CN107056102B - System and method for producing sulphoaluminate cement and co-producing sulfur by utilizing desulfurized gypsum and aluminum ash - Google Patents
System and method for producing sulphoaluminate cement and co-producing sulfur by utilizing desulfurized gypsum and aluminum ash Download PDFInfo
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- CN107056102B CN107056102B CN201710159992.6A CN201710159992A CN107056102B CN 107056102 B CN107056102 B CN 107056102B CN 201710159992 A CN201710159992 A CN 201710159992A CN 107056102 B CN107056102 B CN 107056102B
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- aluminum ash
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- 229910052602 gypsum Inorganic materials 0.000 title claims abstract description 108
- 239000010440 gypsum Substances 0.000 title claims abstract description 108
- 239000004568 cement Substances 0.000 title claims abstract description 88
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 71
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 239000011593 sulfur Substances 0.000 title claims abstract description 46
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 46
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 26
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 43
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000001354 calcination Methods 0.000 claims abstract description 30
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003546 flue gas Substances 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 239000003245 coal Substances 0.000 claims abstract description 15
- 238000000227 grinding Methods 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000010531 catalytic reduction reaction Methods 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 31
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 21
- 239000002918 waste heat Substances 0.000 claims description 18
- 239000002994 raw material Substances 0.000 claims description 17
- 239000000428 dust Substances 0.000 claims description 14
- 238000011084 recovery Methods 0.000 claims description 14
- 229910052925 anhydrite Inorganic materials 0.000 claims description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 13
- 229910052742 iron Inorganic materials 0.000 claims description 12
- 239000005864 Sulphur Substances 0.000 claims description 11
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 10
- 239000011575 calcium Substances 0.000 claims description 10
- 229910052791 calcium Inorganic materials 0.000 claims description 10
- 238000006722 reduction reaction Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 230000009467 reduction Effects 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 238000003860 storage Methods 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 229910052918 calcium silicate Inorganic materials 0.000 claims description 6
- 229910052681 coesite Inorganic materials 0.000 claims description 6
- 229910052906 cristobalite Inorganic materials 0.000 claims description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 6
- 239000011707 mineral Substances 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 229910052682 stishovite Inorganic materials 0.000 claims description 6
- 229910052905 tridymite Inorganic materials 0.000 claims description 6
- 239000003034 coal gas Substances 0.000 claims description 4
- 239000000446 fuel Substances 0.000 claims description 4
- GQCYCMFGFVGYJT-UHFFFAOYSA-N [AlH3].[S] Chemical compound [AlH3].[S] GQCYCMFGFVGYJT-UHFFFAOYSA-N 0.000 claims description 3
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- 239000008236 heating water Substances 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims 1
- 150000004706 metal oxides Chemical class 0.000 claims 1
- 238000010298 pulverizing process Methods 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 abstract description 5
- 239000001301 oxygen Substances 0.000 abstract description 5
- 238000002485 combustion reaction Methods 0.000 abstract description 3
- 239000002956 ash Substances 0.000 description 49
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 17
- 239000007789 gas Substances 0.000 description 15
- 239000000292 calcium oxide Substances 0.000 description 14
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 14
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 14
- 238000000354 decomposition reaction Methods 0.000 description 13
- 239000006227 byproduct Substances 0.000 description 10
- 238000006477 desulfuration reaction Methods 0.000 description 10
- 230000023556 desulfurization Effects 0.000 description 10
- 235000019738 Limestone Nutrition 0.000 description 8
- 239000006028 limestone Substances 0.000 description 8
- 239000011398 Portland cement Substances 0.000 description 7
- 230000008901 benefit Effects 0.000 description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 238000010248 power generation Methods 0.000 description 7
- 239000002910 solid waste Substances 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 6
- JHLNERQLKQQLRZ-UHFFFAOYSA-N calcium silicate Chemical compound [Ca+2].[Ca+2].[O-][Si]([O-])([O-])[O-] JHLNERQLKQQLRZ-UHFFFAOYSA-N 0.000 description 5
- 235000012241 calcium silicate Nutrition 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- 238000010276 construction Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000003723 Smelting Methods 0.000 description 3
- XOCUXOWLYLLJLV-UHFFFAOYSA-N [O].[S] Chemical compound [O].[S] XOCUXOWLYLLJLV-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000001117 sulphuric acid Substances 0.000 description 3
- 235000011149 sulphuric acid Nutrition 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910001570 bauxite Inorganic materials 0.000 description 2
- 238000012824 chemical production Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000007791 dehumidification Methods 0.000 description 2
- 150000004683 dihydrates Chemical class 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000010881 fly ash Substances 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 230000001502 supplementing effect Effects 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- GBAOBIBJACZTNA-UHFFFAOYSA-L calcium sulfite Chemical compound [Ca+2].[O-]S([O-])=O GBAOBIBJACZTNA-UHFFFAOYSA-L 0.000 description 1
- 235000010261 calcium sulphite Nutrition 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000002817 coal dust Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000012761 high-performance material Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 235000012054 meals Nutrition 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 238000005380 natural gas recovery Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000004391 petroleum recovery Methods 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/32—Aluminous cements
- C04B7/323—Calcium aluminosulfate cements, e.g. cements hydrating into ettringite
-
- 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
- C01B17/02—Preparation of sulfur; Purification
- C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
-
- 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
- C01B17/02—Preparation of sulfur; Purification
- C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
- C01B17/0473—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by reaction of sulfur dioxide or sulfur trioxide containing gases with reducing agents other than hydrogen sulfide
-
- 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
- C01B17/02—Preparation of sulfur; Purification
- C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
- C01B17/0473—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by reaction of sulfur dioxide or sulfur trioxide containing gases with reducing agents other than hydrogen sulfide
- C01B17/0482—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by reaction of sulfur dioxide or sulfur trioxide containing gases with reducing agents other than hydrogen sulfide with carbon or solid carbonaceous materials
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Ceramic Engineering (AREA)
- Structural Engineering (AREA)
- Processing Of Solid Wastes (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Treating Waste Gases (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a system and a method for producing sulphoaluminate cement and co-producing sulfur by utilizing desulfurized gypsum and aluminum ash, 1) drying the aluminum ash, heating and dehydrating the desulfurized gypsum to convert the desulfurized gypsum into semi-hydrated gypsum; 2) uniformly mixing the aluminum ash and the semi-hydrated gypsum according to a set proportion, and then grinding and homogenizing; 3) calcining the mixture of the aluminum ash and the semi-hydrated gypsum after grinding and homogenizing, and during calcining, adding coal powder into the mixture for oxygen-enriched combustion to obtain sulphoaluminate cement clinker and flue gas containing sulfur dioxide; 4) mixing the sulphoaluminate cement clinker with the desulfurized gypsum in proportion, and grinding to obtain sulphoaluminate cement; 5) dedusting and catalytic reduction are carried out on the flue gas containing sulfur dioxide to prepare a sulfur product; wherein the mass ratio of the aluminum ash, the desulfurized gypsum and the carbon powder is as follows: 33-39: 61-66: 1.
