CN104556173B - A kind of flyash sintering hydrothermal method produces the method for xonotlite and aluminum oxide - Google Patents
A kind of flyash sintering hydrothermal method produces the method for xonotlite and aluminum oxide Download PDFInfo
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Abstract
Flyash sintering hydrothermal method produces a method for xonotlite and aluminum oxide, comprises the following steps: flyash is put the batching with chemical mineral processing solvent by (1), carries out chemical mineral processing process, then be separated and wash, make flyash concentrate; (2) prepare charge pulp (3) sintering and prepare grog; (4) Clinker digestion and separating, washing; (5) the original slurry of xonotlite presoma is prepared; (6) Hydrothermal Synthesis prepares xonotlite presoma; (7) Hydrothermal Synthesis prepares xonotlite filter cake.Present method efficiently solves the problem and defect that in prior art, consumption of limestone amount is large, energy-output ratio is large and the quantity of slag is large; Total utilization of PCA both can produce xonotlite, can also produce aluminum oxide, had both achieved substituted for silicon mineral wealth, achieved again and instead of bauxite resource, also a saving the resources such as soil, can also achieve economy of large scale and produce.
Description
Technical field
The present invention relates to a kind of method of comprehensive utilization of flyash, particularly a kind of flyash sintering hydrothermal method produces the method for xonotlite and aluminum oxide.
Background technology
Abundant high alumina coal resources are contained in the part coalfield in the areas such as China's Middle-west Inner Mongolia, North of Shanxi, nearly 1,000 hundred million tons of prospective reserves, amount to aluminous fly-ash amount about 15,000,000,000 tons, be equivalent to more than 8 times of the current bauxite retained reserve of China, and the alumina content in part flyash can reach 40 ~ 50%, this flyash is generally called aluminous fly-ash.Flyash is main solid waste from power plants generating electricity angle, but due to high alumina coal burning produce aluminous fly-ash in alumina content can reach 35 ~ 45%, have even up to more than 50%, silicone content is generally more than 35%.Aluminous fly-ash is valuable silicon-containing material and aluminum-containing raw material, has higher economic development value.
Current high alumina coal is mainly as the fuel combustion of thermal power generation, and the aluminous fly-ash solid waste that above-mentioned area is accumulated already more than 100,000,000 tons, and is also increasing with the scale of about 2,500 ten thousand tons every year.2010, as in 100,000,000 tons of coal productions that Zhungeer coal field is produced, except 4,000 ten thousand tons for covering 16 fuel-burning power plant in area, west, year output aluminous fly-ash 1,270 ten thousand tons, other 6,000 ten thousand tons of high alumina coals are transported to disperses combustion outside district.Burning mixed by high alumina coal in large quantities disperses combustion, multifuel combustion, reduces the alumina content of aluminous fly-ash, compromises aluminium element high-endization utility value, also compromises the high-endization utility value of element silicon simultaneously, gives and concentrates exploitation to bring difficulty.In recent years, although China's comprehensive utilization flyash technological development makes great progress, on the whole, comprehensive utilization flyash mainly restricts by technical progress, affects by region, economy and market environment.Domestic existing total utilization of PCA is roughly the same with the total utilization of PCA mode in external power station, is generally used as cement raw material, paves the way or make building block, brick etc., but mostly main based on the stacking of grey field, belongs to simple simple utilization.This considerably reduce aluminum oxide and element silicon in aluminous fly-ash added value, equal indirectly to waste bauxite resource and silicon resource.Meanwhile, a large amount of stackings of aluminous fly-ash had not only wasted land resources but also waste water resource, also contaminate environment, and it is still very severe that the degree of depth of flyash fully utilizes the situation faced.
Aluminium is modern energy-saving and environmental protection, green metal material, and China has been aluminium the biggest in the world and alumina producing state; China's metallic aluminium annual production in 2013 has reached 2,194 ten thousand tons, is greater than 47% in international accounting; Within 2013, China's aluminum oxide is greater than 42% in international accounting; Within 2014, production capacity 6,470 ten thousand tons built by aluminum oxide, runs production capacity more than 5,340 ten thousand tons.But, China's bauxite resource is quite deficient, about 5% of bauxite reserves Jin Zhan world total reserves, and mostly be unmanageable low-grade diasporite type bauxite, add that the limit of Abroad in Recent Years bauxite purchases policy, bauxite resource problem has become the maximum bottleneck of China's aluminum oxide and aluminum i ndustry Sustainable development.
