production low value in the documents 3 as waste residue, silica component does not obtain high value added utilization.
3, in utilizing the flyash process, all occurred because energy consumption is high, life cycle of the product is long, and the powdered coal ash utilization ratio is lower in addition, makes the cost of unit output product increase the problem that production cost is difficult to reduce.
4, all need repeatedly use water washing in the production technique, and washings fails to recycle, and has not only expended a large amount of valuable water resourcess, add the abandoning of staple silicon-dioxide of flyash in the documents 1,2, all cause second environmental pollution.
This shows that studying a kind of resource utilization is high, utilization of resources added value is high, production cost is low, production process does not have secondary pollution fly ash development, to utilize method be necessary.
Summary of the invention: the deficiency that the objective of the invention is to overcome prior art; Develop that a kind of resource utilization is high, utilization of resources added value is high, production cost is low, production process does not have the fly ash development of secondary pollution to utilize method again, particularly a kind of process method of utilizing flyash to produce white lake and silicic acid and soda ash.
The objective of the invention is to realize like this: a kind of process method of utilizing flyash to produce white lake and silicic acid and soda ash; Be characterised in that utilization soda ash round-robin principle; Adopt sintering process technology; Melt-caustic soda alkali fusion-carbonization-hydrolysis through soda ash alkali, realize extracting simultaneously aluminum oxide and the silicon-dioxide in the flyash, produce white lake and silicic acid and soda ash.
Description of drawings: Fig. 1 is a technological principle synoptic diagram of the present invention, and Fig. 2 is the Production Flow Chart synoptic diagram of practical implementation of the present invention.
As shown in fig. 1:
1, soda ash alkali melts: flyash-soda ash mixed material powder heating is carried out alkali and melted processing, obtain the molten mass grog.The input of molten mass grog is road shrend operation down.
2, shrend: soda ash alkali melted handle the molten mass grog obtain and take advantage of high temperature and carry out shrend rapidly, obtain the solid fine grain material.The input of solid fine grain material is road wet-milling operation down.
3, wet-milling: the solid fine grain material that shrend is obtained carries out wet-milling, obtains dense thick slurry.Dense thick slurry input is road slurry dissolution process down.
4, slurry dissolving: the underflow material that wet-milling is obtained dilutes, dissolves; After the dissolving, filter, obtain filter cake and filtrating.The filter cake input is road caustic soda alkali fusion procedure down, the thick white lake of the filtrating input back road first carbonation process production.
5, caustic soda alkali fusion: the filter cake with the slurry dissolving obtains, add caustic soda soln, the alkali fusion processing is carried out in heating, obtains dry powder.The dry powder input is road dry powder dissolution process down.
6, dry powder dissolving: the dry powder that the caustic soda alkali fusion is obtained dissolves.After the dissolving, filter, obtain filter cake and filtrating.Include part white lake in the filter cake, after washing, input is road white lake stripping operation down; The thick white lake of the filtrating input back road first carbonation process production.
7, white lake stripping: the filter cake that the dry powder dissolving is obtained dissolves with caustic soda soln, makes the white lake dissolving get into solution.After the dissolving, filter, obtain filter cake and filtrating.Filter cake is through washing as filter residue; The filtrating input is the thick white lake of the road first carbonation process production down.
8, first carbonization: the filtrating that the dissolving of front slurry, dry powder dissolving and white lake stripping three process are obtained merges, and after diluting, carries out the carbonating processing first time with dioxide gas.After first carbonization finishes, filter, obtain filter cake and filtrating.For containing the thick white lake of silicon-dioxide, input is road filter cake dissolution process down through washing for filter cake; Road, filtrating input back second carbonation process.
9, filter cake dissolving: the filter cake with first carbonization obtains, dissolve with caustic soda soln and the dense filtrating that road, back filtrating enrichment process obtains, obtain containing the sodium aluminate solution of silicon-dioxide, input is road desiliconization purification process down.
10, desiliconization is purified: the sodium aluminate solution that contains silicon-dioxide with the filter cake dissolving obtains, add unslaked lime or white lime and stirring heating, and carry out desiliconization and handle.After the desiliconization processing finishes, filter, obtain filter cake desiliconization slag and filtrating.Desiliconization slag contains aluminum oxide and silicon-dioxide, directly imports preceding road caustic soda alkali fusion procedure, with the filter cake that the slurry dissolution process obtains, carries out the caustic soda alkali fusion again and handles; Filtrating is the raffinal acid sodium solution, and white lake is produced in input road dilution hydrolyzing process down.