Description
Technical Field
The invention relates to the fields of chemical engineering, building material technology, comprehensive utilization of desulfurized gypsum and aluminum ash resources and environmental protection and treatment, in particular to a system and a method for producing sulphoaluminate cement and co-producing sulfur by utilizing desulfurized gypsum and aluminum ash.
Background
In the current society with increasingly tense land resources and increasingly important environmental protection, the ministry of industry and trust in China lists tailings, coal gangue, fly ash, smelting slag, byproduct gypsum and red mud from five industries as the major industrial solid wastes in the 'twelve five major industrial solid waste comprehensive utilization special project' and takes the tailings, the coal gangue, the fly ash, the smelting slag, the byproduct gypsum and the red mud as the main objects of treatment. Among them, red mud, aluminum ash and desulfurized gypsum are typical industrial solid wastes which are more and more focused.
The desulfurized gypsum is a byproduct generated by flue gas desulfurization in industrial production, and the main component of the desulfurized gypsum is crystalline calcium sulfate (CaSO)4·2H2O) the water content is generally 10-20%, the color is light yellow, the particles are fine, the pH value of the gypsum is equivalent to that of natural gypsum, the mass fraction of calcium sulfate and calcium sulfate dihydrate is generally more than 90%, and the mass fraction of calcium sulfate and calcium sulfate dihydrate of natural gypsum is generally 70-80%. The desulfurized gypsum has higher purity and stable components, contains main impurities of unreacted calcium oxide and calcium sulfite, and has the main differences of higher water content, smaller granularity and more water-soluble salts compared with natural gypsum. The shape of the desulfurized gypsum is greatly influenced by the temperature, the desulfurized gypsum loses crystal water from 135 ℃ to 185 ℃ to remove all crystal water, and the main mineral component of the desulfurized gypsum dried at the temperature of 140 ℃ is changed into semi-hydrated gypsum from dihydrate gypsum. With the continuous improvement of the infrastructure of China, the demand for electric power is continuously intensified, the thermal power generation capacity of China accounts for about 80% of the total power generation capacity, the existing industrial byproduct desulfurized gypsum is estimated to reach 6 hundred million tons according to the corresponding thermal power generation capacity, the average sulfur content of thermal power generation fire coal and the average desulfurization efficiency of desulfurization facilities in nearly 10 years, if the thermal power generation capacity, the average sulfur content of the thermal power generation fire coal and the average desulfurization efficiency of the desulfurization facilities cannot be comprehensively utilized, a large amount of land is occupied, the environment is polluted, and the required land amount is only stacked, so. Because the desulfurized gypsum contains various harmful impurities which are harmful to human health and biological growth, the desulfurized gypsum not only occupies a large amount of land and wastes valuable sulfur resources, but also pollutes the environment and brings harm to ecology when being stacked.
The aluminum ash is a waste produced in primary and secondary aluminum industries, the content of aluminum element can reach 30-55%, and the aluminum ash is a renewable resource. Along with the rapid development of the aluminum industry in China, the yield of aluminum ash is more and more. In 2012For example, the yield of raw aluminum in China is about 2000 ten thousand tons, and about 30 kg of aluminum ash is generated for every 1 ton of raw aluminum; in the secondary aluminum industry, the yield of recycled aluminum in 2012 of China is about 480 ten thousand tons, and about 300 kilograms of aluminum ash can be correspondingly generated when 1 ton of recycled aluminum is produced; the two are added together, and the aluminum ash yield in China reaches about 200 ten thousand tons in 2012. The main chemical components of the aluminum ash comprise: al (Al)2O340-60 wt%, AlN 15-30 wt%, metallic Al 5-10 wt%, and part of SiO2And hydrochloride of Na, Mg and K, the content is more than 10 wt%, the components are complex, and the heavy metal impurities polluting the environment are contained. The primary aluminum ash is white, the secondary aluminum ash is mostly black gray, the aluminum ash slag has good grindability, low hardness, irregular particle appearance and appearance, various shapes, uneven particle size and obvious difference in size, so that the flowability is poor. Although the discharge amount of the aluminum ash is large, the aluminum ash is complex in components and difficult to dispose, and an efficient utilization way is lacked, so that the aluminum ash is accumulated at present, on one hand, the aluminum ash occupies land, pollutes soil, and granular dust also affects the atmosphere, and on the other hand, the aluminum ash also wastes resources.
