CN104556171B - A kind of flyash sintering hydrothermal method produces the method for tobermorite and aluminum oxide - Google Patents

A kind of flyash sintering hydrothermal method produces the method for tobermorite and aluminum oxide Download PDF

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CN104556171B
CN104556171B CN201410846092.5A CN201410846092A CN104556171B CN 104556171 B CN104556171 B CN 104556171B CN 201410846092 A CN201410846092 A CN 201410846092A CN 104556171 B CN104556171 B CN 104556171B
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tobermorite
sodium
flyash
presoma
washing
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CN104556171A (en
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李光柱
崔德成
涂赣峰
于海燕
潘晓林
毕诗文
黎娜
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Northeast University Design and Research Institute Co Ltd
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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
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Abstract

Flyash sintering hydrothermal method produces a method for tobermorite and aluminum oxide, comprises the following steps: (1) chemical mineral processing; (2) charge pulp is prepared; (3) sintering prepares grog; (4) Clinker digestion and separating, washing; (5) the original slurry of tobermorite presoma is prepared; (6) Hydrothermal Synthesis prepares tobermorite presoma; (7) Hydrothermal Synthesis prepares tobermorite filter cake.Present method comprehensive utilization flyash, both tobermorite can be produced, aluminum oxide can also be produced, both substituted for silicon mineral wealth had been achieved, achieve again and instead of bauxite resource, also a saving the resources such as soil, economy of large scale can also be achieved produce, for large-scale comprehensive utilizes the silicon-dioxide in flyash and alumina composition, realizes the recycling establish a firm foundation of solid waste.