11, dilution hydrolysis:, dilute hydrolysis with the filtrating that desiliconization is purified and obtained.After hydrolysis finishes, filter, obtain filter cake and filtrating.Filter cake is a product white lake after washing, oven dry, pulverizing; Filtrating is for containing the dilute solution of sodium hydroxide of sodium aluminate, and input is road filtrating enrichment process down.
12, filtrating concentrates: dilution water is separated the filtrating that obtains, and heating evaporation concentrates, and obtains strong solution.Strong solution is imported preceding road filter cake dissolution process.
13, second carbonization:, carry out the carbonating processing second time with dioxide gas with the filtrating that first carbonization obtains.After second carbonization finishes, filter, obtain filter cake and filtrating.Filter cake is a product silicic acid after washing, oven dry, pulverizing; The filtrating input is road filtrating evaporization process down.
14, filtrating evaporation: with the filtrating that second carbonization obtains, heating evaporation concentrates, and obtains oversaturated strong solution.The strong solution input is road crystallisation by cooling operation down.
15, crystallisation by cooling: the strong solution that the evaporation of will filtrating obtains is cooled off, crystallization.After the crystallization, filter, obtain filter cake and filtrating.Filter cake is a sodium hydrogencarbonate, and input is road filtration cakes torrefaction operation down; Filtrating is saturated solution of sodium bicarbonate, road, input back tail gas spray operation.
16, filtration cakes torrefaction: the filter cake that crystallisation by cooling is obtained carries out drying treatment, obtains the tail gas of product light ash and carbonated sodium dust.Road, tail gas input back tail gas spray operation.
17, tail gas spray: the filtrating that crystallisation by cooling is obtained is used for the tail gas of the carbonated sodium dust of upper track filtration cakes torrefaction operation is sprayed tail gas after being purified and spray liquid.Spray liquid is the saturated solution of sodium bicarbonate of carbonated sodium, and directly road batching drying process is used for batching, drying under the input; Tail gas after the purification directly discharges.
18, batching is dry: the spray liquid that the tail gas spray is obtained mixes with flyash, obtains mixed slurry; Mixed slurry is carried out drying, and sodium hydrogencarbonate discharges dioxide gas, and is decomposed into yellow soda ash, obtains flyash-soda ash mixed material powder, and the soda ash alkali that is used for next batch melts, and realizes the soda ash circulation.
Embodiment: combine Fig. 2, the present invention is so further realization:
Flyash among said Fig. 2 be meant use granularity as 80-200 purpose flyash dry ash as the raw material powder coal ash, wherein aluminum oxide and dioxide-containing silica all less than the restriction.
Soda ash alkali among said Fig. 2 melts and is meant 80-200 purpose flyash and light ash according to quality than flyash: light ash=1: 0.5-2.6 prepares burden, and concrete consumption is according to the Al in the mol ratio raw material
2O
3: the Na of adding
2CO
3=1: 1 with raw material in SiO
2: the Na of adding
2CO
3=1: the 0.4-2.3 sum is calculated, and obtains flyash-soda ash mixed material powder, and reaction is 40-60 minute under 1050-1450 ℃ of temperature, keeps drop temperature more than 1000 ℃, obtains the molten mass grog.The input of molten mass grog is road shrend operation down.
As shown in Figure 2; The high-temperature flue gas that produces during soda ash alkali melts carries out heat exchange with normal temperature air at first respectively: high-temperature flue gas is through the air heat exchange; Normal temperature air heated respectively obtain the 400-800 ℃ of warm air with 300-400 ℃ of two kinds of temperature; The high-temperature flue gas temperature reduces, and becomes warm stack gas in 500-600 ℃; In the warm stack gas spray liquid that is used for again back road tail gas spray operation is obtained and the mixed slurry of fine coal ashes carry out drying, obtain flyash-soda ash mixed material powder, middle temperature effluent gas temperature is reduced to below 200 ℃.Low temperature flue gas below 200 ℃ obtains carbonated normal temperature clean flue gas through washing, purifying treatment.
400-800 ℃ warm air is used for the heating of caustic soda alkali fusion process section;
300-400 ℃ clean hot air is used for the heating of natrii bicarbonas filter cake drying process section;
Carbonated normal temperature clean flue gas is used for first carbonization, the second carbonization technique section, makes the CO 2 raw material gas body.