China hardly has natural sulfur ores, and sulfur is mainly recovered from petroleum refining and natural gas purification, and is obtained from environment-friendly byproducts in industries such as coal chemical industry, chemical fertilizer production, thermal power generation, non-ferrous metal smelting and the like. The sulfur recovery and tail gas treatment technology has been developed by a simple environmental protection technology into an important process technology with environmental protection benefit and economic benefit. The annual output of the domestic sulfur is only more than 1000 ten thousand tons, the annual consumption amount exceeds 1000 ten thousand tons, about 900 ten thousand tons are imported from foreign countries every year, and a serious supply and demand situation is presented. At present, sulfur is no longer used as a byproduct of petroleum and natural gas recovery at home and abroad, but is circulated as an important resource.
In recent years, sulphoaluminate cement becomes a new direction for research and development of the domestic and foreign cement industry, and cement clinker has a series of excellent performances of low heat consumption, high early strength, short setting time, excellent freeze-thaw resistance, low alkalinity and the like required by production. Because the prior sulphoaluminate cement has obvious advantages and complete varieties, the prior sulphoaluminate cement is widely applied to rush repair and rush construction projects, winter construction projects and corrosion-resistant projects. The technology of decomposing and co-producing cement and sulfuric acid by using gypsum in China starts late, the mature technology at present is to mix dried powdery materials with other raw materials, grind the mixture into a hollow rotary kiln for decomposition and calcination, the atmosphere in the kiln is difficult to control, the problem of high oxygen content in the kiln is easy to generate, and the like, so that carbon added into the raw materials partially reacts with oxygen in a combustion manner, the problem of insufficient carbon required by the gypsum decomposition reaction is caused, and the problem of reduction of the decomposition rate and the desulfurization rate is caused.
Meanwhile, the shortage of sulfur resources in China generally adopts natural gypsum ore to produce sulfur, but the cost for producing sulfur by adopting natural gypsum ore is higher, and the chemical production mainly depends on imported sulfur, so that the sulfur price is continuously increased, and the cost for chemical production is increased.
Disclosure of Invention
The basic raw materials used for producing sulphoaluminate cement in the prior art are limestone, bauxite and gypsum, the limestone serving as a calcium raw material mainly provides a calcium oxide component required in the forming process of sulphoaluminate cement clinker, and the bauxite serving as an aluminum raw material mainly provides an aluminum oxide component required in the forming process of the sulphoaluminate cement clinker; the gypsum is used as a sulfur raw material to mainly provide sulfur trioxide components required in the forming process of the sulphoaluminate cement clinker. In actual production, limestone is decomposed at 850-900 ℃ to generate CaO and CO2，CO2Escaping from the waste, the sulphoaluminate cement clinker, due to the large quantity of limestone used in its preparation, releases a large quantity of CO2Greatly aggravating the greenhouse effect of the environment.
The 4CaO 2Si of the common sulphoaluminate cement is calcined at 1250-1300 DEG C2O2·CaSO2Disappear and decompose into alpha' -2 CaO. SiO2And free CaSO4The main mineral of the clinker is 3CaO 3Al2O3·CaSO4And 2 CaO. SiO2And also a small amount of iron phase and CaSO4And trace amount of MgO, ordinary sulphoaluminate cement is completely formed, and when the mixture is continuously heated to 1300-1400 ℃, the mineral clinker does not obviously change(ii) a Heating to above 1400 deg.C to 3 CaO.3 Al2O3·CaSO4And CaSO4Decomposition is started to generate 12CaO 7Al2O3And the like, the clinker appears. Therefore, the calcination temperature of the ordinary sulphoaluminate cement is generally 1250-1300 ℃, and a small amount of CaSO is generated in the process4The decomposition occurs, so that in order to avoid the pollution of the discharged flue gas containing sulfur dioxide to the environment, the sulfur dioxide in the flue gas is generally recovered to be prepared into sulfuric acid or sulfur. However, since CaSO4The decomposition is very little at 1250 ℃ and 1300 ℃, namely the concentration of sulfur dioxide in the flue gas is very small, so that only a very small amount of sulfur or sulfuric acid can be obtained, and the industrial production cannot be carried out. If a special device is arranged to absorb and convert the sulfur dioxide, the economic benefit brought by the prepared sulfur or sulfuric acid is difficult to make up for the cost increased by arranging the special absorption device.
Therefore, the inventor considers that whether a process method can be developed or not, so that the sulphoaluminate cement clinker and the sulphur or the sulphuric acid can be simultaneously prepared in large quantity, the excessive emission of carbon dioxide can be prevented, the greenhouse effect of the environment is aggravated, a large quantity of sulphur or sulphuric acid can be produced, and the production cost of the sulphur or sulphuric acid is reduced.
Aiming at the technical problems in the prior art, the invention aims to provide a system and a method for producing sulphoaluminate cement and co-producing sulphur by utilizing desulfurized gypsum and aluminum ash. The method can fully utilize the aluminum ash and the desulfurized gypsum which are few in application and serious in stockpiling at present, and realize the co-production of the sulphoaluminate cement and the sulfur.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a system for producing sulphoaluminate cement and co-producing sulfur by utilizing desulfurized gypsum and aluminum ash comprises a dryer, a pulverizer, a rotary kiln, a cement pulverizer, a cement storage tank, a dust remover and a reduction fixed bed, wherein after the aluminum ash and the desulfurized gypsum are dried by the dryer, the aluminum ash, activated carbon and the desulfurized gypsum are mixed according to a specific proportion, the mixture is sent to the pulverizer for grinding, the ground mixture is conveyed to the rotary kiln for calcination, and pulverized coal is conveyed to the rotary kiln; mixing the calcined sulphoaluminate clinker with the desulfurized gypsum according to a specific proportion, grinding the mixture in a cement grinding machine, and conveying the obtained sulphoaluminate cement to a cement storage tank for storage;
and (3) dedusting the gas containing sulfur dioxide obtained by calcination in the rotary kiln through a deduster, and conveying the gas into a reduction fixed bed for reduction to obtain sulfur.
