CN108557779A - 一种磷石膏和粉煤灰制酸联产莫来石耐火砖的方法 - Google Patents
一种磷石膏和粉煤灰制酸联产莫来石耐火砖的方法 Download PDFInfo
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- CN108557779A CN108557779A CN201810712721.3A CN201810712721A CN108557779A CN 108557779 A CN108557779 A CN 108557779A CN 201810712721 A CN201810712721 A CN 201810712721A CN 108557779 A CN108557779 A CN 108557779A
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- China
- Prior art keywords
- ardealite
- flyash
- parts
- mullite firebrick
- relieving haperacidity
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000010881 fly ash Substances 0.000 title claims abstract description 64
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 229910052863 mullite Inorganic materials 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 36
- 239000002994 raw material Substances 0.000 claims abstract description 47
- 239000007788 liquid Substances 0.000 claims abstract description 43
- 238000000926 separation method Methods 0.000 claims abstract description 32
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 27
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 25
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 239000000654 additive Substances 0.000 claims abstract description 12
- 230000000996 additive effect Effects 0.000 claims abstract description 12
- 238000004090 dissolution Methods 0.000 claims abstract description 12
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052901 montmorillonite Inorganic materials 0.000 claims abstract description 10
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 5
- 229920006248 expandable polystyrene Polymers 0.000 claims abstract description 4
- 239000010453 quartz Substances 0.000 claims abstract description 4
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052900 illite Inorganic materials 0.000 claims abstract description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052622 kaolinite Inorganic materials 0.000 claims abstract description 3
- VGIBGUSAECPPNB-UHFFFAOYSA-L nonaaluminum;magnesium;tripotassium;1,3-dioxido-2,4,5-trioxa-1,3-disilabicyclo[1.1.1]pentane;iron(2+);oxygen(2-);fluoride;hydroxide Chemical compound [OH-].[O-2].[O-2].[O-2].[O-2].[O-2].[F-].[Mg+2].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[K+].[K+].[K+].[Fe+2].O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2 VGIBGUSAECPPNB-UHFFFAOYSA-L 0.000 claims abstract description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 22