Through heat exchange utilization and purifying treatment, realized the utilization again of used heat and waste gas to stack gas.
Shrend among said Fig. 2 is meant melts the high-temperature fusion body grog that process section generates with soda ash alkali, melts the furnace discharge mouth from alkali and flows out automatically, gets into cooling suddenly in the water quenching pool that fills washings, and high temperature chamotte is fragmented into the fine particle of 1-5 millimeter.Road, shrend liquid input back slurry dissolution process, the slurry that the dissolving wet-milling obtains; The fine particle input of 1-5 millimeter is road wet-milling operation down.
Wet-milling among said Fig. 2 is meant that the fine granules that the water quenching technology section is obtained takes out from water quenching pool, carry out wet-milling with washings, is ground to more than fineness 80 orders, obtains dense thick slurry.Dense thick slurry input is road slurry dissolution process down.
Slurry dissolving among said Fig. 2 is meant that the dense thick slurry that the wet-grinding technology and relative device section is obtained dilutes with shrend liquid and washings.During dilution, active Na in the control solution
2O>=200 grams per liters stirred 20-30 minute under natural temperature, in 2 hours, filtered as early as possible.After the filtration, obtain filter cake and filtrating.The filter cake input is road caustic soda alkali fusion procedure down; Road, filtrating input back first carbonation process.
Active Na
2O is meant by Na
2CO
3The Na that conversion provides
2O; Active Na
2The Na that drops into when the O quality is melted according to alkali
2CO
3Quality is at Na
2CO
3Value is calculated between the transformation efficiency 70-75%, and the numerical value of being got can comprise 70% or 75%.
Caustic soda soln among said Fig. 2 is meant the NaOH solution of mass percent concentration >=30%.
Caustic soda alkali fusion among said Fig. 2 is meant that filter cake that slurry dissolution process section is obtained and caustic soda soln are according to the SiO in the mol ratio filter cake
2: the NaOH=1 of adding: 1-1.4 prepares burden, and 400-800 ℃ of warm air beating reaction with the heat exchange through high-temperature flue gas obtains becomes dry powder up to material.The dry powder input is road dry powder dissolution process down.
Dry powder dissolving among said Fig. 2 is meant dissolves the dry powder that obtains through caustic soda alkali fusion process section with washings.During the dry powder dissolving, Na in the solution of control dissolving back
2O>=250 grams per liters; After the dry powder dissolving, at 4 hours inner filtrations.After the filtration, obtain filter cake and filtrating.Filter cake with 95 ℃ of hot washes to PH=11.Washings is concentrated and is used for recycle.Filter cake after the washing is the impurity that contains white lake, and input is road white lake stripping operation down; Road, filtrating input back first carbonation process.
White lake stripping among said Fig. 2 is meant the filter cake that obtains through dry powder dissolution process section, dissolves with caustic soda soln again.Filter cake when dissolving, the caustic soda soln amount of adding according to filter cake with after caustic soda soln mixes, mol ratio Al in the solution
2O
3: Na
2O=1: 1.4-1.6 calculates, Na in the control solution
2O concentration between the 230-250 grams per liter, 110 ℃ of temperature, dissolution time 3 hours.After the filter cake dissolving, filter, obtain filter cake and filtrating.Filter cake with 95 ℃ of hot washes to PH=11.Washings is concentrated and is used for recycle.Filter cake after the washing is alkalescence as filter residue, wherein still contains a small amount of Al (OH)
3, input back road WWT operation is used for that the sewage after the washing stack gas is carried out flocculating and purifying and handles; The filtrating input is road first carbonation process down.
First carbonization among said Fig. 2 is meant that the filtrating that filtrating that slurry dissolution process section is obtained, filtrating that dry powder dissolution process section obtains and white lake dissolving-out process section obtain merges; Dilute with washings earlier, carry out the carbonating processing first time with carbonated normal temperature clean flue gas again.During dilution, Na in the control solution
2The mass percent concentration of O≤8.5%; During carbonization, the starting temperature 60-80 of solution ℃; Pressure 0.25-0.3MP; 40 ℃ of terminal temperatures, PH=10.8-11.First carbonization at normal pressure, 20 minutes after-filtration of about 40 ℃ of following ageings, obtains filter cake and filtrating after finishing.Filter cake with 95 ℃ of hot washes to PH=9.5-9.8.Washings is concentrated and is used for recycle.Filter cake after the washing is for containing a small amount of SiO
2Thick white lake, input is road filter cake dissolution process down; Road, filtrating input back second carbonation process.
