CN104477926A - Method for producing xonotlite and aluminum oxide by using coal ash alkaline leaching sintering hydrothermal method - Google Patents
Method for producing xonotlite and aluminum oxide by using coal ash alkaline leaching sintering hydrothermal method Download PDFInfo
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- UGGQKDBXXFIWJD-UHFFFAOYSA-N calcium;dihydroxy(oxo)silane;hydrate Chemical compound O.[Ca].O[Si](O)=O UGGQKDBXXFIWJD-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 238000002386 leaching Methods 0.000 title claims abstract description 53
- 238000001027 hydrothermal synthesis Methods 0.000 title claims abstract description 40
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000005245 sintering Methods 0.000 title claims abstract description 33
- 239000010883 coal ash Substances 0.000 title claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 title abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 60
- 238000005406 washing Methods 0.000 claims abstract description 54
- 239000002002 slurry Substances 0.000 claims abstract description 51
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 36
- 239000011707 mineral Substances 0.000 claims abstract description 36
- 239000000126 substance Substances 0.000 claims abstract description 34
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 28
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000010703 silicon Substances 0.000 claims abstract description 23
- 239000002893 slag Substances 0.000 claims abstract description 21
- 239000012065 filter cake Substances 0.000 claims abstract description 20
- 238000000926 separation method Methods 0.000 claims abstract description 16
- 239000000243 solution Substances 0.000 claims description 76
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 72
- 239000003513 alkali Substances 0.000 claims description 71
- 239000011734 sodium Substances 0.000 claims description 69
- 239000007788 liquid Substances 0.000 claims description 60
- 239000010881 fly ash Substances 0.000 claims description 45
- 230000029087 digestion Effects 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- 238000012545 processing Methods 0.000 claims description 34
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 239000000463 material Substances 0.000 claims description 27
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 27
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 27
- 239000007787 solid Substances 0.000 claims description 24
- 239000004115 Sodium Silicate Substances 0.000 claims description 22
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 22
- 229910052782 aluminium Inorganic materials 0.000 claims description 21
- 239000000047 product Substances 0.000 claims description 21
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 20
- 239000000835 fiber Substances 0.000 claims description 20
- 230000035484 reaction time Effects 0.000 claims description 20
- 239000007790 solid phase Substances 0.000 claims description 20
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 18
- 238000000354 decomposition reaction Methods 0.000 claims description 18
- 238000001704 evaporation Methods 0.000 claims description 18
- 230000008020 evaporation Effects 0.000 claims description 18
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 14
- 239000012141 concentrate Substances 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 14
- 235000019739 Dicalciumphosphate Nutrition 0.000 claims description 12
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 12
- 239000001506 calcium phosphate Substances 0.000 claims description 12
- NEFBYIFKOOEVPA-UHFFFAOYSA-K dicalcium phosphate Chemical compound [Ca+2].[Ca+2].[O-]P([O-])([O-])=O NEFBYIFKOOEVPA-UHFFFAOYSA-K 0.000 claims description 12
- 229940038472 dicalcium phosphate Drugs 0.000 claims description 12
- 229910000390 dicalcium phosphate Inorganic materials 0.000 claims description 12
- 238000007865 diluting Methods 0.000 claims description 12
- 229910052708 sodium Inorganic materials 0.000 claims description 12
- 238000010790 dilution Methods 0.000 claims description 11
- 239000012895 dilution Substances 0.000 claims description 11
- 239000011230 binding agent Substances 0.000 claims description 10
- 239000003245 coal Substances 0.000 claims description 10
- 239000007921 spray Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 8
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 8
- 241001330002 Bambuseae Species 0.000 claims description 8
- 229920000742 Cotton Polymers 0.000 claims description 8
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 229920002522 Wood fibre Polymers 0.000 claims description 8
- 229910021536 Zeolite Inorganic materials 0.000 claims description 8
- 239000011425 bamboo Substances 0.000 claims description 8
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 8
- 239000003365 glass fiber Substances 0.000 claims description 8
- 239000007791 liquid phase Substances 0.000 claims description 8
- 238000011084 recovery Methods 0.000 claims description 8
- 239000002918 waste heat Substances 0.000 claims description 8
- 239000010457 zeolite Substances 0.000 claims description 8
- 238000000605 extraction Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000000465 moulding Methods 0.000 claims description 6
- 239000005432 seston Substances 0.000 claims description 6
- 238000007493 shaping process Methods 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 239000004568 cement Substances 0.000 claims description 5
- 238000004090 dissolution Methods 0.000 claims description 5
- 235000019353 potassium silicate Nutrition 0.000 claims description 5
- 238000013459 approach Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000012423 maintenance Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 229910010413 TiO 2 Chemical group 0.000 claims description 3
- 238000000748 compression moulding Methods 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 238000007670 refining Methods 0.000 claims description 3
- 238000004062 sedimentation Methods 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 3
- 238000001238 wet grinding Methods 0.000 claims description 3
- 239000002994 raw material Substances 0.000 abstract description 8
- 235000019738 Limestone Nutrition 0.000 abstract description 3
- 239000006028 limestone Substances 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 239000002689 soil Substances 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract 2