Active development comprehensive utilization aluminous fly-ash new technology, turns waste into wealth aluminous fly-ash, and resource value is maximized, and for alternative China bauxite, silicon mine resource, Economization on land, guarantee China aluminium Industrial Security are significant.
For many years, under national policy guides, its representative processes route of research that Duo Jia university of China, scientific research institution and enterprise have actively developed aluminous fly-ash extraction aluminum oxide novel process can be divided into: pre-desiliconizing-soda-lime sintering process, acid system, ammonium method, limestone sintering process etc.Except pre-desiliconizing-soda-lime sintering process realizes Industrial demonstration production capacity, other technology level mostly still rests on and expands examination or pilot-plant test stage, be difficult to production metallurgy grade aluminum oxide and realize large-scale industrial production for the moment, all there is the problems such as tailings not easily utilizes; Pre-desiliconizing-soda-lime sintering process is the processing method that can realize at present suitability for industrialized production, but this technique still exists that consumption of limestone amount is large, lime calcining power consumption is higher, tailings the amount greatly and not easily problem such as utilization.
Traditional technology produces xonotlite and goods, its siliceous raw material is generally use diatomite or quartz sand and alkali to generate industrial waterglass under melting condition, in the preparation process of raw material, need to use the high quality silicon ores such as a large amount of quartz sand, diatomite and soda ash or sodium sulfate melting congruent melting in kiln, then cooling crush is obtained after dissolving; Make the selection of siliceous raw material need exploitation like this and consume the silicon mine resource non-renewable in a large number such as quartz and diatomite; Calcareous raw material generally also needs with the independent lime calcining of the high-grade fuel such as coke or anthracite and refined lime breast simultaneously, and production energy consumption and cost are greatly, large on resources and environment impact.
The various techniques that existing aluminous fly-ash produces aluminium hydroxide or aluminum oxide all produce a large amount of calcium silicate slags or white residue, and the extensive Appropriate application of a large amount of calcium silicate slags or white residue has become polytechnic huge bottleneck.
Summary of the invention
The object of this invention is to provide the method that a kind of flyash sintering hydrothermal method produces xonotlite and aluminum oxide, by flyash is first extracted silicon, then xonotlite is produced, co-production aluminium hydroxide or aluminum oxide, and zeolite, while making full use of flyash, reduce environmental pollution, and reduce the production cost of the products such as xonotlite.
The method that flyash sintering hydrothermal method of the present invention produces xonotlite and aluminum oxide mainly comprises the following steps:
1, chemical mineral processing: flyash is put into the dosing vessel that chemical mineral processing solvent is housed and prepare burden, chemical mineral processing solvent is containing Na
2o30 ~ 120g/L, containing SiO
2≤ 5g/L; Proportion scale is 3 ~ 9 by chemical mineral processing solvent and flyash weight ratio; Then chemical mineral processing process is carried out, temperature of reaction 70 ~ 120 DEG C, reaction times 30 ~ 600min; The chemical mineral processing slurries obtained carry out being continuously separated and washing through horizontal belt filter, obtain washing filter residue and rough sodium silicate solution; By washing filter residue again wash after make water weight content 30 ~ 45% flyash concentrate;
2, prepare charge pulp: by flyash concentrate and the sodium aluminate solution containing sodium carbonate or crystallize sodium carbonate, Wingdale, hard coal, mix containing sodium aluminosilicate of water slag and calcium aluminium white residue after be mixed with charge pulp: configuration proportion is by CaO and SiO main in charge pulp
2mol ratio be 1.95 ~ 2.05, secondary CaO and TiO
2mol ratio be 1, main CaO and secondary CaO sum is the whole CaO in charge pulp; Na
2o and K
2the total mole number of O is total alkali mole number, Al
2o
3and Fe
2o
3total mole number be total ferro-aluminum mole number, the ratio of total alkali mole number and total ferro-aluminum mole number is 0.85 ~ 1.1, and in charge pulp, the weight content of water is 35 ~ 45%, and in the solid part of charge pulp, the material of granularity>=300 μm accounts for all solids partial material≤5%; The described sodium aluminate solution containing sodium carbonate or crystallize sodium carbonate is prepare the carbon formed in aluminium hydroxide process to divide decomposition evaporation mother liquor; Described containing sodium aluminosilicate of water slag be carry out when preparing aluminium hydroxide that normal pressure or middle pressure stop that desilication reaction produces containing sodium aluminosilicate of water slag; Described calcium aluminium white residue prepares the calcium aluminium white residue that in aluminium hydroxide process, secondary desilication reaction produces;