Filter cake dissolving among said Fig. 2 is meant that the filter cake that the first carbonization technique section is obtained with the dense filtrating dissolving that caustic soda soln and road, back filtrating enrichment process obtain, obtains crude sodium aluminate solution.During the filter cake dissolving, the caustic soda soln of adding and the dense amount of filtrate that road, back filtrating enrichment process obtains mix Al in the solution of back according to filter cake with caustic soda
2O
3≤150 grams per liters, Na
2O≤210 grams per liters calculate, 110 ℃ of temperature, dissolution time 3 hours.The input of crude sodium aluminate solution is road desiliconization purification process down.
Desiliconization among said Fig. 2 is purified and is meant that adding unslaked lime quicklime or white lime calcium hydroxide in the crude sodium aluminate solution that filter cake dissolution process section is obtained carries out desiliconization and handle.During desiliconization, quicklime consumption 6-8 grams per liter, 100 ℃ of temperature, 1 hour time.After desiliconization is purified, filter, obtain desiliconization slag and filtrating.Desiliconization slag is directly imported preceding road caustic soda alkali fusion process section, with the filter cake that the slurry dissolution process obtains, carries out the caustic soda alkali fusion again and handles; The filtrating input is road dilution hydrolyzing process down.
Dilution hydrolysis among said Fig. 2 is meant the filtrating that desiliconization purifying technique section is obtained, and dilutes hydrolysis with 95 ℃ of hot water.NaAlO in control solution during hydrolysis
2Concentration≤0.5M; Time 20-30 minute.After the hydrolysis, filter, obtain filter cake and filtrating.Filter cake with 95 ℃ of hot washes to PH=7-8.Washings is concentrated and is used for recycle.Filter cake after the washing is a white lake; The filtrating input is road filtrating enrichment process down.
Filtrating among said Fig. 2 concentrating is meant the filtrating that dilution hydrolysis process section is obtained, and evaporation concentration is carried out in heating.When concentrating, Na in the control solution
2It is striking point that O concentration reaches 310 grams per liters, obtains containing the soda-lye of sodium aluminate, is recycled to preceding road filter cake dissolving workshop section, is used for replacing caustic soda soln to carry out the filter cake dissolving.
Second carbonization among said Fig. 2 is meant the filtrating that the first carbonization technique section is obtained, and carries out the carbonating processing second time with carbonated normal temperature clean flue gas again.During carbonization, starting temperature 60-80 ℃; Pressure 0.25-0.3MP; 40 ℃ of terminal temperatures, PH=8.7-9.Second carbonization at normal pressure, 20 minutes after-filtration of about 40 ℃ of following ageings, obtains filter cake and filtrating after finishing.Filter cake with 95 ℃ of hot washes to PH=7-8.Washings is concentrated and is used for recycle.Filter cake after the washing is a silicic acid; Filtrating being contained the sodium hydrogen carbonate solution of a small amount of yellow soda ash, and input is road filtrating evaporization process down.
Filtrating evaporation among said Fig. 2 is meant the filtrating that the second carbonization technique section is obtained, and evaporation concentration is carried out in heating.When concentrating, control solution density d=1.11-1.12g/cm
3Be striking point, obtain containing the sodium hydrogencarbonate supersaturated solution of a small amount of yellow soda ash.Strong solution input after concentrating is road crystallisation by cooling operation down.
Crystallisation by cooling among said Fig. 2 is meant that water cools off, crystallization with the upper track strong solution that the evaporation technology section obtains of filtrating.After the crystallization, filter, obtain filter cake and filtrating.Filter cake is a sodium bicarbonate crystal, directly road filtration cakes torrefaction operation under the input; Filtrating is for containing the saturated solution of sodium bicarbonate of a small amount of yellow soda ash, road, input back tail gas spray operation.
Filtration cakes torrefaction among said Fig. 2 is meant the natrii bicarbonas filter cake that the crystallisation by cooling process section is obtained, and carries out drying treatment with the 300-400 ℃ of clean hot air that the heat exchange through stack gas obtains, and obtains dry powder and the tail gas that contains dust.Dry powder is light ash; Dust in the tail gas is the soda ash sodium carbonate dust, and the tail gas input is road tail gas spray operation down.