The system can realize the co-production of the sulphoaluminate cement and the sulphur by utilizing the solid wastes of the aluminum ash and the desulfurized gypsum, thereby realizing the treatment of the solid wastes, preparing a high-performance material and the sulphur and simultaneously reducing the production cost of the sulphur.
Because the waste heat recovery equipment is adopted, the aluminum ash and the desulfurized gypsum are preheated in the process of utilizing the waste heat, and the semi-hydrated gypsum is formed when the waste heat of the desulfurized gypsum is heated to about 200 ℃. Thus, part of heat required by calcination can be saved, and energy is saved.
During the calcination process, the pulverized coal is conveyed into the rotary kiln, the pulverized coal can react with oxygen in the rotary kiln to enable a reaction chamber of the rotary kiln to be in a weak oxidation atmosphere, and the addition of the activated carbon enables the desulfurized gypsum to reach a sufficient decomposition rate and desulfurization rate.
Preferably, a waste heat recovery device is connected between the rotary kiln and the dust remover, water in the waste heat recovery device is heated by smoke discharged from the rotary kiln, the obtained high-temperature steam is introduced into the dryer to be used as a heating medium, and the cooled smoke enters the dust remover for dust removal.
The waste heat recovery device is similar to a heat exchanger, liquid such as water in the waste heat recovery device is heated by waste heat in the flue gas, high-temperature steam is obtained, the temperature of the flue gas is reduced, the subsequent dust remover and the reduction fixed bed cannot be greatly damaged by the lower temperature (not lower than 850 ℃) of the flue gas, and the service life of the subsequent device is prolonged. The obtained high-temperature steam can be used for heating and drying the aluminum ash and the desulfurized gypsum. Since it is necessary to control the conversion of the dihydrate desulfurized gypsum into the hemihydrate desulfurized gypsum, the temperature of the heating medium needs to be strictly controlled. The temperature of the high-temperature steam is far lower than that of the flue gas, so that the process control is facilitated.
A method for producing sulphoaluminate cement and co-producing sulphur by utilizing desulfurized gypsum and aluminum ash comprises the following steps:
1) drying the aluminum ash, and heating and dehydrating the desulfurized gypsum to convert the desulfurized gypsum into semi-hydrated gypsum;
2) uniformly mixing the activated carbon, the aluminum ash and the semi-hydrated gypsum according to a set proportion, and then grinding and homogenizing;
3) calcining the mixture of the aluminum ash and the semi-hydrated gypsum after grinding and homogenizing at 1250-1300 ℃ for 30-60min to obtain sulphoaluminate cement clinker and flue gas containing sulfur dioxide;
4) dedusting and catalytic reduction are carried out on the flue gas containing sulfur dioxide to prepare a sulfur product;
wherein the mass ratio of the aluminum ash to the desulfurized gypsum to the activated carbon is as follows: 33-39: 61-67: 0.5-1.
Under the calcination condition, the combination of all components in the cement clinker obtained by calcination can be ensured to meet the requirement of preparing sulphoaluminate cement, and the excessive sulfur dioxide can be released to prepare more sulfur, so that the joint production of cement and sulfur becomes possible.
The inventor thought that more desulfurized gypsum was used instead of the original limestone in order to make his own idea, but if only desulfurized gypsum was used, calcination was carried out in a rotary kiln, CaSO4Decomposition occurs at 1250-2O3·CaSO4The formation stage of (a) provides an insufficient amount of CaO, affecting the quality of the produced sulphoaluminate cement. CaSO4The more thorough decomposition can occur at the temperature of 1350-2O3·CaSO4The decomposition temperature of (a) produces impurities, and the sulphoaluminate cement cannot be prepared.
Therefore, how to prepare a large amount of sulfur dioxide while preparing a large amount of sulphoaluminate cement by using the desulfurized gypsum to replace limestone is a problem which needs to be solved urgently.
Repeated experiments prove that when the active carbon is added into the raw material, the active carbon and the desulfurized gypsum can perform oxidation-reduction reaction at a lower temperature, and when the mass ratio of the aluminum ash to the desulfurized gypsum to the active carbon is as follows: 33-39: 61-67: 0.5-1, the calcination temperature is 1250-.
In the cement calcination process, because limestone is not used as a raw material for providing calcium base, when the cement clinker is produced and sulfuric acid is CO-produced with the traditional desulfurized gypsum, the CaO content in the ordinary portland cement clinker is usually 64-67%, while the CaO content in the sulphoaluminate cement clinker is only 38-48%, and the difference of the calcium content means that CO released by calcium carbonate calcination is released2Reduction; and the firing temperature is 150 ℃ and 200 ℃ lower than that of portland cement, the energy consumption is low, and the CO is further reduced2Discharging; applying life cycle evaluation theory to obtain CO released by unit production of cement clinker2The discharge amount is only 40% of the conventional portland cement clinker.