- 235000010755 mineral Nutrition 0.000 description 26
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 11
- 229910001570 bauxite Inorganic materials 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 239000004411 aluminium Substances 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000011575 calcium Substances 0.000 description 4
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 235000017550 sodium carbonate Nutrition 0.000 description 3
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- 239000006004 Quartz sand Substances 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- 239000000378 calcium silicate Substances 0.000 description 2
- 229910052918 calcium silicate Inorganic materials 0.000 description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 description 1
- 239000003830 anthracite Substances 0.000 description 1
- 239000002802 bituminous coal Substances 0.000 description 1
- 210000000481 breast Anatomy 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000002817 coal dust Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001648 diaspore Inorganic materials 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000009856 non-ferrous metallurgy Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- 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
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
Landscapes
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention discloses a method for producing xonotlite and aluminum oxide by using a coal ash alkaline leaching sintering hydrothermal method. The method comprises the following steps: (1) performing chemical ore separation; (2) producing aluminum oxide through alkaline leaching; (3) preparing raw material slurry; (4) sintering to prepare clinker; (5) dissolving, separating and washing the clinker; (6) preparing xonotlite precursor raw material slurry; (7) performing hydro-thermal synthesis to prepare a xonotlite precursor; (8) performing hydro-thermal synthesis to prepare xonotlite filter cakes. By adopting the method, the problems and the defects that in the prior art a great deal of limestone is consumed, the energy consumption is large and a great deal of slag is generated, are effectively solved, coal ash is comprehensively utilized, both xonotlite and aluminum oxide can be produced, a silicon mineral resource is saved, a monohydrallite resource is replaced, sources such as soil are also saved, and large-scale economic production is achieved.
Description
Technical field
The present invention relates to a kind of method of comprehensive utilization of flyash, particularly a kind of coal ash alkali leaching 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.
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 coal ash alkali leaching sintering hydrothermal method produces xonotlite and aluminum oxide, by aluminous fly-ash is first extracted silicon, then aluminum oxide is produced in alkali leaching, prepare xonotlite again, while making full use of aluminous fly-ash, reduce environmental pollution, and reduce the production cost of the products such as xonotlite.
The method that coal ash alkali leaching sintering hydrothermal method of the present invention produces xonotlite and aluminum oxide 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
2o 30 ~ 120g/L, containing SiO
2≤ 5g/L; Proportion scale is 3 ~ 9 by chemical mineral processing solvent and flyash weight ratio; Then through chemical mineral processing process, temperature of reaction 70 ~ 120 DEG C, reaction times 30 ~ 600 min; 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, aluminum oxide is produced in alkali leaching: leached by flyash concentrate sodium aluminate solution, the middle Na of described sodium aluminate solution
2o
kconcentration is 180 ~ 245g/L, Na
2o+K
2o and Al
2o
3mol ratio be 2.5 ~ 3.2, the blending ratio of flyash concentrate and sodium aluminate solution is by Na in whole material
2o+K
2o and Al
2o
3mol ratio be 1.53 ~ 1.6, extraction temperature is 255 ~ 280 DEG C, and the reaction times is 30 ~ 120min; After multistage flash evaporation recovery waste heat, drop to atmospheric pressure state after leaching completes, obtain alkali soaking paste liquid; In alkali soaking paste liquid, add diluting soln obtain dilution alkali leaching dreg slurry, the add-on of diluting soln is by Na in dilution alkali leaching dreg slurry
2o
kconcentration is that 130 ~ 165g/L controls; Then dilution alkali leaching dreg slurry is carried out atmospheric silicon removing reaction, obtain atmospheric silicon removing slurries; Carry out repeatedly backflush with horizontal rubber belt formula filter to be separated, obtain separation solution, alkali leaching slag washings and coal ash alkali leaching slag washing material; Separation solution is refined through automatic leaf filter, obtains the wrought aluminum acid sodium solution that solid seston is less than 15mg/L; Wrought aluminum acid sodium solution adopts adding aluminum hydroxide crystal seed gradient cooling decomposition for producing sand-like aluminium hydroxide and aluminum oxide, and the decomposition nut liquid produced in this process carries out evaporation process, obtains Na
2o
kconcentration is the sodium aluminate solution of 180 ~ 245 g/L, then recycles; Na in alkali leaching slag washings
2o
kconcentration is 50 ~ 70g/L;
3, charge pulp is prepared: be mixed with charge pulp after coal ash alkali being soaked the mixing of slag washing material, Wingdale and hard coal: 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%; Add industrial sodium carbonate when total alkali mole number is not enough to regulate;
4, 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 ~ 60 min, be cooled to normal temperature sieving approach after having sintered to granularity≤15 mm, obtain sintering powder as grog;
5, 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; Using the diluting soln of alkali leaching slag washings in step 4 in the Clinker digestion liquid of siliceous sodium aluminate or step 2;
6, 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 its 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;
7, 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;
8, 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, when producing sandy aluminium hydroxide and aluminum oxide in step 2, the decomposition nut liquid of generation carries out evaporation process, controls the Na of decomposition nut liquid
2o
kconcentration is 180 ~ 245 g/L, then recycles.