- 229910052799 carbon Inorganic materials 0.000 claims description 20
- 238000001556 precipitation Methods 0.000 claims description 19
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 16
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 239000002002 slurry Substances 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 11
- 239000011449 brick Substances 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 235000012239 silicon dioxide Nutrition 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 9
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 8
- 238000005188 flotation Methods 0.000 claims description 8
- 239000003546 flue gas Substances 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 238000006555 catalytic reaction Methods 0.000 claims description 7
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 7
- 239000004793 Polystyrene Substances 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 229920002223 polystyrene Polymers 0.000 claims description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052593 corundum Inorganic materials 0.000 claims description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 3
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical group C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 claims description 2
- 239000003830 anthracite Substances 0.000 claims description 2
- 238000010304 firing Methods 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 6
- 239000007787 solid Substances 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract description 2
- 238000012805 post-processing Methods 0.000 abstract 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 7
- 238000001354 calcination Methods 0.000 description 5
- 238000004512 die casting Methods 0.000 description 5
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 description 4
- 229910001388 sodium aluminate Inorganic materials 0.000 description 4
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 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 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 229920006389 polyphenyl polymer Polymers 0.000 description 2
- 229940068984 polyvinyl alcohol Drugs 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- HLLSOEKIMZEGFV-UHFFFAOYSA-N 4-(dibutylsulfamoyl)benzoic acid Chemical compound CCCCN(CCCC)S(=O)(=O)C1=CC=C(C(O)=O)C=C1 HLLSOEKIMZEGFV-UHFFFAOYSA-N 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 229910001570 bauxite Inorganic materials 0.000 description 1
- 235000012241 calcium silicate Nutrition 0.000 description 1
- JHLNERQLKQQLRZ-UHFFFAOYSA-N calcium silicate Chemical compound [Ca+2].[Ca+2].[O-][Si]([O-])([O-])[O-] JHLNERQLKQQLRZ-UHFFFAOYSA-N 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 1
- GJYLKIZKRHDRER-UHFFFAOYSA-N calcium;sulfuric acid Chemical group [Ca].OS(O)(=O)=O GJYLKIZKRHDRER-UHFFFAOYSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000010883 coal ash Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000009970 fire resistant effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000002367 phosphate rock Substances 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 235000015424 sodium Nutrition 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/74—Preparation
- C01B17/76—Preparation by contact processes
- C01B17/78—Preparation by contact processes characterised by the catalyst used
- C01B17/79—Preparation by contact processes characterised by the catalyst used containing vanadium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/04—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom
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- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/04—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom
- C01F7/06—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom by treating aluminous minerals or waste-like raw materials with alkali hydroxide, e.g. leaching of bauxite according to the Bayer process
- C01F7/0693—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom by treating aluminous minerals or waste-like raw materials with alkali hydroxide, e.g. leaching of bauxite according to the Bayer process from waste-like raw materials, e.g. fly ash or Bayer calcination dust
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- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/04—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom
- C01F7/08—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom by treating aluminous minerals with sodium carbonate, e.g. sinter processes
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- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/04—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom
- C01F7/14—Aluminium oxide or hydroxide from alkali metal aluminates
- C01F7/141—Aluminium oxide or hydroxide from alkali metal aluminates from aqueous aluminate solutions by neutralisation with an acidic agent
- C01F7/142—Aluminium oxide or hydroxide from alkali metal aluminates from aqueous aluminate solutions by neutralisation with an acidic agent with carbon dioxide
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- C04B33/00—Clay-wares
- C04B33/02—Preparing or treating the raw materials individually or as batches
- C04B33/13—Compounding ingredients
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/16—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay
- C04B35/18—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay rich in aluminium oxide
- C04B35/185—Mullite 3Al2O3-2SiO2
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
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- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
- C04B2235/3218—Aluminium (oxy)hydroxides, e.g. boehmite, gibbsite, alumina sol
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- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3418—Silicon oxide, silicic acids or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
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Abstract
本发明提供了一种磷石膏和粉煤灰制酸联产莫来石耐火砖的方法，包括如下步骤：将磷石膏、粉煤灰、添加剂和改性剂混合并研磨制成生料，送入窑内焙烧，制得熟料，对熟料进行水磨溶出，并进行固液分离，分离得到的固体焙烧后加工制得硫酸，分离得到的液体加CO2得到氢氧化铝，氢氧化铝再与高岭石、伊利石、蒙脱石、刚玉粉、石英石、滑石粉、锯末、可发性聚苯乙烯球和聚乙烯醇制得莫来石耐火砖。本发明将磷石膏和粉煤灰进行综合利用，具有可减少环境污染，附加值高，且制得的氢氧化铝是生产莫来石耐火砖的良好原料，制备的莫来石耐火砖有生产成本低的优点。
Description
技术领域
本发明涉及一种磷石膏和粉煤灰制酸联产莫来石耐火砖的方法，属于冶金化工领域。
背景技术
磷石膏是指在磷酸生产中用硫酸处理磷矿时产生的固体废渣，其主要成分为硫酸钙，此外还含有多种其他杂质。目前，全世界每年排放磷石膏总量约为1.2-1.4亿吨，我国约为5000万吨左右，占全球年排放磷石膏总量的25-29%，这一数量呈增加趋势，且目前国内磷石膏堆放量达2.5亿吨，排出的磷石膏渣占用大量土地，形成渣山，严重污染环境。
粉煤灰是从煤燃烧后的烟气中收捕下来的细灰，粉煤灰是燃煤电厂排出的主要固体废物。随着电力工业的发展，燃煤电厂的粉煤灰排放量逐年增加，粉煤灰已成为我国当前排量较大的工业废渣之一。现目前，我国粉煤灰年产量已超过6亿吨，给我国的国民经济建设及生态环境造成巨大的压力。
莫来石耐火砖具有荷重软化温度高、高温蠕变率低、抗热震性好等优点， 广泛应用于高炉热风炉、玻璃熔窑、干熄焦及加热炉等工业炉窑上。为了追求更高质量的的莫来石耐火砖，现目前市场上出现了一种莫来石轻质隔热耐火砖，这种耐火砖中主要由耐火黏土和氢氧化铝烧制而成，但是现目前由于氢氧化铝的的市场价格较为昂贵，导致了其生产成本高的问题。