In addition, the amount of the added desulfurized gypsum is small in the traditional method, only calcium sulfate in the desulfurized gypsum is utilized, and limestone needs to be added to meet the formula of the sulphoaluminate cement, but under the method, the use amount of the desulfurized gypsum is small (generally 5-15% of the total mass of the ingredients), and the desulfurized gypsum with rich stockpiling amount cannot be fully utilized. The dosage of the desulfurized gypsum is more (61% -67%), during the production process, one part of desulfurized gypsum exists in the mixture in the form of calcium sulfate, and the other part of desulfurized gypsum is reduced and decomposed to generate calcium oxide, and the formula requirements of the sulphoaluminate cement can be met through reasonable proportioning. The use amount of the desulfurized gypsum is large, the aim of preparing the sulphoaluminate cement by using a large amount of desulfurized gypsum is fulfilled, and great contribution is made to the desulfurized gypsum stored in the digestion reactor.
Sufficient amount of coal powder is added in the calcining process of the desulfurized gypsum to burn the coal powder, so that redundant oxygen in the rotary kiln can be consumed, the rotary kiln is in a weak oxidizing atmosphere, and meanwhile, the decomposition rate and the desulfurization rate of the desulfurized gypsum are guaranteed due to the existence of the activated carbon.
Preferably, in the step 1), the temperature for converting the desulfurized gypsum into the semi-hydrated desulfurized gypsum through heating dehydration is 120-140 ℃.
Preferably, in the step 2), the chemical composition of the raw material obtained by uniformly mixing the aluminum ash and the semi-hydrated gypsum is as follows: SiO 223-10 parts by weight; 36-43 parts of CaO; al (Al)2O328-40 parts by weight; fe2O31-3 parts by weight; SO (SO)38 to 15 parts by weight of
Further preferably, the values of the raw meal are: coefficient of basicity Cm0.95-0.98, the aluminum-sulfur ratio P is between 1.05-1.22 (the aluminum-sulfur ratio is far less than the control value of 3.86 in the conventional preparation of sulphoaluminate because the calcium source is obtained by partial decomposition of desulfurized gypsum), and the aluminum-silicon ratio is 2-3.
Wherein,
Preferably, in the step 2), the particle size after grinding is less than 8 μm.
The currently accepted grain composition for the optimum performance of cement is as follows: 3-32 mu m, because the 3-32 mu m particles play a main role in strength increase, especially the 3-8 mu m particles are particularly important for cement performance, and the more the content is, the better the performance is.
Preferably, in step 3), the prepared sulphoaluminate cement clinker is prepared by mixing calcium sulphoaluminate (3CaO 3 Al)2O3·CaSO4) Dicalcium silicate (2 CaO. SiO)2) And the iron phase is a main mineral phase, and the iron phase accounts for 30-50%, 25-40% and 0-4% respectively.
The later strength of the prepared sulphoaluminate cement is continuously increased, and the compressive strength can reach 53.4MPa in 3 days and 75.2MPa in 28 days through a compressive strength test.
Preferably, in step 3), the fuel used for calcination is coal powder or coal gas.
Preferably, in step 3), the excess air factor for the combustion of coal dust is less than 1.05.
The excess air factor is the ratio of the mass of air actually supplied to burn 1kg of fuel to the mass of air required to theoretically fully burn 1kg of fuel.
Preferably, the step 3) further comprises a step of heating water by using the flue gas containing sulfur dioxide to obtain high-temperature steam, wherein the high-temperature steam is used as a heating medium for heating the aluminum ash and the desulfurized gypsum.
Preferably, in the step 4), the mass ratio of the sulphoaluminate cement clinker to the desulfurized gypsum is 100: 5.
Preferably, in the step 5), the dust concentration in the flue gas after dust removal is less than 10g/NM3。
The flue gas discharged from the rotary kiln is dedusted, and the activated carbon fixed bed with the granularity of 10 meshes is reused for reduction, so that the service life of the activated carbon fixed bed can be prolonged, and the purity of the sulfur can be improved, and the purity of the prepared sulfur can reach more than 97%.
The sulphoaluminate cement prepared by the preparation method.
The preparation principle of reducing sulfur dioxide in kiln gas containing sulfur dioxide into sulfur by a waste heat recycling device and an active carbon fixed bed is as follows:
C+SO2＝0.5S2+CO2；
in addition to the main reaction, there are many by-products, such as CO, COS, H2S、CS2Etc., the formation reaction mainly comprises:
CO2+C＝2CO；
CO+0.5S2＝COS；
5SO2+H2O+7C＝5CO2+0.5S2+H2S+COS+CS2；
S2+C＝CS2。
due to H2S，COS，CS2Are all reducing agents, they are all capable of reacting with SO2Reacting at a certain temperature to generate elemental sulfur, namely:
2H2S+SO2＝1.5S2+2H2O；
2COS+SO2＝1.5S2+2CO2；
CS2+SO2＝1.5S2+CO2。
the beneficial technical effects of the invention are as follows:
the invention comprehensively utilizes the desulfurized gypsum and the aluminum ash to produce the sulphoaluminate special cement and coproduce the sulfur, the raw materials required for production mainly come from the desulfurized products of the power plant, the waste residue aluminum ash generated by the electrolytic aluminum plant and the reducing agent active carbon, and the raw materials are wide in material availability and low in price. The method not only recycles industrial solid wastes, but also produces high-performance sulphoaluminate cement clinker, the produced sulphoaluminate cement clinker can produce special cement or additives of conventional cement, and is widely applied to rush repair, rush construction engineering, winter construction engineering and corrosion-resistant engineering, and the co-produced sulfur can meet the high-purity quality requirement while producing the sulphoaluminate cement clinker, and can be used in the chemical industry, food industry and pharmaceutical industry.
Drawings
FIG. 1 is a schematic process flow diagram of a method for producing sulphoaluminate cement and co-producing sulphur by using desulfurized gypsum and aluminum ash in example 1 and example 2;
FIG. 2 is a schematic view of the process flow of the method for producing sulphoaluminate cement and co-producing sulphur by using desulfurized gypsum and aluminum ash in example 3.