Tail gas spray among said Fig. 2 is meant that the tail gas that upper track filtration cakes torrefaction process section is obtained sprays with the filtrating that the crystallisation by cooling process section obtains.Behind the spray, tail gas that is purified and spray liquid, spray liquid are the saturated solution of sodium bicarbonate of carbonated sodium.Tail gas after the purification directly discharges; The spray liquid input is road batching drying process down.
Batching drying among said Fig. 2 is meant that tail gas is sprayed the spray liquid that process section obtains to be mixed with the fine coal ashes, obtains mixed slurry; The middle temperature stack gas that cools to 500-600 ℃ after the heat exchange of mixed slurry usefulness process air is carried out drying, sodium hydrogencarbonate is decomposed, discharge dioxide gas; And be decomposed into soda ash yellow soda ash; Obtain flyash-soda ash mixed material powder, the soda ash alkali that is used for next batch melts, and realizes the soda ash circulation.
The dried exhaust temperature of preparing burden is reduced to below 200 ℃; Be the low temperature flue gas that contains dry tail dirt, after washing, purifying treatment, obtain containing the normal temperature clean flue gas of more dioxide gas; As the CO 2 raw material gas body, be used for first carbonization, the second carbonization technique section.
To prepare burden dried temperature below 200 ℃, the low temperature flue gas that contains dry tail dirt washes, after the purifying treatment, the sewage of generation, the filter residue that obtains after the filter cake washing with white lake dissolving-out process section carry out flocculating and purifying to be handled; The clear water circulation that obtains after the purifying treatment is used for follow-up flue gas scrubbing, has realized the circulation of washes.
Be the principles of chemistry in each technical process among Fig. 1, Fig. 2 below:
Soda ash alkali melts: Na
2CO
3+ SiO
2→ Na
2SiO
3+ CO
2↑
Na
2CO
3+Al
2O
3→NaAlO
2+CO
2↑
NaAlO
2+Na
2SiO
3→Na
2O·Al
2O
3·2SiO
2
Na
2CO
3+Fe
2O
3→NaFeO
2+CO
2↑
NaFeO
2+Al
2O
3→NaAlO
2+Fe
2O
3
CaO+SiO
2→2CaO·SiO
2
CaO+Al
2O
3→CaO·Al
2O
3
CaO+Fe
2O
3→2CaO·Fe
2O
3
Na
2CO
3+SiO
2+CaO→Na
2O·CaO·SiO
2+CO
2↑
CaO+Na
2O·Al
2O
3·2SiO
2→NaAlO
2+2CaO·SiO
2
MgO+SiO
2→MgO·SiO
2
MgO+CaO+Fe
2O
3→MgO·2CaO·Fe
2O
3
Slurry dissolving: NaAlO
2+ H
2O → Al (OH)
3↓+NaOH
NaFeO
2+H
2O→Fe(OH)
3↓+NaOH
Na
2O·Al
2O
3·2SiO
2+NaOH→NaAlO
2+Na
2SiO
3+H
2O
Caustic soda alkali fusion: Na
2OAl
2O
32SiO
2+ NaOH → NaAlO
2+ Na
2SiO
3+ H
2O
Al(OH)
3+NaOH→NaAlO
2+H
2O
Fe(OH)
3+NaOH→NaFeO
2+H
2O
Dry powder dissolving: NaAlO
2+ H
2O → Al (OH)
3↓+NaOH
NaFeO
2+H
2O→Fe(OH)
3↓+NaOH
White lake stripping: Al (OH)
3+ NaOH → NaAlO
2+ H
2O
First carbonization: NaOH+CO
2→ Na
2CO
3+ H
2O
NaAlO
2+CO
2+H
2O→Na
2CO
3+Al(OH)
3↓
Na
2SiO
3+CO
2+H
2O→Na
2CO
3+NaHSiO
3
Filter cake dissolving: Al (OH)
3+ NaOH → NaAlO
2+ H
2O
Desiliconization is purified: NaAlO
2+ CaO+H
2O → 3CaOAl
2O
36H
2O ↓+NaOH
NaAlO
2+Na
2SiO
3+CaO+H
2O→3CaO·Al
2O
3·xSiO
2·(6-2x)H
2O↓+NaOH
Dilution hydrolysis: NaAlO
2+ H
2O → Al (OH)
3↓+NaOH
Second carbonization: NaHSiO
3+ CO
2+ H
2O → Na
2CO
3+ H
2SiO
3↓
Na
2CO
3+CO
2+H
2O→NaHCO
3
Filtration cakes torrefaction: NaHCO
3→ Na
2CO
3+ CO
2↑+H
2O ↑
Batching is dry: NaHCO
3→ Na
2CO
3+ CO
2↑+H
2O ↑
The present invention has received following effect through practical probation:
1, the resource utilization of flyash is high.Compare with documents 1,2,3, the present invention has not only utilized the aluminum oxide that accounts for powdered coal ash total amount about 30%, and has utilized simultaneously and account for the silica component of powdered coal ash more than 50%, is applicable to the exploitation of various fly ashs; More than the extraction rate reached to 95% of aluminum oxide, more than the extraction rate reached to 90% of silicon-dioxide.