In aforesaid method, make chemical mineral processing solvent after the siliceous sodium hydroxide solution that step 7 obtains adds sodium hydroxide, return step 1 and use.
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 6 and use as sodium silicate solution.
In aforesaid method, the filtrate of in step 5, 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 7 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.
Above-mentioned flyash by weight percentage salic 32 ~ 52%, silicon oxide-containing 28 ~ 60%.
In aforesaid method, the main reaction formula of step 7 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 8 is:
6Ca（OH）
2+ 6Na
2SiO
3+ aq → 6CaO·6SiO
2·H
2O+ 12NaOＨaq。
In aforesaid method, not as the part of diluting soln in the Clinker digestion liquid of the siliceous sodium aluminate of step 5 acquisition, for the preparation of zeolite product.
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.The present invention 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, can also large-scale industrial production being realized, meeting society to having the synthetic xonotlite mineral of function such as insulation, heat insulation, fire-retardant, body of wall or the demand of goods 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 coal ash alkali of the present invention leaching sintering hydrothermal method produces xonotlite and aluminum oxide.
Embodiment
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.
The flyash adopted in the embodiment of the present invention be coal dust after pulverized coal firing boiler high-temp combustion, from flue gas receive catch the grey powder mass got off.
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
2o 30g/L, containing SiO
2≤ 5g/L; Proportion scale is 3 by chemical mineral processing solvent and flyash weight ratio; Then through chemical mineral processing process, temperature of reaction 70 DEG C, reaction times 600 min; 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 6 and use as sodium silicate solution;
2, aluminum oxide is produced in alkali leaching: leached by flyash concentrate sodium aluminate solution, the middle Na of described sodium aluminate solution
2o
kconcentration is 180g/L, Na
2o+K
2o and Al
2o
3mol ratio be 2.5, the blending ratio of flyash concentrate and sodium aluminate solution is by Na in whole material
2o+K
2o and Al
2o
3mol ratio be 1.53, extraction temperature is 255 DEG C, and the reaction times is 120min; After multistage flash evaporation recovery waste heat, drop to atmospheric pressure state after leaching completes, obtain alkali soaking paste liquid; In alkali soaking paste liquid, add diluting soln obtain dilution alkali leaching dreg slurry, the add-on of diluting soln is by Na in dilution alkali leaching dreg slurry
2o
kconcentration is that 130g/L controls; Then dilution alkali leaching dreg slurry is carried out atmospheric silicon removing reaction, obtain atmospheric silicon removing slurries; Carry out repeatedly backflush with horizontal rubber belt formula filter to be separated, obtain separation solution, alkali leaching slag washings and coal ash alkali leaching slag washing material; Separation solution is refined through automatic leaf filter, obtains the wrought aluminum acid sodium solution that solid seston is less than 15mg/L; Wrought aluminum acid sodium solution adopts adding aluminum hydroxide crystal seed gradient cooling decomposition for producing sand-like aluminium hydroxide and aluminum oxide, and the decomposition nut liquid produced in this process carries out evaporation process, obtains Na
2o
kconcentration is the sodium aluminate solution of 180 g/L, then recycles; Na in alkali leaching slag washings
2o
kconcentration is 50g/L;
When producing sandy aluminium hydroxide and aluminum oxide, the decomposition nut liquid of generation carries out evaporation process, controls the Na of decomposition nut liquid
2o
kconcentration is 180g/L, then recycles;
3, charge pulp is prepared: be mixed with charge pulp after coal ash alkali being soaked the mixing of slag washing material, Wingdale and hard coal: 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%; Add industrial sodium carbonate when total alkali mole number is not enough to regulate;
4, 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 60 min, be cooled to normal temperature sieving approach after having sintered to granularity≤15 mm, obtain sintering powder as grog;
5, 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; Using the diluting soln of alkali leaching slag washings in step 4 in the Clinker digestion liquid of siliceous sodium aluminate or step 2;
The filtrate that solid phase carries out carrying out washing treatment acquisition is adjusted liquid as Clinker digestion;
6, 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;