Detailed Description
The invention is further described with reference to the following figures and specific examples.
Example 1
As shown in fig. 1, the aluminum ash and the desulfurized gypsum are respectively fed into a dryer, and the desulfurized gypsum is calculated by the dried solid matter: 61%, aluminum ash: 38% and 1% of activated carbon. Directly conveying the mixture into a hollow rotary kiln for calcination, wherein the calcination temperature is 1280 ℃, and the calcination time is 60 minutes. The generated high-temperature kiln gas passes through waste heat recovery equipment, and high-temperature steam and hot water as byproducts are used for indirectly drying the original aluminum ash and the desulfurized gypsum. And (3) discharging kiln gas from the waste heat recovery equipment, reducing the gas temperature to 860 ℃, performing dust removal, dehumidification and purification, supplementing air, adjusting the oxygen-sulfur ratio, drying, then feeding the gas into an active carbon fixed bed with the granularity of 10 meshes, performing catalytic reduction to generate elemental sulfur, wherein the purity of the prepared sulfur reaches 98%, heating by adopting microwave, evaporating the sulfur attached to the active carbon fixed bed, and cooling and collecting the sulfur in a collecting device. The sulphoaluminate clinker generated in the rotary kiln is cooled by a grate cooler, so that the sulphoaluminate cement clinker is rapidly cooled, and the cooled and sintered clinker has main phases of calcium sulphoaluminate, dicalcium silicate and iron phases with the contents of 40 percent, 40 percent and 4 percent respectively, and belongs to high-silicon high-iron sulphoaluminate cement.
The compressive strength of the cement is 53.4MPa and 75.2MPa respectively in 3 days and 28 days through a cement standard mortar strength test (GB/T17671-1999).
Example 2
Send into aluminium ash, desulfurization gypsum respectively in the drying-machine to the solid matter after the stoving counts, desulfurization gypsum: 66%, aluminum ash: 33% and 1% of activated carbon. Directly conveying the mixture into a hollow rotary kiln for calcination, wherein the calcination temperature is 1250 ℃, and the calcination time is 50 minutes. The generated high-temperature kiln gas passes through waste heat recovery equipment, and high-temperature steam and hot water as byproducts are used for indirectly drying the original aluminum ash and the desulfurized gypsum. And (3) discharging kiln gas from the waste heat recovery equipment, reducing the gas temperature to 855 ℃, performing dust removal, dehumidification and purification, supplementing air, adjusting the oxygen-sulfur ratio, drying, then feeding the gas into an active carbon fixed bed with the granularity of 10 meshes, performing catalytic reduction to generate elemental sulfur, wherein the purity of the prepared sulfur reaches 99%, heating by adopting microwaves, evaporating the sulfur attached to the active carbon fixed bed, and cooling and collecting the sulfur in a collecting device. The sulphoaluminate clinker generated in the rotary kiln is cooled by a grate cooler, so that the sulphoaluminate cement clinker is rapidly cooled, and the cooled and sintered clinker has main phases of calcium sulphoaluminate, dicalcium silicate and iron phases with the contents of 50 percent, 45 percent and 3 percent respectively, and belongs to high-silicon high-iron sulphoaluminate cement.
The compressive strength of the cement is 55.4MPa and 80.2MPa respectively in 3 days and 28 days through a cement standard mortar strength test (GB/T17671-1999).
Example 3
As shown in fig. 2, the aluminum ash and the desulfurized gypsum are respectively fed into the dryer, and the desulfurized gypsum is calculated by the dried solid matter: 65% of aluminum ash: 34% and 1% of activated carbon. Directly conveying the mixture into a hollow rotary kiln, and introducing coal gas into the rotary kiln for calcination at 1300 ℃ for 30 minutes. The generated high-temperature kiln gas passes through waste heat recovery equipment, and high-temperature steam and hot water as byproducts are used for indirectly drying the original aluminum ash and the desulfurized gypsum. The kiln gas discharged from the waste heat recovery equipment is cooled to 860 ℃, and enters a two-stage reactor after being dedusted, dehumidified, purified, supplemented with air to adjust the oxygen-sulfur ratio and dried, wherein each reactor is filled with Cu/Al2O3Introducing coal gas into the two-section reactor, performing catalytic reduction to generate elemental sulfur, wherein the purity of the prepared sulfur reaches 98%, heating by microwave to evaporate the sulfur attached to the active carbon fixed bed, and cooling and collecting in a collecting device. The sulphoaluminate clinker generated in the rotary kiln is cooled by a grate cooler, so that the sulphoaluminate cement clinker is rapidly cooled, and the cooled and sintered clinker has main phases of calcium sulphoaluminate, dicalcium silicate and iron phases with the contents of 50 percent, 40 percent and 4 percent respectively, and belongs to high-silicon high-iron sulphoaluminate cement.
The compressive strength of the cement is 53.4MPa and 75.2MPa respectively in 3 days and 28 days through a cement standard mortar strength test (GB/T17671-1999).
The invention has the following remarkable characteristics:
(1) the production process of the present invention is different from the previous production technology of producing sulfur and cement, and the cement product prepared by the present invention belongs to sulphoaluminate cement, rather than the conventional portland cement. The mineral composition of the sulphoaluminate cement is different from that of ordinary portland cement and is prepared by calcium sulphoaluminate (3CaO 3 Al)2O3·CaSO4) Dicalcium silicate (2 CaO. SiO)2) And iron phase as main mineralThe phase is sintered at low temperature of 1250-;
(2) the production of the cement has easy operability, and when the gypsum raw materials are used for producing the sulfuric acid and the Portland cement, the clinker can not contain high SO3The decomposition rate of gypsum needs to be strictly controlled, a reducing agent needs to be added, and the calcining process needs to be controlled to be in a weak reducing atmosphere, otherwise the problems of unstable kiln conditions or unqualified clinker quality can be caused; when the sulphoaluminate cement is co-produced, the clinker per se requires higher SO3Content, so that it is not necessary to control the calcining atmosphere intentionally, and thus the operability of production is greatly improved.