2, the added value of the utilization of resources is high.Compare with documents 1,2,3; Use known acid to dissolve and dissolve technology with alkali; White lake and silicic acid through the present invention is obtained carry out further deep processing, are easy to obtain the Chemicals such as various aluminium salt and silicate and aluminum oxide, aluminate, precipitated silica, silica gel of A wide selection of colours and designs, high added value that specification is various.The commercial value of technical application is high.
3, product cost is low.Compare with documents 1,2,3, the present invention adopts alkali process, and technical process is succinct, and life cycle of the product is short, as long as 4-6 hour; The product yield is high; The recycle and reuse of raw material soda ash, and to the recycling of the carbonic acid gas in the stack gas, waste heat, washings makes resulting white lake and silicic acid cost all reduce significantly than other process method production costs both at home and abroad.
4, cleaner production.Compare with documents 1,2,3, technological process of the present invention has realized the material closed cycle, and production process does not have secondary pollution to environment.
White lake, silicic acid and the soda ash product that the present invention implements to obtain and used by white lake and silicic acid that known acid is dissolved, alkali dissolves various aluminium salt, aluminate, aluminum oxide, silicate, WHITE CARBON BLACK, the silica gel product that technology obtains can be that industries such as printing ink, papermaking, printing and dyeing, weaving, medicine, grease, catalyzer, plastics, rubber, daily use chemicals, oil are used.
Claims (9)
1. process method of utilizing flyash to produce white lake and silicic acid and soda ash; Be characterised in that utilization soda ash round-robin principle; Adopt sintering process technology; Melt-caustic soda alkali fusion-carbonization-hydrolysis through soda ash alkali, realize extracting simultaneously aluminum oxide and the silicon-dioxide in the flyash, produce white lake and silicic acid and soda ash:
(1) soda ash alkali melts: flyash-soda ash mixed material powder heating is carried out alkali and melted processing, obtain the molten mass grog; The input of molten mass grog is road shrend operation down;
(2) shrend: soda ash alkali melted handle the molten mass grog obtain and take advantage of high temperature and carry out shrend rapidly, obtain the solid fine grain material; The input of solid fine grain material is road wet-milling operation down;
(3) wet-milling: the solid fine grain material that shrend is obtained carries out wet-milling, obtains dense thick slurry; Dense thick slurry input is road slurry dissolution process down;
(4) slurry dissolving: the underflow material that wet-milling is obtained dilutes, dissolves; After the dissolving, filter, obtain filter cake and filtrating; The filter cake input is road caustic soda alkali fusion procedure down, the thick white lake of the filtrating input back road first carbonation process production;
(5) caustic soda alkali fusion: the filter cake with the slurry dissolving obtains, add caustic soda soln, the alkali fusion processing is carried out in heating, obtains dry powder; The dry powder input is road dry powder dissolution process down;
(6) dry powder dissolving: the dry powder that the caustic soda alkali fusion is obtained dissolves; After the dissolving, filter, obtain filter cake and filtrating; Include part white lake in the filter cake, after washing, input is road white lake stripping operation down; The thick white lake of the filtrating input back road first carbonation process production;
(7) white lake stripping: the filter cake that the dry powder dissolving is obtained dissolves with caustic soda soln, makes the white lake dissolving get into solution; After the dissolving, filter, obtain filter cake and filtrating; Filter cake is through washing as filter residue; The filtrating input is the thick white lake of the road first carbonation process production down;
(8) first carbonizations: the filtrating that the dissolving of front slurry, dry powder dissolving and white lake stripping three process are obtained merges, and after diluting, carries out the carbonating processing first time with dioxide gas; After first carbonization finishes, filter, obtain filter cake and filtrating; For containing the thick white lake of silicon-dioxide, input is road filter cake dissolution process down through washing for filter cake; Road, filtrating input back second carbonation process;
(9) filter cake dissolving: the filter cake with first carbonization obtains, dissolve with caustic soda soln and the dense filtrating that road, back filtrating enrichment process obtains, obtain containing the sodium aluminate solution of silicon-dioxide, input is road desiliconization purification process down;