3, sintering prepares grog: shurry pump charge pulp top hole pressure being reached 2.0 ~ 5.0MPa sprays into method feeding clinkersintering kiln through spray gun and sinters, sintering temperature is 1040 ~ 1350 DEG C, sintering time is 10 ~ 60min, be cooled to normal temperature sieving approach after having sintered to granularity≤15mm, obtain sintering powder as grog;
4, Clinker digestion and separating, washing: prepare Clinker digestion adjustment liquid, Al in Clinker digestion adjustment liquid
2o
3concentration is 45 ~ 70g/L, and the weight ratio of whole Clinker digestion adjustment liquid and grog is 3 ~ 6; While grog being sent into rod mill or ball mill, add the Clinker digestion adjustment liquid of clinker weight 0.6 ~ 2 times, carry out wet milling stripping; Remaining Clinker digestion adjustment liquid joins in rod mill or the supporting grading machine of ball mill; Controlling leaching temperature is 68 ~ 78 DEG C, and dissolution time is 10 ~ 30min; The solids content of the stripping slurries obtained after stripping is 100 ~ 300g/L; Stripping slurries, through sedimentation or filtering separation, obtain solid phase and liquid phase; Solid phase is carried out carrying out washing treatment, obtain water weight content 30 ~ 45% Dicalcium Phosphate (Feed Grade) washing material; Liquid phase is the Clinker digestion liquid of siliceous sodium aluminate, containing Al
2o
380 ~ 140g/L, containing SiO
23 ~ 7g/L;
5, the original slurry of xonotlite presoma is prepared: Dicalcium Phosphate (Feed Grade) washing material and sodium silicate solution are prepared burden, ratio of components is 0.85 ~ 1.05 by the mol ratio of Ca and Si, then be that the water of 3 ~ 20 times mixes and stirs with weight, obtain the original slurry of xonotlite presoma; The Na of described sodium silicate solution
2o concentration is 30 ~ 120g/L, SiO
2concentration is 15 ~ 60g/L;
6, Hydrothermal Synthesis prepares xonotlite presoma: by original for xonotlite presoma slurry steam jacket preheater or tubulation preheater indirect preheating to 80 ~ 120 DEG C, carry out hydrothermal synthesis reaction, reaction times 30 ~ 300min; As hydrothermal synthesis reaction temperature >105 DEG C, after having reacted, obtain solid phase and siliceous sodium hydroxide solution through flashed down, filtering separation washing; When hydrothermal synthesis reaction temperature≤105 DEG C, directly carry out filtering separation and obtain solid phase and siliceous sodium hydroxide solution; Xonotlite presoma is obtained by after solid phase washing;
7, Hydrothermal Synthesis prepares xonotlite filter cake: xonotlite presoma and water are mixed with form slurry, the weight ratio of water and xonotlite presoma is 5 ~ 15, again use steam jacket preheater or tubulation preheater preheats to 160 ~ 265 DEG C, carry out hydrothermal synthesis reaction, reaction times 60 ~ 600min, then after multistage flash evaporation recovery waste heat, drop to normal pressure, finally by press filtration obtain water weight content 6 ~ 32% xonotlite filter cake; The xonotlite filter cake obtained directly as xonotlite product, or is dried and is removed as xonotlite product after moisture, or add fiber and binding agent in xonotlite filter cake after, reshaping xonotlite goods are made in maintenance.
Above-mentioned in xonotlite filter cake, add fiber and binding agent after, reshaping the method that xonotlite goods are made in maintenance are: in xonotlite filter cake, add bamboo fibers, wood fibre or cotton fibre, add alkali resistant glass fibre again, then add binding agent, finally mix and obtain the shaping slurry of xonotlite; The add-on of bamboo fibers, wood fibre or cotton fibre is 1.5 ~ 8% of solid weight in xonotlite, and the add-on of alkali resistant glass fibre is 1.5 ~ 8% of solid weight in xonotlite; Binding agent is Dicalcium Phosphate (Feed Grade), cement and/or water glass, and add-on is 1.5 ~ 15%; Injected by shaping for xonotlite slurry in press die, by the density compression moulding of setting, the demoulding is xonotlite product molding blank; Xonotlite product molding blank is sent in the steam-cured tunnel furnace of mechanize and carries out steam curing
,obtain xonotlite goods.
In aforesaid method, Na in the rough sodium silicate solution that step 1 obtains
2o concentration is 30 ~ 120g/L, SiO
2concentration is 15 ~ 60g/L; Rough sodium silicate solution is carried out leaf filter refining, obtain the purified silicon acid sodium solution that solid seston is less than 15mg/L, then enter in step 5 and use as sodium silicate solution.