现目前，我国一方面磷石膏和粉煤灰都存在大量堆积，污染环境的问题，另一方面磷石膏和粉煤灰中都还存在许多有用组分。目前人们对磷石膏和粉煤灰的利用，主要都是用于建材方面，不过磷石膏中存在的酸会导致建材质量不佳，且这种利用方式的附加产值较低。目前综合利用磷石膏和粉煤灰制酸并联产莫来石耐火砖的工艺，未见报道。
发明目的
本发明的目的在于，提供一种磷石膏和粉煤灰制酸联产莫来石耐火砖的方法。本发明将磷石膏和粉煤灰进行综合利用，具有可减少环境污染，附加值高，且制得的氢氧化铝是生产莫来石耐火砖的良好原料，制备的莫来石耐火砖有生产成本低的优点。
本发明的技术方案
一种磷石膏和粉煤灰制酸联产莫来石耐火砖的方法，包括如下步骤：
A、将磷石膏、粉煤灰、添加剂和改性剂混合并研磨制成生料，送入窑内焙烧，制得熟料，对熟料进行水磨溶出，并进行固液分离；
B、将步骤A中固液分离得到的沉淀进行浮选，分离出硫化物，将分离出的硫化物进行焙烧，再将焙烧产生的烟气经五氧化二钒催化反应后，采用浓硫酸进行吸收，制得硫酸；
C、向步骤A中固液分离得到的液体中加入CO2至沉淀不再产生，然后将沉淀烘干，粉碎，制得氢氧化铝；
D、将高岭石、伊利石、蒙脱石、刚玉粉、石英石和滑石粉进行粉碎，然后投入混料机中混合均匀得混合料，混合料再与步骤C制得的氢氧化铝混合均匀，然后加入再加入锯末、可发性聚苯乙烯球和聚乙烯醇混合均匀得原料粉，加入水，继续混合得到浆料，将浆料注入模具浇注成砖坯，干燥砖坯，然后烧制，制得莫来石耐火砖。
前述的磷石膏和粉煤灰制酸联产莫来石耐火砖的方法，步骤A中，所述添加剂为碳酸钠、硫酸钠或烧碱；所述改性剂为无烟煤、碳或煤矸石；所述窑为工业回转窑、工业隧道窑或工业立窑。
前述的磷石膏和粉煤灰制酸联产莫来石耐火砖的方法，步骤A中，所述的生料中，磷石膏和粉煤灰按照1:1-1.7重量比的比例混合，添加剂添加比例按生料中所含Na2O和Al2O3+Fe2O3总和的分子比为1:1添加，改性剂的混合比例为生料总重量的12-23%；所述焙烧的温度为1130-1380℃，时间为2-5h；所述水磨溶出时的液固体积比为5-8:1。
前述的磷石膏和粉煤灰制酸联产莫来石耐火砖的方法，步骤B中，所述焙烧的温度1000-1200℃；时间为2-5h；条件为将硫化物置于40-45%的富氧环境下。
前述的磷石膏和粉煤灰制酸联产莫来石耐火砖的方法，步骤C中，所述烘干的温度为100-120℃，沉淀烘干后水分低于0.5%。
前述的磷石膏和粉煤灰制酸联产莫来石耐火砖的方法，按重量份计，步骤D中，所述莫来石耐火砖包括20-25份高岭石、6-8份伊利石、7-9份蒙脱石、12-15份刚玉粉、14-18份石英石、3-5份滑石粉、40-50份氢氧化铝、5-10份锯末、6-12份可发性聚苯乙烯球和3-5份聚乙烯醇。
前述的磷石膏和粉煤灰制酸联产莫来石耐火砖的方法，步骤D中，所述原料粉与水的质量比为1:1-1.2。
前述的磷石膏和粉煤灰制酸联产莫来石耐火砖的方法，步骤D中，所述粉碎过100-120目筛网。
前述的磷石膏和粉煤灰制酸联产莫来石耐火砖的方法，步骤D中，所述锯末过80-100目筛；可发性聚苯乙烯球的粒径为1-2mm。
前述的磷石膏和粉煤灰制酸联产莫来石耐火砖的方法，步骤D中，所述烧制是在5-10h内升温至1300-1400℃，然后保温2-5h，然后在10-15h内降温至700-800℃，最后自然冷却。
本发明通过将磷石膏和高硫铝土矿反应、重组，使之成为有用物质。原理的总反应式为：
CaSO4（磷石膏）+Na2O·SiO2·Al2O3（粉煤灰）→Na2O·Al2O3+CaO·SiO2↓+[硫]
从该反应式可知，用磷石膏中的CaO与粉煤灰中的SiO2生成原硅酸钙（CaO·SiO2↓）后，得到可溶性极好的铝酸钠（Na2O·Al2O3）。反应式中的[硫]，是指通过生料加改性剂工艺，生成的金属硫化物，其主要成分为FeS；浸出熟料中的铝酸钠后，将得到的沉淀物浮选即可得到FeS。
有益效果
1、本发明通过将磷石膏和粉煤灰综合利用，混合添加剂和改性剂后经研磨，水磨溶出后进行固液分离，即可得到成分分明的产物，可大量消耗磷石膏和粉煤灰，减少磷石膏和粉煤灰对环境的污染。
2、本发明通过将工业废渣磷石膏、粉煤灰、添加剂和改性剂混合研磨后焙烧，再进行水磨溶出和固液分离，原料成本低廉，工艺简单，且焙烧过程形成的主要成分金属硫化物、偏铝酸盐和硅酸盐成分分明，均可单独提取回收，大大提高了磷石膏和粉煤灰的附加值。
3、本发明利用废料磷石膏和粉煤灰，加上添加剂和改性剂作为原料，焙烧后经过水磨溶出和固液分离就能得到成分分明的产物，焙烧过后产物中不含有机物，非常利于后期对产物各组分进行分别提取，尤其是固液分离中得到液体，几乎只含有可溶的偏铝酸钠，通入CO2气体后即可得到纯度很高的氢氧化铝，纯度可达98%以上，是制备莫来石耐火砖的良好原料。
4、本发明通过廉价的工业废渣磷石膏和粉煤灰，加上一定的添加剂和改性剂制得氢氧化铝的工艺简单，原料成本低廉，所得氢氧化铝的成本很低，用于生产莫来石耐火砖，可大大降低莫来石耐火砖的生产成本。
5、本发明通过将工业废渣磷石膏、粉煤灰、添加剂和改性剂混合研磨后焙烧，再水磨溶出后进行固液分离，再从分离出的沉淀中提取得到硫酸，生产成本低，工艺简单。
性能检测
取样实施例1-5制得的莫来石耐火砖，进行耐火度、常温耐压强度和高温抗折强度的检测。得表1结果。