7, 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;
Make chemical mineral processing solvent after the siliceous sodium hydroxide solution obtained adds sodium hydroxide, return step 1 and use;
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;
8, 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
2o 80g/L, containing SiO
2≤ 5g/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 100 min; 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) the middle Na of sodium aluminate solution
2o
kconcentration is 210g/L, Na
2o+K
2o and Al
2o
3mol ratio be 2.8, the blending ratio of flyash concentrate and sodium aluminate solution is by Na in whole material
2o+K
2o and Al
2o
3mol ratio be 1.58, extraction temperature is 270 DEG C, and the reaction times is 60min; The add-on of diluting soln is by Na in dilution alkali leaching dreg slurry
2o
kconcentration is that 150g/L controls; Produce the decomposition nut liquid produced in sandy aluminium hydroxide and alumina process and carry out evaporation process, obtain Na
2o
kconcentration is the sodium aluminate solution of 210 g/L; Na in alkali leaching slag washings
2o
kconcentration is 60g/L;
When producing sandy aluminium hydroxide and aluminum oxide, the decomposition nut liquid of generation carries out evaporation process, controls the Na of decomposition nut liquid
2o
kconcentration is 210 g/L;
(3) 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%;
(4) 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 1220 DEG C, and sintering time is 30 min;
(5) 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; 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;
(6) 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, obtains the original slurry of xonotlite presoma; The Na of described sodium silicate solution
2o concentration is 80g/L, SiO
2concentration is 40g/L;
(7) by original for xonotlite presoma slurry steam jacket preheater or tubulation preheater indirect preheating to 100 DEG C, hydrothermal synthesis reaction is carried out, reaction times 100min;
(8) xonotlite presoma and water are mixed with form slurry, the weight ratio of water and xonotlite presoma is 10, again use steam jacket preheater or tubulation preheater preheats to 210 DEG C, carry out hydrothermal synthesis reaction, reaction times 180min, then after multistage flash evaporation recovery waste heat, drop to normal pressure, finally by press filtration obtain water weight content 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
2o 120g/L; Proportion scale is 9 by chemical mineral processing solvent and flyash weight ratio; Then through chemical mineral processing process, temperature of reaction 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) the middle Na of sodium aluminate solution
2o
kconcentration is 245g/L, Na
2o+K
2o and Al
2o
3mol ratio be 3.2, the blending ratio of flyash concentrate and sodium aluminate solution is by Na in whole material
2o+K
2o and Al
2o
3mol ratio be 1.6, extraction temperature is 280 DEG C, and the reaction times is 30min; The add-on of diluting soln is by Na in dilution alkali leaching dreg slurry
2o
kconcentration is that 165g/L controls; Produce the decomposition nut liquid produced in sandy aluminium hydroxide and alumina process and carry out evaporation process, obtain Na
2o
kconcentration is the sodium aluminate solution of 245 g/L, then recycles; Na in alkali leaching slag washings
2o
kconcentration is 70g/L;
When producing sandy aluminium hydroxide and aluminum oxide, the decomposition nut liquid of generation carries out evaporation process, controls the Na of decomposition nut liquid
2o
kconcentration is 245 g/L;
(3) 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%;
(4) 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;
(5) 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;
(6) 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, obtains the original slurry of xonotlite presoma; The Na of described sodium silicate solution
2o concentration is 120g/L, SiO
2concentration is 60g/L;
(7) by original for xonotlite presoma slurry steam jacket preheater or tubulation preheater indirect preheating to 120 DEG C, hydrothermal synthesis reaction is carried out, reaction times 30min;
(8) xonotlite presoma and water are mixed with form slurry, the weight ratio of water and xonotlite presoma is 15, again use steam jacket preheater or tubulation preheater preheats to 265 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% 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 (8)
1. coal ash alkali leaching sintering hydrothermal method produces a method for xonotlite 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
2o 30 ~ 120g/L, containing SiO