In aforesaid method, the filtrate of in step 4, solid phase being carried out carrying out washing treatment acquisition adjusts liquid as Clinker digestion.
In aforesaid method, the Na of xonotlite presoma
2o content≤3g/L.
In aforesaid method, the siliceous sodium hydroxide solution that step 6 obtains evaporates, and then adds sodium hydroxide and is deployed into chemical mineral processing solvent, return step 1 and use; In the Clinker digestion liquid that step 4 obtains, except the Clinker digestion liquid preparing aluminium hydroxide, remaining part synthesizes one or more zeolite products with above-mentioned purified silicon acid sodium solution after automatic leaf filter is refined, the solution that synthetic zeolite process produces evaporates as siliceous sodium hydroxide solution, then add sodium hydroxide and be deployed into chemical mineral processing solvent, return step 1 and use.
In aforesaid method, the main reaction formula of step 6 is:
2CaO·SiO
2+2NaOH+aq→2Ca(OH)
2+Na
2SiO
3+aq。
In aforesaid method, the main reaction formula of the hydrothermal synthesis reaction of step 7 is:
6Ca（OH）
2+6Na
2SiO
3+aq→6CaO·6SiO
2·H
2O+12NaOH+aq。
The technology of the present invention route is that comprehensive utilization flyash more paid attention to the extraction of aluminum oxide by the past, forwards the high efficiency extraction and utilization that give priority to element silicon to and coproduction aluminum oxide develops simultaneously; More pay attention to technology can large-scale industrialization promotion and application.Present method Aided design develops current advanced ore dressing, material, fine chemistry industry and nonferrous metallurgy and produces many latest notions and the technology such as the technique of the association areas such as aluminum oxide, equipment and information control, makes the through engineering approaches of present method more stable, more advanced.Present method efficiently solves the problem and defect that in prior art, consumption of limestone amount is large, energy-output ratio is large and the quantity of slag is large; Once not only produce xonotlite product but also produce aluminum oxide and zeolite product with raw limestone simultaneously; Both the element silicon in flyash had been reclaimed, reclaim again aluminium element wherein, large-scale industrial production can also be realized, meet society to having the synthetic xonotlite mineral of function or the demands of goods such as insulation, heat insulation, fire-retardant, body of wall, and the great demand to aluminium hydroxide and aluminum oxide; Comprehensive utilization flyash had both achieved substituted for silicon mineral wealth, achieved again and instead of bauxite resource, also a saving the resources such as soil, can also achieve economy of large scale and produce.
Accompanying drawing explanation
Fig. 1 is the method flow schematic diagram that flyash of the present invention sintering hydrothermal method produces xonotlite and aluminum oxide.
Embodiment
Flyash by weight percentage salic 32 ~ 52% in the embodiment of the present invention, silicon oxide-containing 28 ~ 60%.
When mixing with water after batching in step 5 in the embodiment of the present invention and stir, control stirring intensity and make the solid weight concentration difference of in mixture any 2 be not more than 5%.
In the embodiment of the present invention, sintering prepares grog is adopt bituminous coal to sinter.