(3) Because the temperature required for calcining the sulphoaluminate cement clinker is 1250-1300 ℃ and is 100 ℃ lower than the temperature for calcining the portland cement, the tail part of the rotary kiln is additionally provided with a waste heat recycling device for drying the raw materials entering the kiln, the use amount of coal and electric energy is greatly reduced, and energy conservation and consumption reduction can be fundamentally realized.
(4) Because the raw materials in the production process of the product are completely from industrial solid wastes, the cost of the produced raw materials is low, the market value of the prepared high-performance sulphoaluminate cementing material is high, and meanwhile, the elemental sulfur is co-produced, so that the added value of the whole produced product is high.
In view of the technical advantages in various aspects, the method utilizes the aluminum ash and the desulfurized gypsum to produce the special sulphoaluminate cement and co-produce the sulfur, has obvious application value, and can form outstanding economic benefit and environmental benefit when being implemented. The method for preparing the kiln gas into the sulfur can effectively solve the problem of storage and transportation of sulfuric acid which is difficult to solve in the acid making industry.
Although the embodiments of the present invention have been described with reference to the accompanying drawings, it is not intended to limit the scope of the invention, and it should be understood by those skilled in the art that various modifications and variations can be made without inventive faculty, based on the technical solutions of the present invention.
Claims (7)
1. A method for producing sulphoaluminate cement and co-producing sulphur by using desulfurized gypsum and aluminum ash is characterized by comprising the following steps: the method is carried out in a sulfur co-production device, the device comprises a dryer, a pulverizer, a rotary kiln, a cement pulverizer, a cement storage tank, a dust remover and a reduction fixed bed, a waste heat recovery device is connected between the rotary kiln and the dust remover,
the method comprises the following steps:
1) drying the aluminum ash in a dryer, and heating and dehydrating the desulfurized gypsum in the dryer to convert the desulfurized gypsum into semi-hydrated gypsum;
2) uniformly mixing the activated carbon, the aluminum ash and the semi-hydrated gypsum according to a set proportion, and sending the mixture to a pulverizer for pulverizing and homogenizing;
3) delivering the mixture of the aluminum ash and the semi-hydrated gypsum after grinding and homogenizing to a rotary kiln for calcining at 1250-1300 ℃ for 30-60min to obtain sulphoaluminate cement clinker and flue gas containing sulfur dioxide;
conveying the pulverized coal into the rotary kiln in the process; mixing the calcined sulphoaluminate clinker and the desulfurized gypsum according to the mass ratio of 100:5, grinding in a cement grinding machine, and conveying the obtained sulphoaluminate cement to a cement storage tank for storage;
4) the flue gas containing sulfur dioxide is dedusted by a deduster and conveyed to a reduction fixed bed for catalytic reduction to prepare a sulfur product;
the flue gas discharged from the rotary kiln heats water in the waste heat recovery equipment, the obtained high-temperature steam is introduced into the dryer to be used as a heating medium, and the cooled flue gas enters a dust remover for dust removal;
wherein the mass ratio of the aluminum ash, the desulfurized gypsum and the active carbon is as follows: 33-39: 61-67: 0.5-1.
2. The method of claim 1, wherein: in the step 1), the temperature for converting the desulfurized gypsum into the semi-hydrated gypsum through heating and dehydration is 120-140 ℃.
3. The method of claim 1, wherein the step of removing the metal oxide is performed in a batch processThe method comprises the following steps: in the step 2), the chemical composition of the raw material obtained by uniformly mixing the aluminum ash and the semi-hydrated gypsum is as follows: SiO 223-10 parts by weight; 36-43 parts of CaO; al (Al)2O328-40 parts by weight; fe2O31-3 parts by weight; SO (SO)38-15 parts by weight.
4. The method of claim 3, wherein: the raw material rate values were: coefficient of basicity Cm0.95-0.98, 1.05-1.22 of aluminum-sulfur ratio P and 2-3 of aluminum-silicon ratio.
5. The method of claim 1, wherein: in the step 3), the fuel during calcination is coal powder or coal gas.
6. The method of claim 1, wherein: in the step 3), the prepared sulphoaluminate cement clinker is prepared by calcium sulphoaluminate 3 CaO.3Al2O3·CaSO4Dicalcium silicate 2CaO SiO2And the iron phase is a main mineral phase, and the iron phase accounts for 30-50%, 25-40% and 0-4% respectively.
7. The method of claim 1, wherein: in the step 3), the method also comprises a step of heating water by using the flue gas containing sulfur dioxide to obtain high-temperature steam, wherein the high-temperature steam is used as a heating medium for heating the aluminum ash and the desulfurized gypsum.