(10) desiliconization is purified: the sodium aluminate solution that contains silicon-dioxide with the filter cake dissolving obtains, add unslaked lime or white lime and stirring heating, and carry out desiliconization and handle; After the desiliconization processing finishes, filter, obtain filter cake desiliconization slag and filtrating; Desiliconization slag contains aluminum oxide and silicon-dioxide, directly imports preceding road caustic soda alkali fusion procedure, with the filter cake that the slurry dissolution process obtains, carries out the caustic soda alkali fusion again and handles; Filtrating is the raffinal acid sodium solution, and white lake is produced in input road dilution hydrolyzing process down;
(11) dilution hydrolysis:, dilute hydrolysis with the filtrating that desiliconization is purified and obtained; After hydrolysis finishes, filter, obtain filter cake and filtrating; Filter cake is a product white lake after washing, oven dry, pulverizing; Filtrating is for containing the dilute solution of sodium hydroxide of sodium aluminate, and input is road filtrating enrichment process down;
(12) filtrating concentrates: dilution water is separated the filtrating that obtains, and heating evaporation concentrates, and obtains strong solution; Strong solution is imported preceding road filter cake dissolution process;
(13) second carbonizations:, carry out the carbonating processing second time with dioxide gas with the filtrating that first carbonization obtains; After second carbonization finishes, filter, obtain filter cake and filtrating; Filter cake is a product silicic acid after washing, oven dry, pulverizing; The filtrating input is road filtrating evaporization process down;
(14) filtrating evaporation: with the filtrating that second carbonization obtains, heating evaporation concentrates, and obtains oversaturated strong solution; The strong solution input is road crystallisation by cooling operation down;
(15) crystallisation by cooling: the strong solution that the evaporation of will filtrating obtains is cooled off, crystallization; After the crystallization, filter, obtain filter cake and filtrating; Filter cake is a sodium hydrogencarbonate, and input is road filtration cakes torrefaction operation down; Filtrating is saturated solution of sodium bicarbonate, road, input back tail gas spray operation;
(16) filtration cakes torrefaction: the filter cake that crystallisation by cooling is obtained carries out drying treatment, obtains the tail gas of product light ash and carbonated sodium dust; Road, tail gas input back tail gas spray operation;
(17) tail gas spray: the filtrating that crystallisation by cooling is obtained is used for the tail gas of the carbonated sodium dust of upper track filtration cakes torrefaction operation is sprayed tail gas after being purified and spray liquid; Spray liquid is the saturated solution of sodium bicarbonate of carbonated sodium, and directly road batching drying process is used for batching, drying under the input; Tail gas after the purification directly discharges;
(18) batching is dry: the spray liquid that the tail gas spray is obtained mixes with flyash, obtains mixed slurry; Mixed slurry is carried out drying, and sodium hydrogencarbonate discharges dioxide gas, and is decomposed into yellow soda ash, obtains flyash-soda ash mixed material powder, and the soda ash alkali that is used for next batch melts, and realizes the soda ash circulation.
2. method according to claim 1; It is characterized in that describedly alkali is carried out in the heating of flyash-soda ash mixed material powder melting processing, obtain the molten mass grog, be meant 80-200 purpose flyash and light ash according to quality than flyash: light ash=1: 0.5-2.6 prepares burden; Obtain flyash-soda ash mixed material powder; Reaction is 40-60 minute under 1050-1450 ℃ of temperature, keeps drop temperature more than 1000 ℃, obtains the molten mass grog.
3. method according to claim 1, it is characterized in that described slurry dissolving: the underflow material that wet-milling is obtained dilutes, dissolves, and after the dissolving, filters, and is meant that the dense thick slurry that wet-milling is obtained dilutes; During dilution, active Na in the control solution
2O>=200 grams per liters was at 2 hours inner filtrations.
4. method according to claim 1; It is characterized in that described caustic soda alkali fusion: the filter cake with the slurry dissolving obtains, add caustic soda soln, heating is carried out alkali fusion and is handled; Obtain dry powder, be meant that filter cake that slurry dissolution process section is obtained and caustic soda soln are according to the SiO in the mol ratio filter cake
2: the NaOH=1 of adding: 1-1.4 prepares burden, and 400-800 ℃ of reacting by heating, becomes dry powder up to material.