Embodiment 1
1, chemical mineral processing: flyash is put into the dosing vessel that chemical mineral processing solvent is housed and prepare burden, chemical mineral processing solvent is containing Na
2o30g/L, containing SiO
2≤ 5g/L; Proportion scale is 3 by chemical mineral processing solvent and flyash weight ratio; Then chemical mineral processing process is carried out, temperature of reaction 70 DEG C, reaction times 600min; The chemical mineral processing slurries obtained carry out being continuously separated and washing through horizontal belt filter, obtain washing filter residue and rough sodium silicate solution; By washing filter residue again wash after make water weight content 30% flyash concentrate;
Na in the rough sodium silicate solution obtained
2o concentration is 30g/L, SiO
2concentration is 15g/L; Rough sodium silicate solution is carried out leaf filter refining, obtain the purified silicon acid sodium solution that solid seston is less than 15mg/L, then enter in step 5 and use as sodium silicate solution;
2, prepare charge pulp: by flyash concentrate and the sodium aluminate solution containing sodium carbonate or crystallize sodium carbonate, Wingdale, hard coal, mix containing sodium aluminosilicate of water slag and calcium aluminium white residue after be mixed with charge pulp: configuration proportion is by CaO and SiO main in charge pulp
2mol ratio be 1.95, secondary CaO and TiO
2mol ratio be 1, main CaO and secondary CaO sum is the whole CaO in charge pulp; Na
2o and K
2the total mole number of O is total alkali mole number, Al
2o
3and Fe
2o
3total mole number be total ferro-aluminum mole number, the ratio of total alkali mole number and total ferro-aluminum mole number is 0.85, and in charge pulp, the weight content of water is 35%, and in the solid part of charge pulp, the material of granularity>=300 μm accounts for all solids partial material≤5%; The described sodium aluminate solution containing sodium carbonate or crystallize sodium carbonate is prepare the carbon formed in aluminium hydroxide process to divide decomposition evaporation mother liquor; Described containing sodium aluminosilicate of water slag be carry out when preparing aluminium hydroxide that normal pressure or middle pressure stop that desilication reaction produces containing sodium aluminosilicate of water slag; Described calcium aluminium white residue prepares the calcium aluminium white residue that in aluminium hydroxide process, secondary desilication reaction produces;
3, sintering prepares grog: shurry pump charge pulp top hole pressure being reached 2.0MPa sprays into method feeding clinkersintering kiln through spray gun and sinters, sintering temperature is 1040 DEG C, sintering time is 60min, be cooled to normal temperature sieving approach after having sintered to granularity≤15mm, obtain sintering powder as grog;
4, Clinker digestion and separating, washing: prepare Clinker digestion adjustment liquid, Al in Clinker digestion adjustment liquid
2o
3concentration is 45g/L, and the weight ratio of whole Clinker digestion adjustment liquid and grog is 3; While grog being sent into rod mill or ball mill, add the Clinker digestion adjustment liquid of clinker weight 0.6 times, carry out wet milling stripping; Remaining Clinker digestion adjustment liquid joins in rod mill or the supporting grading machine of ball mill; Controlling leaching temperature is 68 DEG C, and dissolution time is 30min; The solids content of the stripping slurries obtained after stripping is 100g/L; Stripping slurries, through sedimentation or filtering separation, obtain solid phase and liquid phase; Solid phase is carried out carrying out washing treatment, obtain water weight content 30% Dicalcium Phosphate (Feed Grade) washing material; Liquid phase is the Clinker digestion liquid of siliceous sodium aluminate, containing Al
2o
380g/L, containing SiO
23g/L;
The filtrate that solid phase carries out carrying out washing treatment acquisition is adjusted liquid as Clinker digestion;
5, prepare the original slurry of xonotlite presoma: Dicalcium Phosphate (Feed Grade) washing material and sodium silicate solution are prepared burden, ratio of components is 0.85 by the mol ratio of Ca and Si, is then that the water of 3 times mixes and stirs with weight, obtains the original slurry of xonotlite presoma; The Na of described sodium silicate solution
2o concentration is 30g/L, SiO
2concentration is 15g/L;
6, Hydrothermal Synthesis prepares xonotlite presoma: by original for xonotlite presoma slurry steam jacket preheater or tubulation preheater indirect preheating to 80 DEG C, carry out hydrothermal synthesis reaction, reaction times 300min; As hydrothermal synthesis reaction temperature >105 DEG C, after having reacted, obtain solid phase and siliceous sodium hydroxide solution through flashed down, filtering separation washing; When hydrothermal synthesis reaction temperature≤105 DEG C, directly carry out filtering separation and obtain solid phase and siliceous sodium hydroxide solution; Xonotlite presoma is obtained by after solid phase washing; The Na of xonotlite presoma
2o content≤3g/L;
The siliceous sodium hydroxide solution obtained evaporates, and then adds sodium hydroxide and is deployed into chemical mineral processing solvent, return step 1 and use; In the Clinker digestion liquid that step 4 obtains, except the Clinker digestion liquid preparing aluminium hydroxide, remaining part synthesizes one or more zeolite products with above-mentioned purified silicon acid sodium solution after automatic leaf filter is refined, the solution that synthetic zeolite process produces evaporates as siliceous sodium hydroxide solution, then add sodium hydroxide and be deployed into chemical mineral processing solvent, return step 1 and use;
7, Hydrothermal Synthesis prepares xonotlite filter cake: xonotlite presoma and water are mixed with form slurry, the weight ratio of water and xonotlite presoma is 5, again use steam jacket preheater or tubulation preheater preheats to 160 DEG C, carry out hydrothermal synthesis reaction, reaction times 600min, then after multistage flash evaporation recovery waste heat, drop to normal pressure, finally by press filtration obtain water weight content 6% xonotlite filter cake; The xonotlite filter cake obtained is directly as xonotlite product.
