CN116425123A - Device system and method for preparing calcium sulfide by utilizing industrial byproduct gypsum - Google Patents
Device system and method for preparing calcium sulfide by utilizing industrial byproduct gypsum Download PDFInfo
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- CN116425123A CN116425123A CN202310397840.5A CN202310397840A CN116425123A CN 116425123 A CN116425123 A CN 116425123A CN 202310397840 A CN202310397840 A CN 202310397840A CN 116425123 A CN116425123 A CN 116425123A
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- 229910052602 gypsum Inorganic materials 0.000 title claims abstract description 98
- 239000010440 gypsum Substances 0.000 title claims abstract description 98
- 238000000034 method Methods 0.000 title claims abstract description 74
- 239000006227 byproduct Substances 0.000 title claims abstract description 58
- JGIATAMCQXIDNZ-UHFFFAOYSA-N calcium sulfide Chemical compound [Ca]=S JGIATAMCQXIDNZ-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000006243 chemical reaction Methods 0.000 claims abstract description 86
- 238000010438 heat treatment Methods 0.000 claims abstract description 85
- 239000007789 gas Substances 0.000 claims abstract description 73
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000003546 flue gas Substances 0.000 claims abstract description 48
- 238000002156 mixing Methods 0.000 claims abstract description 48
- 239000002002 slurry Substances 0.000 claims abstract description 47
- 238000001035 drying Methods 0.000 claims abstract description 46
- 239000000428 dust Substances 0.000 claims abstract description 35
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 33
- 238000001354 calcination Methods 0.000 claims abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 10
- 238000006477 desulfuration reaction Methods 0.000 claims description 47
- 230000023556 desulfurization Effects 0.000 claims description 47
- 239000007787 solid Substances 0.000 claims description 40
- 230000008569 process Effects 0.000 claims description 39
- 238000002485 combustion reaction Methods 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 239000012495 reaction gas Substances 0.000 claims description 24
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 claims description 23
- 230000003009 desulfurizing effect Effects 0.000 claims description 18
- 239000012065 filter cake Substances 0.000 claims description 11
- 238000003825 pressing Methods 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 239000000571 coke Substances 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000003245 coal Substances 0.000 claims description 6
- 239000000956 alloy Substances 0.000 claims description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 229910052814 silicon oxide Inorganic materials 0.000 claims 1
- 238000004064 recycling Methods 0.000 abstract description 3
- 230000009471 action Effects 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 9
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 235000011941 Tilia x europaea Nutrition 0.000 description 8
- 239000004571 lime Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000008267 milk Substances 0.000 description 7
- 210000004080 milk Anatomy 0.000 description 7
- 235000013336 milk Nutrition 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 7
- 239000011593 sulfur Substances 0.000 description 7
- 238000000354 decomposition reaction Methods 0.000 description 6
- 206010039509 Scab Diseases 0.000 description 5
- 238000009825 accumulation Methods 0.000 description 5
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Inorganic materials [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000004566 building material Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 231100000241 scar Toxicity 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000002817 coal dust Substances 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 208000032544 Cicatrix Diseases 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000011426 gypsum mortar Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000941 radioactive substance Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000037387 scars Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Images
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
- C01B17/42—Sulfides or polysulfides of magnesium, calcium, strontium, or barium
- C01B17/44—Sulfides or polysulfides of magnesium, calcium, strontium, or barium by reduction of sulfates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
- B01D46/02—Particle separators, e.g. dust precipitators, having hollow filters made of flexible material
- B01D46/023—Pockets filters, i.e. multiple bag filters mounted on a common frame
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/80—Semi-solid phase processes, i.e. by using slurries
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J6/00—Heat treatments such as Calcining; Fusing ; Pyrolysis
- B01J6/001—Calcining
- B01J6/002—Calcining using rotating drums
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F26—DRYING
- F26B—DRYING SOLID MATERIALS OR OBJECTS BY REMOVING LIQUID THEREFROM
- F26B21/00—Arrangements or duct systems, e.g. in combination with pallet boxes, for supplying and controlling air or gases for drying solid materials or objects
- F26B21/004—Nozzle assemblies; Air knives; Air distributors; Blow boxes
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27B—FURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
- F27B7/00—Rotary-drum furnaces, i.e. horizontal or slightly inclined
- F27B7/08—Rotary-drum furnaces, i.e. horizontal or slightly inclined externally heated
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27B—FURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
- F27B7/00—Rotary-drum furnaces, i.e. horizontal or slightly inclined
- F27B7/20—Details, accessories, or equipment peculiar to rotary-drum furnaces
- F27B7/2075—Removing incrustations
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
- F27D17/00—Arrangements for using waste heat; Arrangements for using, or disposing of, waste gases
- F27D17/008—Arrangements for using waste heat; Arrangements for using, or disposing of, waste gases cleaning gases
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
- F27D25/00—Devices or methods for removing incrustations, e.g. slag, metal deposits, dust; Devices or methods for preventing the adherence of slag
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
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- Chemical & Material Sciences (AREA)
- General Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
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- Inorganic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention provides a device system and a method for preparing calcium sulfide by utilizing industrial byproduct gypsum. The reaction unit comprises a reducing agent crusher and a slurry mixing tank; the drying and dedusting unit comprises a rotary dryer, a cyclone collector and a gas treatment device; the external heat calcination unit comprises an external heat type rotary kiln reaction cylinder. According to the invention, the external heating type rotary kiln heating medium is isolated from the reaction materials, the generated gas quantity is very small, the reaction dust is prevented from being raised by high-temperature flue gas, the dust quantity is small, and the problem of equipment height Wen Jieba can be effectively solved by knocking the external part of the external heating type rotary kiln; the clean high-temperature flue gas heated by the external heating type rotary kiln is used as a heat source of the rotary flash dryer, so that the heat utilization rate can be greatly improved; in addition, the invention can realize the recycling of industrial byproduct gypsum and eliminate the hidden danger of the environment.