5. method according to claim 1 is characterized in that described white lake stripping: the filter cake that the dry powder dissolving is obtained dissolves with caustic soda soln, makes the white lake dissolving get into solution; After the dissolving, filter, obtain filter cake and filtrating; Filter cake is meant the filter cake that obtains through dry powder dissolution process section through washing, dissolves with caustic soda soln; Filter cake when dissolving, the caustic soda soln amount of adding according to filter cake with after caustic soda soln mixes, mol ratio Al in the solution
2O
3: Na
2O=1: 1.4-1.6 calculates, Na in the control solution
2O concentration between the 230-250 grams per liter, 110 ℃ of temperature, dissolution time 3 hours; After the filter cake dissolving, filter, obtain filter cake, filter cake is washed with water to pH=11.
6. method according to claim 1; It is characterized in that described first carbonization: the filtrating that the dissolving of front slurry, dry powder dissolving and white lake stripping three process are obtained merges; After diluting, carry out first time carbonating with dioxide gas and handle, be meant that the filtrating that filtrating that slurry dissolution process section is obtained, filtrating that dry powder dissolution process section obtains and white lake dissolving-out process section obtain merges; Dilute earlier, carbonic acid gas carries out the carbonating processing first time again; During dilution, Na in the control solution
2The mass percent concentration of O≤8.5%; During carbonization, the starting temperature 60-80 of solution ℃; Pressure 0.25-0.3MPa; 40 ℃ of terminal temperatures, pH=10.8-11.
7. method according to claim 1; It is characterized in that the dissolving of described filter cake: the filter cake that first carbonization is obtained; Dissolve with caustic soda soln and the dense filtrating that back road filtrating enrichment process obtains, be meant that the filter cake that the first carbonization technique section is obtained dissolves with caustic soda soln and the dense filtrating that road, back filtrating enrichment process obtains; During the filter cake dissolving, the caustic soda soln of adding and the dense amount of filtrate in road, back mix Al in the solution of back according to filter cake with caustic soda
2O
3≤150 grams per liters, Na
2O≤210 grams per liters calculate, 110 ℃ of temperature, dissolution time 3 hours.
8. method according to claim 1; It is characterized in that described desiliconization purification: filter cake is dissolved the sodium aluminate solution that contains silicon-dioxide that obtains; Add unslaked lime or white lime and stirring heating; Carry out desiliconization and handle, be meant that adding lime in the solution that filter cake dissolution process section is obtained carries out the desiliconization processing; During desiliconization, quicklime consumption 6-8 grams per liter, 100 ℃ of temperature, 1 hour time.
9. method according to claim 1 is characterized in that described filtrating concentrating: dilution water is separated the filtrating that obtains, and heating evaporation concentrates, and obtains strong solution, is meant the filtrating that dilution hydrolysis process section is obtained, and evaporation concentration is carried out in heating; When concentrating, Na in the control solution
2It is striking point that O concentration reaches 310 grams per liters.
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| CN107662935A (en) * | 2017-11-06 | 2018-02-06 | 秦皇岛出入境检验检疫局煤炭检测技术中心 | A kind of method that aluminum oxide and silicic acid are extracted from flyash |
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| CN1281820A (en) * | 2000-02-01 | 2001-01-31 | 刘成长 | Technological process for producing aluminium salt and silicate by using coal gangue |
| CN101172634A (en) * | 2007-10-11 | 2008-05-07 | 刘成长 | Technique for producing hydroted alumina and silicic acid with coal ash |
| CN101172633A (en) * | 2007-10-11 | 2008-05-07 | 刘成长 | Technique for producing hydroted alumina and silicic acid with high-silicon low-aluminium mineral raw material |
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| CN1281820A (en) * | 2000-02-01 | 2001-01-31 | 刘成长 | Technological process for producing aluminium salt and silicate by using coal gangue |
| CN101172634A (en) * | 2007-10-11 | 2008-05-07 | 刘成长 | Technique for producing hydroted alumina and silicic acid with coal ash |
| CN101172633A (en) * | 2007-10-11 | 2008-05-07 | 刘成长 | Technique for producing hydroted alumina and silicic acid with high-silicon low-aluminium mineral raw material |
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