Embodiment 2
Method is with embodiment 1, and difference is:
(1) chemical mineral processing solvent is containing Na
2o80g/L; Proportion scale is 6 by chemical mineral processing solvent and flyash weight ratio; Chemical mineral processing processing reaction temperature 90 DEG C, reaction times 200min; By washing filter residue again wash after make water weight content 40% flyash concentrate;
Na in the rough sodium silicate solution obtained
2o concentration is 80g/L, SiO
2concentration is 40g/L;
(2) configuration proportion of charge pulp presses main CaO and SiO in charge pulp
2mol ratio be 2.00; The ratio of total alkali mole number and total ferro-aluminum mole number is 0.95, and in charge pulp, the weight content of water is 40%;
(3) shurry pump charge pulp top hole pressure being reached 4.0MPa sprays into method feeding clinkersintering kiln through spray gun and sinters, and sintering temperature is 1220 DEG C, and sintering time is 30min;
(4) Al in Clinker digestion adjustment liquid
2o
3concentration is 60g/L, and the weight ratio of whole Clinker digestion adjustment liquid and grog is 5; While grog being sent into rod mill or ball mill, add the Clinker digestion adjustment liquid of clinker weight 1 times; Controlling leaching temperature is 73 DEG C, and dissolution time is 20min; The solids content of the stripping slurries obtained after stripping is 200g/L; Obtain water weight content 40% Dicalcium Phosphate (Feed Grade) washing material; Containing Al in the Clinker digestion liquid of siliceous sodium aluminate
2o
3110g/L, containing SiO
25g/L;
(5) Dicalcium Phosphate (Feed Grade) washing material and sodium silicate solution are prepared burden, ratio of components is 0.95 by the mol ratio of Ca and Si, is then that the water of 10 times mixes and stirs with weight; The Na of described sodium silicate solution
2o concentration is 80g/L, SiO
2concentration is 40g/L;
(6) by original for xonotlite presoma slurry steam jacket preheater or tubulation preheater indirect preheating to 100 DEG C, hydrothermal synthesis reaction time 100min;
(7) weight ratio of water and xonotlite presoma is 10, again uses steam jacket preheater or tubulation preheater preheats to 215 DEG C, hydrothermal synthesis reaction time 180min, the weight content finally obtaining water 18% xonotlite filter cake; As xonotlite product after the xonotlite filter cake oven dry removal moisture obtained.
Embodiment 3
Method is with embodiment 1, and difference is:
(1) chemical mineral processing solvent is containing Na
2o120g/L; Proportion scale is 9 by chemical mineral processing solvent and flyash weight ratio; Chemical mineral processing processing reaction temperature 120 DEG C, reaction times 30min; By washing filter residue again wash after make water weight content 45% flyash concentrate;
Na in the rough sodium silicate solution obtained
2o concentration is 120g/L, SiO
2concentration is 60g/L;
(2) configuration proportion of charge pulp presses main CaO and SiO in charge pulp
2mol ratio be 2.05; The ratio of total alkali mole number and total ferro-aluminum mole number is 1.1, and in charge pulp, the weight content of water is 45%;
(3) shurry pump charge pulp top hole pressure being reached 5.0MPa sprays into method feeding clinkersintering kiln through spray gun and sinters, and sintering temperature is 1350 DEG C, and sintering time is 10min;
(4) Al in Clinker digestion adjustment liquid
2o
3concentration is 70g/L, and the weight ratio of whole Clinker digestion adjustment liquid and grog is 6; While grog being sent into rod mill or ball mill, add the Clinker digestion adjustment liquid of clinker weight 2 times; Controlling leaching temperature is 78 DEG C, and dissolution time is 10min; The solids content of the stripping slurries obtained after stripping is 300g/L; Obtain water weight content 45% Dicalcium Phosphate (Feed Grade) washing material; Containing Al in the Clinker digestion liquid of siliceous sodium aluminate
2o
3140g/L, containing SiO
27g/L;
(5) Dicalcium Phosphate (Feed Grade) washing material and sodium silicate solution are prepared burden, ratio of components is 1.05 by the mol ratio of Ca and Si, is then that the water of 20 times mixes and stirs with weight; The Na of described sodium silicate solution
2o concentration is 120g/L, SiO
2concentration is 60g/L;
(6) by original for xonotlite presoma slurry steam jacket preheater or tubulation preheater indirect preheating to 120 DEG C, hydrothermal synthesis reaction time 30min;
(7) weight ratio of water and xonotlite presoma is 15, again uses steam jacket preheater or tubulation preheater preheats to 265 DEG C, hydrothermal synthesis reaction time 60min, the weight content finally obtaining water 32% xonotlite filter cake; In xonotlite filter cake, add bamboo fibers, wood fibre or cotton fibre, then add alkali resistant glass fibre, then add binding agent, finally mix and obtain the shaping slurry of xonotlite; The add-on of bamboo fibers, wood fibre or cotton fibre is 1.5 ~ 8% of solid weight in xonotlite, and the add-on of alkali resistant glass fibre is 1.5 ~ 8% of solid weight in xonotlite; Binding agent is Dicalcium Phosphate (Feed Grade), cement and/or water glass, and add-on is 1.5 ~ 15%; Injected by shaping for xonotlite slurry in press die, by the density compression moulding of setting, the demoulding is xonotlite product molding blank; Xonotlite product molding blank is sent in the steam-cured tunnel furnace of mechanize and carries out steam curing
,obtain xonotlite goods.