Description
Technical Field
The invention belongs to the technical field of recycling of bulk solid wastes, relates to a treatment method of industrial byproduct gypsum, and particularly relates to a device system and a method for preparing calcium sulfide by utilizing industrial byproduct gypsum.
Background
At present, the accumulated accumulation and accumulation amount of the byproduct gypsum in the industry in China is more than 10 hundred million tons, and the accumulated accumulation amount is mainly phosphogypsum, titanium gypsum, fluorine gypsum, salt gypsum and the like. The desulfurization gypsum is used for removing SO in the flue gas by a calcium method 2 The produced waste slag contains heavy metal, chloride ions, silicon dioxide, acid oxide and other impurities, and the annual production amount is about 8000 ten thousand tons; phosphogypsum is waste residue generated in a wet phosphoric acid process, the phosphogypsum has complex composition, wherein more than 90 percent of phosphogypsum is calcium sulfate dihydrate, and contains phosphorus, fluorine, organic matters, oxides, a small amount of heavy metals, radioactive substances and other impurities, the annual production amount is 7800 ten thousand tons, and the accumulation amount is more than 6 hundred million tons; the titanium gypsum is waste residue generated by neutralizing acid waste water with lime or carbide slag in the production of titanium dioxide by a sulfuric acid method, the main impurities are ferric hydroxide, ferrous sulfate, aluminum hydroxide and silicon dioxide, the appearance is yellow red mud-like powder, the annual production amount reaches 2800 ten thousand tons, and the total accumulation amount of the titanium gypsum is approximately 2 hundred million tons. Besides, the method has the advantages that besides the utilization rate of the desulfurized gypsum is relatively high, most of the desulfurized gypsum is in a piling state, and a large amount of land is occupied for outdoor piling, so that the desulfurized gypsum becomes industrial waste residue which seriously pollutes the environment.
The industrial by-product gypsum can be used as cement coagulant, gypsum board, gypsum block, gypsum mortar, etc., and has relatively large application in building material industry. However, the industrial byproduct gypsum has huge production quantity and unstable composition, so that the produced building material product has peculiar smell, easy deformation, mildew, salt flashing and the like, has poor market acceptance, and a plurality of byproduct gypsum production places, such as phosphogypsum which is concentrated in regions of Yunnan, guizhou, hubei, chongqing, sichuan and the like, have low added value of gypsum building materials and small market radiation radius, and severely restrict the expansion of the gypsum building material product in the market.
The preparation of calcium sulfide by using industrial by-product gypsum as raw material is a promising approach to fully utilize calcium and sulfur resources in solid waste phosphogypsum, and its main method is to use coke powder, coal dust, sulfur or reducing gas such as CO and H 2 S and the like are used as reducing agents, and the byproduct gypsum is reduced into calcium sulfide under high-temperature reducing atmosphere. The calcium sulfide further reacts with gypsum to prepare sulfuric acid, which can be directly recycled to form sulfuric acid circulation; the calcium sulfide can also be used for preparing thiourea, sodium sulfide and sulfur, and is a chemical raw material with relatively high added value.
CN 101428767a discloses a method for preparing calcium sulfide by using gypsum, which comprises the steps of uniformly mixing phosphogypsum and coal according to a molar ratio of 1:2-4, grinding, adding water to prepare balls or blocks, and roasting at a high temperature of 800-1100 ℃ to finally obtain a calcium sulfide product. CN 101708825a discloses a method for preparing calcium sulfide by reducing and decomposing gypsum with sulfur, which uses gaseous sulfur as a reducing agent to reduce gypsum into calcium sulfide, and the byproduct sulfur dioxide is used for preparing sulfuric acid. CN 113200522A discloses a method for preparing H by decomposing nonferrous smelting flue gas desulfurization gypsum 2 S, preparing calcium sulfide from the desulfurized gypsum by taking coke as a reducing agent, and further preparing hydrogen sulfide, calcium carbonate and the like by taking the calcium sulfide as a raw material.
In summary, the reaction of the reducing agent with the byproduct gypsum to prepare the raw material of calcium sulfide is relatively simple, but the industrial implementation process still faces more difficulties, for example: 1. the gypsum particles are fine, the fluidity is strong, dust is generated, the control is difficult, the conventional measures are granulation and the like, but the process is complicated and difficult to implement; 2. the reaction process is extremely easy to scar, so that reaction equipment such as a fluidized bed and the like are difficult to operate; 3. independent from drying, low heat utilization rate, etc.