Description

A kind of flyash sintering hydrothermal method produces the method for tobermorite and aluminum oxide
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 tobermorite 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.
Traditional technology produces tobermorite 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 is except carbide slag simultaneously, and generally also need the independent lime calcinings of high-grade fuel such as Wingdale coke or anthracite and refined lime breast, 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 tobermorite and aluminum oxide, by flyash is first extracted silicon, then tobermorite is produced, co-production aluminium hydroxide or aluminum oxide, and zeolite, while making full use of aluminous fly-ash, reduce environmental pollution, and reduce the production cost of the products such as tobermorite.
The method that a kind of flyash sintering hydrothermal method of the present invention produces tobermorite 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 tobermorite presoma is prepared: Dicalcium Phosphate (Feed Grade) washing material and sodium silicate solution are prepared burden, ratio of components is 0.65 ~ 0.84 by the mol ratio of Ca and Si, then be that its water of 3 ~ 20 times mixes and stirs with weight, obtain the original slurry of tobermorite presoma; The Na of described sodium silicate solution 2o concentration is 30 ~ 120g/L, SiO 2concentration is 15 ~ 60g/L;
By original for tobermorite presoma slurry steam jacket preheater or tubulation preheater preheats to 140 ~ 180 DEG C, carry out hydrothermal synthesis reaction, reaction times 60 ~ 600min, then after multistage flash evaporation recovery waste heat, normal pressure is dropped to, the weight content obtaining water finally by separating, washing and press filtration 6 ~ 32% tobermorite filter cake, the filtrate of acquisition is siliceous sodium hydroxide solution; Or original for tobermorite presoma slurry is entered step 6;
6, Hydrothermal Synthesis prepares tobermorite presoma: by original for tobermorite 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; Tobermorite presoma is obtained by after solid phase washing;
7, Hydrothermal Synthesis prepares tobermorite filter cake: tobermorite presoma and water are mixed with form slurry, the weight ratio of water and tobermorite presoma is 5 ~ 15, again use steam jacket preheater or tubulation preheater preheats to 140 ~ 180 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% tobermorite filter cake; The tobermorite filter cake obtained directly as tobermorite product, or is dried and is removed as tobermorite product after moisture, or add fiber and binding agent in tobermorite filter cake after, reshaping tobermorite goods are made in maintenance.
Above-mentioned in tobermorite filter cake, add fiber and binding agent after, reshaping the method that tobermorite goods are made in maintenance are: in tobermorite 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 tobermorite; The add-on of bamboo fibers, wood fibre or cotton fibre is 1.5 ~ 8% of solid weight in tobermorite, and the add-on of alkali resistant glass fibre is 1.5 ~ 8% of solid weight in tobermorite; Binding agent is Dicalcium Phosphate (Feed Grade), cement and/or water glass, and add-on is 1.5 ~ 15%; Injected by shaping for tobermorite slurry in press die, by the density compression moulding of setting, the demoulding is tobermorite product molding blank; Tobermorite product molding blank is sent in the steam-cured tunnel furnace of mechanize and carries out steam curing ,obtain tobermorite goods.
Above-mentioned flyash by weight percentage salic 32 ~ 52%, silicon oxide-containing 28 ~ 60%.
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 tobermorite presoma 2o content≤3g/L.
In aforesaid method, the Clinker digestion liquid that step 4 obtains stops desilication reaction through normal pressure or middle pressure, obtain primary purification sodium aluminate solution, part primary purification sodium aluminate solution adds milk of lime again and carries out secondary desilication reaction and automatic filtering machine is refined, and obtains secondary refining sodium aluminate solution; Sent by primary purification sodium aluminate solution kind of a point decomposer to decompose and produce aluminium hydroxide, sent by secondary refining sodium aluminate solution carbon to decompose and produce aluminium hydroxide; Carbon evaporation mother liquor returns step 2 as the sodium aluminate solution containing sodium carbonate and prepares charge pulp; Stoving oven is sent to produce aluminum oxide after aluminium hydroxide washs after filtration; The calcium aluminium white residue that secondary desilication reaction generates returns step 2 and prepares charge pulp.
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, maintenance refers to that curing temperature is 45 ~ 110 DEG C, and curing time is 12 ~ 48h.
In aforesaid method, step 6 and 7 main reaction formula be:
2CaO·SiO 2+2NaOH+aq→2Ca(OH) 2+Na 2SiO 3+aq。
5Ca（OH） 2+6Na 2SiO 3+aq→Ca 5Si 6O 16(OH) 2·4H 2O↓+12NaOH+aq。
Technological line of the present invention 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; That more payes attention to technology can large-scale industrialization promotion and application; The 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; Efficiently solve 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 tobermorite product but also produce aluminum oxide and zeolite product with raw limestone simultaneously; Both reclaimed the element silicon in aluminous fly-ash, and reclaimed again aluminium element, and can also realize large-scale industrial production, be a kind of green production process without solid waste simultaneously.
Tobermorite (tobermorite), also known as tobermorite, tobermorite, is the one of hydrated calcium silicate, it consists of (Ca 5si 6o 16(OH) 24H 2o); Tobermorite nature exists few, generally by synthetic, is incubated at can be used for 650 DEG C, heat insulation, fire-retardant, body of wall functional materials and more for research in municipal sewage treatment, red tide of sea process adsorption functional material, and the market demand potential is huge; The market requirement of aluminium hydroxide and aluminum oxide is huge; Present method comprehensive utilization flyash had both achieved substituted for silicon mineral wealth, achieve again and instead of bauxite resource, also a saving the resources such as soil, economy of large scale can also be achieved produce, for large-scale comprehensive utilizes the silicon-dioxide in flyash and alumina composition, realizes the recycling establish a firm foundation of solid waste.
Accompanying drawing explanation
Fig. 1 is the method flow schematic diagram of the embodiment of the present invention 1;
Fig. 2 is the method flow schematic diagram of the embodiment of the present invention 4.
Embodiment
Flyash by weight percentage salic 32 ~ 52% in the embodiment of the present invention, silicon oxide-containing 28 ~ 60%.
The bamboo fibers adopted in the embodiment of the present invention, wood fibre, cotton fibre and alkali resistant glass fibre are commercial products.