Claims (5)
1. flyash sintering hydrothermal method produces a method for xonotlite, it is characterized in that comprising the following steps:
(1) chemical mineral processing: flyash is put into the dosing vessel that chemical mineral processing solvent is housed and prepare burden, chemical mineral processing solvent is containing Na
2o30 ~ 120g/L, containing SiO
2≤ 5g/L; Proportion scale is 3 ~ 9 by chemical mineral processing solvent and flyash weight ratio; Then chemical mineral processing process is carried out, temperature of reaction 70 ~ 120 DEG C, reaction times 30 ~ 600min; The chemical mineral processing slurries obtained carry out being continuously separated and washing through horizontal belt filter, obtain washing filter residue and rough sodium silicate solution; By washing filter residue again wash after make water weight content 30 ~ 45% flyash concentrate;
(2) prepare charge pulp: by flyash concentrate and the sodium aluminate solution containing sodium carbonate or crystallize sodium carbonate, Wingdale, hard coal, mix containing sodium aluminosilicate of water slag and calcium aluminium white residue after be mixed with charge pulp: configuration proportion is by CaO and SiO main in charge pulp
2mol ratio be 1.95 ~ 2.05, secondary CaO and TiO
2mol ratio be 1, main CaO and secondary CaO sum is the whole CaO in charge pulp; Na
2o and K
2the total mole number of O is total alkali mole number, Al
2o
3and Fe
2o
3total mole number be total ferro-aluminum mole number, the ratio of total alkali mole number and total ferro-aluminum mole number is 0.85 ~ 1.1, and in charge pulp, the weight content of water is 35 ~ 45%, and in the solid part of charge pulp, the material of granularity>=300 μm accounts for all solids partial material≤5%; The described sodium aluminate solution containing sodium carbonate or crystallize sodium carbonate is prepare the carbon formed in aluminium hydroxide process to divide decomposition evaporation mother liquor; Described containing sodium aluminosilicate of water slag be carry out when preparing aluminium hydroxide that normal pressure or middle pressure stop that desilication reaction produces containing sodium aluminosilicate of water slag; Described calcium aluminium white residue prepares the calcium aluminium white residue that in aluminium hydroxide process, secondary desilication reaction produces;
(3) sintering prepares grog: shurry pump charge pulp top hole pressure being reached 2.0 ~ 5.0MPa sprays into method feeding clinkersintering kiln through spray gun and sinters, sintering temperature is 1040 ~ 1350 DEG C, sintering time is 10 ~ 60min, be cooled to normal temperature sieving approach after having sintered to granularity≤15mm, obtain sintering powder as grog;
(4) Clinker digestion and separating, washing: prepare Clinker digestion adjustment liquid, Al in Clinker digestion adjustment liquid
2o
3concentration is 45 ~ 70g/L, and the weight ratio of whole Clinker digestion adjustment liquid and grog is 3 ~ 6; While grog being sent into rod mill or ball mill, add the Clinker digestion adjustment liquid of clinker weight 0.6 ~ 2 times, carry out wet milling stripping; Remaining Clinker digestion adjustment liquid joins in rod mill or the supporting grading machine of ball mill; Controlling leaching temperature is 68 ~ 78 DEG C, and dissolution time is 10 ~ 30min; The solids content of the stripping slurries obtained after stripping is 100 ~ 300g/L; Stripping slurries, through sedimentation or filtering separation, obtain solid phase and liquid phase; Solid phase is carried out carrying out washing treatment, obtain water weight content 30 ~ 45% Dicalcium Phosphate (Feed Grade) washing material; Liquid phase is the Clinker digestion liquid of siliceous sodium aluminate, containing Al
2o
380 ~ 140g/L, containing SiO
23 ~ 7g/L;
(5) the original slurry of xonotlite presoma is prepared: Dicalcium Phosphate (Feed Grade) washing material and sodium silicate solution are prepared burden, ratio of components is 0.85 ~ 1.05 by the mol ratio of Ca and Si, then be that the water of 3 ~ 20 times mixes and stirs with weight, obtain the original slurry of xonotlite presoma; The Na of described sodium silicate solution