具体实施方式
下面结合实施例对本发明作进一步的说明，但并不作为对本发明限制的依据。
本发明的实施例
实施例1：一种磷石膏和粉煤灰制酸联产莫来石耐火砖的方法，步骤如下：
A、将磷石膏、粉煤灰、碳酸钠和碳混合并研磨制成生料，生料中，磷石膏和粉煤灰按照1:1.7重量比的比例混合，碳酸钠添加比例按生料中所含Na2O和A12O3+Fe2O3总和的分子比为1:1添加，碳的混合比例为生料总重量的12%送入工业立窑内焙烧，焙烧温度为1380℃，焙烧时间为2小时，制得熟料，对熟料进行水磨溶出，并进行固液分离，分离时液固体积比为5:1；
B、将步骤A中固液分离得到的沉淀进行浮选，分离出硫化物，将分离出的硫化物置于40%的富氧环境下，在1000℃下焙烧5小时，焙烧产生的烟气经五氧化二钒催化反应后，采用浓硫酸进行吸收，制得硫酸；
C、向步骤A中固液分离得到的液体中加入CO2至沉淀不再产生，然后将沉淀在100℃下烘干，至水分低于0.5%后，粉碎，制得氢氧化铝；
D、按重量份计，将25份高岭石、8份伊利石、9份蒙脱石、15份刚玉粉、18份石英石和5份滑石粉进行，粉碎，过120目筛网，然后投入混料机中混合均匀得混合料，混合料再与步骤C制得的50份氢氧化铝混合均匀，然后加入再加入10份100目锯末、12份粒径为2mm的可发性聚苯乙烯球和5份聚乙烯醇混合均匀得原料粉，加入原料重量1.2倍的水，继续混合得到浆料，将浆料注入模具浇注成砖坯，干燥砖坯，至含量小于3%，然后送入窑中在10h升温至1400℃，然后保温5h，然后在15h降温至800℃，最后自然冷却，完成烧制，制得莫来石耐火砖。
实施例2：一种磷石膏和粉煤灰制酸联产莫来石耐火砖的方法，步骤如下：
A、将磷石膏、粉煤灰、碳酸钠和碳混合并研磨制成生料，生料中，磷石膏和粉煤灰按照1:1重量比的比例混合，碳酸钠添加比例按生料中所含Na2O和A12O3+Fe2O3总和的分子比为1:1添加，碳的混合比例为生料总重量的23%送入工业立窑内焙烧，焙烧温度为1130℃，焙烧时间为5小时，制得熟料，对熟料进行水磨溶出，并进行固液分离，分离时液固体积比为8:1；
B、将步骤A中固液分离得到的沉淀进行浮选，分离出硫化物，将分离出的硫化物置于45%的富氧环境下，在1200℃下焙烧2小时，焙烧产生的烟气经五氧化二钒催化反应后，采用浓硫酸进行吸收，制得硫酸；
C、向步骤A中固液分离得到的液体中加入CO2至沉淀不再产生，然后将沉淀在120℃下烘干，至水分低于0.5%后，粉碎，制得氢氧化铝；
D、按重量份计，将20份高岭石、6份伊利石、7份蒙脱石、12份刚玉粉、14份石英石和3份滑石粉进行，粉碎，过100目筛网，然后投入混料机中混合均匀得混合料，混合料再与步骤C制得的40份氢氧化铝混合均匀，然后加入再加入5份80目锯末、6份粒径为1mm的可发性聚苯乙烯球和3份聚乙烯醇混合均匀得原料粉，加入原料重量1.2倍的水，继续混合得到浆料，将浆料注入模具浇注成砖坯，干燥砖坯，至含量小于3%，然后送入窑中在5h升温至1300℃，然后保温2h，然后在10h降温至700℃，最后自然冷却，完成烧制，制得莫来石耐火砖。
实施例3：一种磷石膏和粉煤灰制酸联产莫来石耐火砖的方法，步骤如下：
A、将磷石膏、粉煤灰、碳酸钠和碳混合并研磨制成生料，生料中，磷石膏和粉煤灰按照1:1.2重量比的比例混合，碳酸钠添加比例按生料中所含Na2O和A12O3+Fe2O3总和的分子比为1:1添加，碳的混合比例为生料总重量的14%送入工业立窑内焙烧，焙烧温度为1220℃，焙烧时间为3小时，制得熟料，对熟料进行水磨溶出，并进行固液分离，分离时液固体积比为7：1；
B、将步骤A中固液分离得到的沉淀进行浮选，分离出硫化物，将分离出的硫化物置于42%的富氧环境下，在1100℃下焙烧5小时，焙烧产生的烟气经五氧化二钒催化反应后，采用浓硫酸进行吸收，制得硫酸；
C、向步骤A中固液分离得到的液体中加入CO2至沉淀不再产生，然后将沉淀在110℃下烘干，至水分低于0.5%后，粉碎，制得氢氧化铝；
D、按重量份计，将22份高岭石、7份伊利石、8份蒙脱石、13份刚玉粉、15份石英石和4份滑石粉进行，粉碎，过110目筛网，然后投入混料机中混合均匀得混合料，混合料再与步骤C制得的45份氢氧化铝混合均匀，然后加入再加入6份90目锯末、8份粒径为1mm的可发性聚苯乙烯球和4份聚乙烯醇混合均匀得原料粉，加入原料重量1.1倍的水，继续混合得到浆料，将浆料注入模具浇注成砖坯，干燥砖坯，至含量小于3%，然后送入窑中在6h升温至1330℃，然后保温3h，然后在12h降温至730℃，最后自然冷却，完成烧制，制得莫来石耐火砖。
实施例4：一种磷石膏和粉煤灰制酸联产莫来石耐火砖的方法，步骤如下：
A、将磷石膏、粉煤灰、碳酸钠和碳混合并研磨制成生料，生料中，磷石膏和粉煤灰按照1:1.4重量比的比例混合，碳酸钠添加比例按生料中所含Na2O和A12O3+Fe2O3总和的分子比为1:1添加，碳的混合比例为生料总重量的19%送入工业立窑内焙烧，焙烧温度为1250℃，焙烧时间为3小时，制得熟料，对熟料进行水磨溶出，并进行固液分离，分离时液固体积比6:1；
B、将步骤A中固液分离得到的沉淀进行浮选，分离出硫化物，将分离出的硫化物置于43%的富氧环境下，在1150℃下焙烧3小时，焙烧产生的烟气经五氧化二钒催化反应后，采用浓硫酸进行吸收，制得硫酸；