The Dicalcium Phosphate (Feed Grade) adopted in the embodiment of the present invention, cement and water glass are commercial products.
Length≤the 40mm of the bamboo fibers adopted in the embodiment of the present invention, wood fibre, cotton fibre and alkali resistant glass fibre.
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;
The Clinker digestion liquid obtained stops desilication reaction through normal pressure or middle pressure, obtains primary purification sodium aluminate solution, and part primary purification sodium aluminate solution adds milk of lime again and carries out secondary desilication reaction and automatic filtering machine is refined, and obtains secondary refining sodium aluminate solution; Sent by primary purification sodium aluminate solution kind of a point decomposer to decompose and produce aluminium hydroxide, sent by secondary refining sodium aluminate solution carbon to decompose and produce aluminium hydroxide; Carbon evaporation mother liquor returns step 2 as the sodium aluminate solution containing sodium carbonate and prepares charge pulp; Stoving oven is sent to produce aluminum oxide after aluminium hydroxide washs after filtration; The calcium aluminium white residue that secondary desilication reaction generates returns step 2 and prepares charge pulp;
5, prepare the original slurry of tobermorite presoma: Dicalcium Phosphate (Feed Grade) washing material and sodium silicate solution are prepared burden, ratio of components is 0.65 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 tobermorite presoma; The Na of described sodium silicate solution 2o concentration is 30g/L, SiO 2concentration is 15g/L;
6, Hydrothermal Synthesis prepares tobermorite presoma: by original for tobermorite 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; Tobermorite presoma is obtained by after solid phase washing; The Na of tobermorite 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 tobermorite filter cake: tobermorite presoma and water are mixed with form slurry, the weight ratio of water and tobermorite presoma is 5, again use steam jacket preheater or tubulation preheater preheats to 140 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% tobermorite filter cake; The tobermorite filter cake obtained is directly as tobermorite 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; Will
(2) charge pulp configuration proportion 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 3.0MPa sprays into method feeding clinkersintering kiln through spray gun and sinters, and sintering temperature is 1210 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 4; 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; Solid phase washing obtain water weight content 40% Dicalcium Phosphate (Feed Grade) washing material; Liquid phase is the Clinker digestion liquid of siliceous sodium aluminate, containing Al 2o 3110g/L, containing SiO 25g/L;
(5) ratio of components is 0.75 by the mol ratio of Ca and Si, is then that the water of 10 times mixes and stirs with weight, obtains the original slurry of tobermorite presoma; The Na of described sodium silicate solution 2o concentration is 80g/L, SiO 2concentration is 40g/L;
(6) by original for tobermorite presoma slurry steam jacket preheater or tubulation preheater indirect preheating to 100 DEG C, hydrothermal synthesis reaction is carried out, reaction times 100min;
(7) tobermorite presoma and water are mixed with form slurry, the weight ratio of water and tobermorite presoma is 10, again use steam jacket preheater or tubulation preheater preheats to 160 DEG C, carry out hydrothermal synthesis reaction, reaction times 200min, then after multistage flash evaporation recovery waste heat, drop to normal pressure, finally by press filtration obtain water weight content 18% tobermorite filter cake; As tobermorite product after the tobermorite 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 20g/L, SiO 2concentration is 60g/L; Will
(2) charge pulp configuration proportion 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; Solid phase washing obtain water weight content 45% Dicalcium Phosphate (Feed Grade) washing material; Liquid phase is the Clinker digestion liquid of siliceous sodium aluminate, containing Al 2o 3140g/L, containing SiO 27g/L;
(5) ratio of components is 0.84 by the mol ratio of Ca and Si, is then that the water of 20 times mixes and stirs with weight, obtains the original slurry of tobermorite presoma; The Na of described sodium silicate solution 2o concentration is 120g/L, SiO 2concentration is 60g/L;
(6) by original for tobermorite presoma slurry steam jacket preheater or tubulation preheater indirect preheating to 120 DEG C, hydrothermal synthesis reaction is carried out, reaction times 30min;
(7) tobermorite presoma and water are mixed with form slurry, the weight ratio of water and tobermorite presoma is 15, again use steam jacket preheater or tubulation preheater preheats to 180 DEG C, carry out hydrothermal synthesis reaction, reaction times 60min, then after multistage flash evaporation recovery waste heat, drop to normal pressure, finally by press filtration obtain water weight content 32% tobermorite filter cake; In tobermorite 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 tobermorite; The add-on of bamboo fibers, wood fibre or cotton fibre is 1.5 ~ 8% of solid weight in tobermorite, and the add-on of alkali resistant glass fibre is 1.5 ~ 8% of solid weight in tobermorite; Binding agent is Dicalcium Phosphate (Feed Grade), cement and/or water glass, and add-on is 1.5 ~ 15%; Injected by shaping for tobermorite slurry in press die, by the density compression moulding of setting, the demoulding is tobermorite product molding blank; Tobermorite product molding blank is sent in the steam-cured tunnel furnace of mechanize and carries out steam curing ,obtain tobermorite goods.
Embodiment 4
Embodiment of the method 1, difference is:
By original for tobermorite presoma slurry steam jacket preheater or tubulation preheater preheats to 140 DEG C, carry out hydrothermal synthesis reaction, reaction times 600min, then after multistage flash evaporation recovery waste heat, drop to normal pressure, the weight content obtaining water finally by separating, washing and press filtration 6% tobermorite filter cake.
Embodiment 5
Embodiment of the method 2, difference is:
By original for tobermorite presoma slurry steam jacket preheater or tubulation preheater preheats to 160 DEG C, carry out hydrothermal synthesis reaction, reaction times 200min, then after multistage flash evaporation recovery waste heat, drop to normal pressure, the weight content obtaining water finally by separating, washing and press filtration 18% tobermorite filter cake.
Embodiment 6
Embodiment of the method 3, difference is:
By original for tobermorite presoma slurry steam jacket preheater or tubulation preheater preheats to 180 DEG C, carry out hydrothermal synthesis reaction, reaction times 60min, then after multistage flash evaporation recovery waste heat, drop to normal pressure, the weight content obtaining water finally by separating, washing and press filtration 32% tobermorite filter cake.