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| PCT/CN2017/109612 WO2018166220A1 (en) | 2017-03-17 | 2017-11-07 | Method for co-producing sulphoaluminate cement and sulfur by using desulfurized gypsum and aluminum ash |
| ZA2019/06733A ZA201906733B (en) | 2017-03-17 | 2019-10-11 | Method for co-producing sulphoaluminate cement and sulfur by using desulfurized gypsum and aluminum ash |
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| CN107056102B (en) * | 2017-03-17 | 2020-01-24 | 山东卓联环保科技有限公司 | System and method for producing sulphoaluminate cement and co-producing sulfur by utilizing desulfurized gypsum and aluminum ash |
| CN108640175A (en) * | 2018-05-24 | 2018-10-12 | 焦作市远润环保科技有限公司 | A kind of production method of purifying agent |
| CN108863123B (en) * | 2018-07-25 | 2021-08-03 | 西南科技大学 | Process for preparing aluminate cement by replacing part of high alumina bauxite with aluminum ash |
| CN108773849A (en) * | 2018-08-23 | 2018-11-09 | 长沙中硅水泥技术开发有限公司 | The System and method for of cement kiln synergic processing Quadratic aluminum dust |
| CN109987866B (en) * | 2019-04-15 | 2020-03-31 | 山东大学 | Method and system for producing low alkalinity, new mineral system sulfoaluminate cement using steel slag |
| CN111233356B (en) * | 2020-03-10 | 2021-04-06 | 山东大学 | A method and system for preparing sulfoaluminate cement from all solid waste pretreated with aluminum ash |
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| CN112028506B (en) * | 2020-09-15 | 2022-04-15 | 齐鲁工业大学 | Method and system for co-production of sulfoaluminate-potassium magnesium phosphate composite gel material and sulfur |
| CN113149476A (en) * | 2021-04-10 | 2021-07-23 | 浙江红狮环保股份有限公司 | Method for disposing electrolytic aluminum ash in cement clinker production |
| CN113443643B (en) * | 2021-05-25 | 2022-04-01 | 昆明理工大学 | Method for cooperatively treating aluminum ash, carbon slag and desulfurized gypsum slag |
| CN114133196B (en) * | 2021-11-22 | 2023-04-11 | 云南森博混凝土外加剂有限公司 | Cement grouting material and preparation method thereof |
| CN114620753B (en) * | 2021-11-29 | 2023-08-18 | 浙江天石纳米科技股份有限公司 | Low-carbon process method for producing light calcium carbonate by comprehensively utilizing chemical reaction heat |
| CN116835895A (en) * | 2023-06-26 | 2023-10-03 | 中铝郑州有色金属研究院有限公司 | A method for recycling desulfurized gypsum |
| CN116969703B (en) * | 2023-09-18 | 2023-12-19 | 常熟理工学院 | A method for preparing geopolymerized sulfoaluminate cement using lithium slag and secondary aluminum ash |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0838443A1 (en) * | 1996-10-26 | 1998-04-29 | Ardex Gmbh | Utilization of wastes containing alumina |
| CN103304170A (en) * | 2013-06-28 | 2013-09-18 | 重庆大学 | Method for producing sulphate aluminum cement |
| CN103922622A (en) * | 2014-03-20 | 2014-07-16 | 山东大学 | Process for producing sulphoaluminate cement by using aluminum ash |
| CN106365476A (en) * | 2016-09-23 | 2017-02-01 | 金正大诺泰尔化学有限公司 | Combined production method for preparing sulphoaluminate cement and sulfuric acid from flue gas desulfurization gypsum |
| CN106430111A (en) * | 2016-09-18 | 2017-02-22 | 江苏德义通环保科技有限公司 | Method for preparing sulfur by recycling sulfur dioxide from flue gas |
| CN106431031A (en) * | 2016-09-23 | 2017-02-22 | 金正大生态工程集团股份有限公司 | Phosphogypsum sulphoaluminate cement sulfuric acid coproduction method |
| CN206692569U (en) * | 2017-03-17 | 2017-12-01 | 山东卓联环保科技有限公司 | A kind of system using desulfurated plaster and aluminium ash production sulphate aluminium cement coproduction sulphur |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101468792B (en) * | 2007-12-28 | 2013-03-20 | 尹小林 | Novel technique for producing sulfur from industrial waste gypsum |
| CN107056102B (en) * | 2017-03-17 | 2020-01-24 | 山东卓联环保科技有限公司 | System and method for producing sulphoaluminate cement and co-producing sulfur by utilizing desulfurized gypsum and aluminum ash |
-
2017
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- 2017-11-07 WO PCT/CN2017/109612 patent/WO2018166220A1/en not_active Ceased
-
2019
- 2019-10-11 ZA ZA2019/06733A patent/ZA201906733B/en unknown
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0838443A1 (en) * | 1996-10-26 | 1998-04-29 | Ardex Gmbh | Utilization of wastes containing alumina |
| CN103304170A (en) * | 2013-06-28 | 2013-09-18 | 重庆大学 | Method for producing sulphate aluminum cement |
| CN103922622A (en) * | 2014-03-20 | 2014-07-16 | 山东大学 | Process for producing sulphoaluminate cement by using aluminum ash |
| CN106430111A (en) * | 2016-09-18 | 2017-02-22 | 江苏德义通环保科技有限公司 | Method for preparing sulfur by recycling sulfur dioxide from flue gas |
| CN106365476A (en) * | 2016-09-23 | 2017-02-01 | 金正大诺泰尔化学有限公司 | Combined production method for preparing sulphoaluminate cement and sulfuric acid from flue gas desulfurization gypsum |
| CN106431031A (en) * | 2016-09-23 | 2017-02-22 | 金正大生态工程集团股份有限公司 | Phosphogypsum sulphoaluminate cement sulfuric acid coproduction method |
| CN206692569U (en) * | 2017-03-17 | 2017-12-01 | 山东卓联环保科技有限公司 | A kind of system using desulfurated plaster and aluminium ash production sulphate aluminium cement coproduction sulphur |
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| CN107056102A (en) | 2017-08-18 |
| ZA201906733B (en) | 2020-09-30 |
| WO2018166220A1 (en) | 2018-09-20 |
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