C、向步骤A中固液分离得到的液体中加入CO2至沉淀不再产生，然后将沉淀在110℃下烘干，至水分低于0.5%后，粉碎，制得氢氧化铝；
D、按重量份计，将23份高岭石、7份伊利石、8份蒙脱石、13份刚玉粉、16份石英石和4.5份滑石粉进行，粉碎，过110目筛网，然后投入混料机中混合均匀得混合料，混合料再与步骤C制得的46份氢氧化铝混合均匀，然后加入再加入8份90目锯末、9份粒径为1.5mm的可发性聚苯乙烯球和4份聚乙烯醇混合均匀得原料粉，加入原料重量1.1倍的水，继续混合得到浆料，将浆料注入模具浇注成砖坯，干燥砖坯，至含量小于3%，然后送入窑中在7h升温至1350℃，然后保温3h，然后在13h降温至750℃，最后自然冷却，完成烧制，制得莫来石耐火砖。
实施例5：一种磷石膏和粉煤灰制酸联产莫来石耐火砖的方法，步骤如下：
A、将磷石膏、粉煤灰、碳酸钠和碳混合并研磨制成生料，生料中，磷石膏和粉煤灰按照1:1.6重量比的比例混合，碳酸钠添加比例按生料中所含Na2O和A12O3+Fe2O3总和的分子比为1:1添加，碳的混合比例为生料总重量的22%送入工业立窑内焙烧，焙烧温度为1300℃，焙烧时间为2.5小时，制得熟料，对熟料进行水磨溶出，并进行固液分离，分离时液固体积比6:1；
B、将步骤A中固液分离得到的沉淀进行浮选，分离出硫化物，将分离出的硫化物置于43%的富氧环境下，在1150℃下焙烧3小时，焙烧产生的烟气经五氧化二钒催化反应后，采用浓硫酸进行吸收，制得硫酸；
C、向步骤A中固液分离得到的液体中加入CO2至沉淀不再产生，然后将沉淀在120℃下烘干，至水分低于0.5%后，粉碎，制得氢氧化铝；
D、按重量份计，将24份高岭石、7份伊利石、8份蒙脱石、13份刚玉粉、17份石英石和3.5份滑石粉进行，粉碎，过115目筛网，然后投入混料机中混合均匀得混合料，混合料再与步骤C制得的42份氢氧化铝混合均匀，然后加入再加入9份95目锯末、8份粒径为1.5mm的可发性聚苯乙烯球和4份聚乙烯醇混合均匀得原料粉，加入原料重量1.1倍的水，继续混合得到浆料，将浆料注入模具浇注成砖坯，干燥砖坯，至含量小于3%，然后送入窑中在8h升温至1380℃，然后保温4h，然后在14h降温至780℃，最后自然冷却，完成烧制，制得莫来石耐火砖。
Claims (10)
1.一种磷石膏和粉煤灰制酸联产莫来石耐火砖的方法，其特征在于，包括如下步骤：
A、将磷石膏、粉煤灰、添加剂和改性剂混合并研磨制成生料，送入窑内焙烧，制得熟料，对熟料进行水磨溶出，并进行固液分离；
B、将步骤A中固液分离得到的沉淀进行浮选，分离出硫化物，将分离出的硫化物进行焙烧，再将焙烧产生的烟气经五氧化二钒催化反应后，采用浓硫酸进行吸收，制得硫酸；
C、向步骤A中固液分离得到的液体中加入CO2至沉淀不再产生，然后将沉淀烘干，粉碎，制得氢氧化铝；
D、将高岭石、伊利石、蒙脱石、刚玉粉、石英石和滑石粉进行粉碎，然后投入混料机中混合均匀得混合料，混合料再与步骤C制得的氢氧化铝混合均匀，然后加入再加入锯末、可发性聚苯乙烯球和聚乙烯醇混合均匀得原料粉，加入水，继续混合得到浆料，将浆料注入模具浇注成砖坯，干燥砖坯，然后烧制，制得莫来石耐火砖。
2.根据权利要求1所述的磷石膏和粉煤灰制酸联产莫来石耐火砖的方法，其特征在于：步骤A中，所述添加剂为碳酸钠、硫酸钠或烧碱；所述改性剂为无烟煤、碳或煤矸石；所述窑为工业回转窑、工业隧道窑或工业立窑。
3.根据权利要求1所述的磷石膏和粉煤灰制酸联产莫来石耐火砖的方法，其特征在于：步骤A中，所述的生料中，磷石膏和粉煤灰按照1:1-1.7重量比的比例混合，添加剂添加比例按生料中所含Na2O和Al2O3+Fe2O3总和的分子比为1:1添加，改性剂的混合比例为生料总重量的12-23%；所述焙烧的温度为1130-1380℃，时间为2-5h；所述水磨溶出时的液固体积比为5-8:1。
4.根据权利要求1所述的磷石膏和粉煤灰制酸联产莫来石耐火砖的方法，其特征在于：步骤B中，所述焙烧的温度1000-1200℃；时间为2-5h；条件为将硫化物置于40-45%的富氧环境下。
5.根据权利要求1所述的磷石膏和粉煤灰制酸联产莫来石耐火砖的方法，其特征在于：步骤C中，所述烘干的温度为100-120℃，沉淀烘干后水分低于0.5%。
6.根据权利要求1所述的磷石膏和粉煤灰制酸联产莫来石耐火砖的方法，其特征在于：按重量份计，步骤D中，所述莫来石耐火砖包括20-25份高岭石、6-8份伊利石、7-9份蒙脱石、12-15份刚玉粉、14-18份石英石、3-5份滑石粉、40-50份氢氧化铝、5-10份锯末、6-12份可发性聚苯乙烯球和3-5份聚乙烯醇。
7.根据权利要求1所述的磷石膏和粉煤灰制酸联产莫来石耐火砖的方法，其特征在于：步骤D中，所述原料粉与水的质量比为1:1-1.2。
8.根据权利要求1所述的磷石膏和粉煤灰制酸联产莫来石耐火砖的方法，其特征在于：步骤D中，所述粉碎过100-120目筛网。
9.根据权利要求1所述的磷石膏和粉煤灰制酸联产莫来石耐火砖的方法，其特征在于：步骤D中，所述锯末过80-100目筛；可发性聚苯乙烯球的粒径为1-2mm。
10.根据权利要求1所述的磷石膏和粉煤灰制酸联产莫来石耐火砖的方法，其特征在于：步骤D中，所述烧制是在5-10h内升温至1300-1400℃，然后保温2-5h，然后在10-15h内降温至700-800℃，最后自然冷却。
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