Claims (6)

1. flyash sintering hydrothermal method produces a method for tobermorite and aluminum oxide, 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;
The Clinker digestion liquid obtained stops desilication reaction through normal pressure or middle pressure, obtains primary purification sodium aluminate solution, and part primary purification sodium aluminate solution adds milk of lime again and carries out secondary desilication reaction and automatic filtering machine is refined, and obtains secondary refining sodium aluminate solution; Sent by primary purification sodium aluminate solution kind of a point decomposer to decompose and produce aluminium hydroxide, sent by secondary refining sodium aluminate solution carbon to decompose and produce aluminium hydroxide; Carbon evaporation mother liquor returns step (2) as the sodium aluminate solution containing sodium carbonate and prepares charge pulp; Stoving oven is sent to produce aluminum oxide after aluminium hydroxide washs after filtration; The calcium aluminium white residue that secondary desilication reaction generates returns step (2) and prepares charge pulp;
(5) the original slurry of tobermorite presoma is prepared: Dicalcium Phosphate (Feed Grade) washing material and sodium silicate solution are prepared burden, ratio of components is 0.65 ~ 0.84 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 tobermorite presoma; The Na of described sodium silicate solution 2o concentration is 30 ~ 120g/L, SiO 2concentration is 15 ~ 60g/L; By original for tobermorite presoma slurry steam jacket preheater or tubulation preheater preheats to 140 ~ 180 DEG C, carry out hydrothermal synthesis reaction, reaction times 60 ~ 600min, then after multistage flash evaporation recovery waste heat, normal pressure is dropped to, the weight content obtaining water finally by separating, washing and press filtration 6 ~ 32% tobermorite filter cake, the filtrate of acquisition is siliceous sodium hydroxide solution; Or original for tobermorite presoma slurry is entered step (6);
(6) Hydrothermal Synthesis prepares tobermorite presoma: by original for tobermorite 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; Tobermorite presoma is obtained by after solid phase washing;
(7) Hydrothermal Synthesis prepares tobermorite filter cake: tobermorite presoma and water are mixed with form slurry, the weight ratio of water and tobermorite presoma is 5 ~ 15, again use steam jacket preheater or tubulation preheater preheats to 140 ~ 180 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% tobermorite filter cake; The tobermorite filter cake obtained directly as tobermorite product, or is dried and is removed as tobermorite product after moisture, or add fiber and binding agent in tobermorite filter cake after, reshaping tobermorite goods are made in maintenance.
2. a kind of flyash sintering hydrothermal method according to claim 1 produces the method for tobermorite and aluminum oxide, it is characterized in that described in tobermorite filter cake, add fiber and binding agent after, reshaping the method that tobermorite goods are made in maintenance are: in tobermorite 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 tobermorite; The add-on of bamboo fibers, wood fibre or cotton fibre is 1.5 ~ 8% of solid weight in tobermorite, and the add-on of alkali resistant glass fibre is 1.5 ~ 8% of solid weight in tobermorite; Binding agent is Dicalcium Phosphate (Feed Grade), cement and/or water glass, and add-on is 1.5 ~ 15%; Injected by shaping for tobermorite slurry in press die, by the density compression moulding of setting, the demoulding is tobermorite product molding blank; Tobermorite product molding blank is sent in the steam-cured tunnel furnace of mechanize and carries out steam curing ,obtain tobermorite goods.
3. a kind of flyash sintering hydrothermal method according to claim 1 produces the method for tobermorite and aluminum oxide, 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 tobermorite and aluminum oxide, it is characterized in that the Na of described tobermorite presoma 2o content≤3g/L.
5. a kind of flyash sintering hydrothermal method according to claim 1 produces the method for tobermorite and aluminum oxide, 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.
6. a kind of flyash sintering hydrothermal method according to claim 1 produces the method for tobermorite and aluminum oxide, 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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FR2714913B1 (en) * 1994-01-13 1996-03-01 Pechiney Aluminium Manufacture of aluminum salts with whiteness controlled by a coloring additive.
CN101462752A (en) * 2008-12-29 2009-06-24 中国铝业股份有限公司 Thickening method after high pressure digestion of aluminum oxide production using mixed-combination process
EP2123604A1 (en) * 2007-02-13 2009-11-25 Sakai Chemical Industry Co., Ltd., Flaky particle and cosmetic
CN103708478A (en) * 2013-12-30 2014-04-09 大唐国际发电股份有限公司高铝煤炭资源开发利用研发中心 Preparation method of tobermorite

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2714913B1 (en) * 1994-01-13 1996-03-01 Pechiney Aluminium Manufacture of aluminum salts with whiteness controlled by a coloring additive.
EP2123604A1 (en) * 2007-02-13 2009-11-25 Sakai Chemical Industry Co., Ltd., Flaky particle and cosmetic
CN101462752A (en) * 2008-12-29 2009-06-24 中国铝业股份有限公司 Thickening method after high pressure digestion of aluminum oxide production using mixed-combination process
CN103708478A (en) * 2013-12-30 2014-04-09 大唐国际发电股份有限公司高铝煤炭资源开发利用研发中心 Preparation method of tobermorite

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