2o concentration is 30 ~ 120g/L, SiO
2concentration is 15 ~ 60g/L;
(6) Hydrothermal Synthesis prepares xonotlite presoma: by original for xonotlite presoma slurry steam jacket preheater or tubulation preheater indirect preheating to 80 ~ 120 DEG C, carry out hydrothermal synthesis reaction, reaction times 30 ~ 300min; As hydrothermal synthesis reaction temperature >105 DEG C, after having reacted, obtain solid phase and siliceous sodium hydroxide solution through flashed down, filtering separation washing; When hydrothermal synthesis reaction temperature≤105 DEG C, directly carry out filtering separation and obtain solid phase and siliceous sodium hydroxide solution; Xonotlite presoma is obtained by after solid phase washing;
(7) Hydrothermal Synthesis prepares xonotlite filter cake: xonotlite presoma and water are mixed with form slurry, the weight ratio of water and xonotlite presoma is 5 ~ 15, again use steam jacket preheater or tubulation preheater preheats to 160 ~ 265 DEG C, carry out hydrothermal synthesis reaction, reaction times 60 ~ 600min, then after multistage flash evaporation recovery waste heat, drop to normal pressure, finally by press filtration obtain water weight content 6 ~ 32% xonotlite filter cake; The xonotlite filter cake obtained directly as xonotlite product, or is dried and is removed as xonotlite product after moisture, or add fiber and binding agent in xonotlite filter cake after, reshaping xonotlite goods are made in maintenance.
2. a kind of flyash sintering hydrothermal method according to claim 1 produces the method for xonotlite, it is characterized in that described in xonotlite filter cake, add fiber and binding agent after, reshaping the method that xonotlite goods are made in maintenance are: in xonotlite filter cake, add bamboo fibers, wood fibre or cotton fibre, add alkali resistant glass fibre again, then add binding agent, finally mix and obtain the shaping slurry of xonotlite; The add-on of bamboo fibers, wood fibre or cotton fibre is 1.5 ~ 8% of solid weight in xonotlite, and the add-on of alkali resistant glass fibre is 1.5 ~ 8% of solid weight in xonotlite; Binding agent is Dicalcium Phosphate (Feed Grade), cement and/or water glass, and add-on is 1.5 ~ 15%; Injected by shaping for xonotlite slurry in press die, by the density compression moulding of setting, the demoulding is xonotlite product molding blank; Xonotlite product molding blank is sent in the steam-cured tunnel furnace of mechanize and carries out steam curing
,obtain xonotlite goods.
3. a kind of flyash sintering hydrothermal method according to claim 1 produces the method for xonotlite, it is characterized in that Na in the rough sodium silicate solution that step (1) obtains
2o concentration is 30 ~ 120g/L, SiO
2concentration is 15 ~ 60g/L; Rough sodium silicate solution is carried out leaf filter refining, obtain the purified silicon acid sodium solution that solid seston is less than 15mg/L, then enter in step (5) and use as sodium silicate solution.
4. a kind of flyash sintering hydrothermal method according to claim 1 produces the method for xonotlite, it is characterized in that the filtrate of in step (4), solid phase being carried out carrying out washing treatment acquisition adjusts liquid as Clinker digestion.
5. a kind of flyash sintering hydrothermal method according to claim 1 produces the method for xonotlite, it is characterized in that the siliceous sodium hydroxide solution that step (6) obtains evaporates, then add sodium hydroxide and be deployed into chemical mineral processing solvent, return step (1) and use; In the Clinker digestion liquid that step (4) obtains, except the Clinker digestion liquid preparing aluminium hydroxide, remaining part synthesizes one or more zeolite products with above-mentioned purified silicon acid sodium solution after automatic leaf filter is refined, the solution that synthetic zeolite process produces evaporates as siliceous sodium hydroxide solution, then add sodium hydroxide and be deployed into chemical mineral processing solvent, return step (1) and use.
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