2≤ 5g/L; Proportion scale is 3 ~ 9 by chemical mineral processing solvent and flyash weight ratio; Then through chemical mineral processing process, temperature of reaction 70 ~ 120 DEG C, reaction times 30 ~ 600 min; 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) aluminum oxide is produced in alkali leaching: leached by flyash concentrate sodium aluminate solution, the middle Na of described sodium aluminate solution
2o
kconcentration is 180 ~ 245g/L, Na
2o+K
2o and Al
2o
3mol ratio be 2.5 ~ 3.2, the blending ratio of flyash concentrate and sodium aluminate solution is by Na in whole material
2o+K
2o and Al
2o
3mol ratio be 1.53 ~ 1.6, extraction temperature is 255 ~ 280 DEG C, and the reaction times is 30 ~ 120min; After multistage flash evaporation recovery waste heat, drop to atmospheric pressure state after leaching completes, obtain alkali soaking paste liquid; In alkali soaking paste liquid, add diluting soln obtain dilution alkali leaching dreg slurry, the add-on of diluting soln is by Na in dilution alkali leaching dreg slurry
2o
kconcentration is that 130 ~ 165g/L controls; Then dilution alkali leaching dreg slurry is carried out atmospheric silicon removing reaction, obtain atmospheric silicon removing slurries; Carry out repeatedly backflush with horizontal rubber belt formula filter to be separated, obtain separation solution, alkali leaching slag washings and coal ash alkali leaching slag washing material; Separation solution is refined through automatic leaf filter, obtains the wrought aluminum acid sodium solution that solid seston is less than 15mg/L; Wrought aluminum acid sodium solution adopts adding aluminum hydroxide crystal seed gradient cooling decomposition for producing sand-like aluminium hydroxide and aluminum oxide, and the decomposition nut liquid produced in this process carries out evaporation process, obtains Na
2o
kconcentration is the sodium aluminate solution of 180 ~ 245 g/L, then recycles; Na in alkali leaching slag washings
2o
kconcentration is 50 ~ 70g/L;
(3) charge pulp is prepared: be mixed with charge pulp after coal ash alkali being soaked the mixing of slag washing material, Wingdale and hard coal: 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%; Add industrial sodium carbonate when total alkali mole number is not enough to regulate;
(4) 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 ~ 60 min, be cooled to normal temperature sieving approach after having sintered to granularity≤15 mm, obtain sintering powder as grog;
(5) 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; Using the alkali leaching slag washings in the Clinker digestion liquid of siliceous sodium aluminate or step (2) as the diluting soln in step (4);
(6) 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;
(7) 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;
(8) 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 coal ash alkali leaching sintering hydrothermal method according to claim 1 produces the method for xonotlite and aluminum oxide, 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 coal ash alkali leaching sintering hydrothermal method according to claim 1 produces the method for xonotlite and aluminum oxide, when it is characterized in that producing sandy aluminium hydroxide and aluminum oxide in step (2), the decomposition nut liquid produced carries out evaporation process, controls the Na of decomposition nut liquid
2o
kconcentration is 180 ~ 245 g/L, then recycles.
4. a kind of coal ash alkali leaching sintering hydrothermal method according to claim 1 produces the method for xonotlite and aluminum oxide, it is characterized in that siliceous sodium hydroxide solution that step (7) obtains makes chemical mineral processing solvent after adding sodium hydroxide, return step (1) and use.
5. a kind of coal ash alkali leaching sintering hydrothermal method according to claim 1 produces the method for xonotlite 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 (6) and use as sodium silicate solution.
6. a kind of coal ash alkali leaching sintering hydrothermal method according to claim 1 produces the method for xonotlite and aluminum oxide, it is characterized in that the filtrate of in step (5), solid phase being carried out carrying out washing treatment acquisition adjusts liquid as Clinker digestion.
7. a kind of coal ash alkali leaching sintering hydrothermal method according to claim 1 produces the method for xonotlite and aluminum oxide, it is characterized in that the Na of described xonotlite presoma
2o content≤3g/L.
8. a kind of coal ash alkali leaching sintering hydrothermal method according to claim 1 produces the method for xonotlite and aluminum oxide, it is characterized in that the siliceous sodium hydroxide solution that step (7) 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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