Therefore, the device system is used for preparing the calcium sulfide by the byproduct gypsum reaction, so that the defects of high dust amount and low heat utilization rate in the preparation process are overcome, and the device system is one of the problems to be solved in the field.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a device system and a method for preparing calcium sulfide by utilizing industrial byproduct gypsum. According to the invention, equipment such as an external heating rotary kiln and a spin flash dryer are adopted for process coupling, the characteristics that an external heating rotary kiln heating medium is isolated from reaction materials, the generated gas quantity is very small are utilized, reaction dust is prevented from being lifted by high-temperature flue gas, the dust quantity is small, and the problem of equipment height Wen Jieba can be effectively solved by utilizing scar removing structures such as knocking and the like outside the external heating rotary kiln; the clean high-temperature flue gas heated by the external heating type rotary kiln is used as a heat source of the rotary flash dryer, so that the heat utilization rate can be greatly improved.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a device system for preparing calcium sulfide by utilizing industrial byproduct gypsum, which comprises a reaction unit, a drying and dedusting unit and an external heat calcination unit which are sequentially connected;
the reaction unit comprises a reducing agent crusher, a slurry mixing tank, a filter press and a filter cake crusher which are sequentially connected;
the drying and dedusting unit comprises a rotary dryer, a cyclone receiver and a gas treatment device which are sequentially connected;
the solid inlet of the rotary dryer is connected with the filter cake crusher;
the external heat calcination unit comprises an external heat type rotary kiln reaction cylinder body, and an external heat type rotary kiln external heating chamber and a reaction gas secondary combustion chamber which are arranged on the periphery of the external heat type rotary kiln reaction cylinder body;
the solid outlet of the cyclone receiver is connected with the solid inlet of the externally heated rotary kiln reaction cylinder; and a gas outlet of the external heating chamber of the external heating rotary kiln is connected with a gas inlet of the rotary dryer.
The device system provided by the invention utilizes the characteristics that the heating medium of the external heating rotary kiln is isolated from the reaction materials and the generated gas quantity is very small by carrying out process coupling on the equipment such as the external heating rotary kiln, the rotary flash dryer and the like, so that the reaction dust is prevented from being raised by high-temperature flue gas, and the dust quantity is small.
As a preferable technical scheme of the invention, a mixing tank discharging pump is arranged between the slurry mixing tank and the filter press;
preferably, the gas treatment device comprises a bag-type dust collector, a desulfurizing tower and a drying induced draft fan which are sequentially connected;
preferably, a desulfurization circulating pump is arranged on the desulfurization tower;
preferably, a gas outlet of the desulfurizing tower is connected with the drying induced draft fan;
preferably, the liquid outlet of the desulfurizing tower is divided into two branches, one branch is connected with the desulfurizing circulating pump, and the other branch is connected with the inlet of the slurry mixing tank.
As a preferable technical scheme of the invention, a conveyor is arranged between the solid outlet of the cyclone collector and the solid inlet of the externally heated rotary kiln reaction cylinder.
Preferably, the head part and the tail part of the externally heated rotary kiln reaction cylinder are respectively and independently provided with a reaction cylinder knocking hammer.
The invention can effectively solve the problem of high Wen Jieba of the equipment by utilizing the structure of removing scars by the knocking hammer arranged outside the cylinder.
Preferably, a gas outlet of the externally heated rotary kiln reaction cylinder is sequentially connected with a high-temperature metal dust remover and a high-temperature flue gas fan.
Preferably, the outlet of the high-temperature flue gas fan is respectively connected with the gas inlet of the externally-heated rotary kiln reaction cylinder and the gas inlet of the reaction gas secondary combustion chamber.
Preferably, the outlet of the reaction gas secondary combustion chamber is connected with the inlet of the external heating chamber of the external heating rotary kiln.
As a preferable technical scheme of the invention, the material of the external heating rotary kiln cylinder comprises high-temperature resistant alloy.
Preferably, the reaction gas secondary combustion chamber and the external heating chamber of the external heating rotary kiln are respectively and independently provided with at least one external heating burner.
In a second aspect, the present invention provides a method for producing calcium sulfide using industrial by-product gypsum, the method being carried out using the apparatus system provided in the first aspect.
As a preferred embodiment of the present invention, the method comprises the steps of:
(1) Mixing industrial byproduct gypsum, water and a reducing agent in a slurry state in a slurry mixing tank, and then sequentially carrying out filter pressing, crushing and drying to obtain dry solids and dry flue gas;
(2) Calcining the dried solid obtained in the step (1) in a reducing atmosphere to obtain calcium sulfide.
The dry solid in the step (1) is a drying process byproduct gypsum and a reducing agent after free water and crystal water are removed; the calcination process in the step (2) needs to be carried out under a reducing atmosphere, otherwise, the positive hexavalent sulfur of the calcium sulfate in the gypsum does not become negative bivalent sulfur in the calcium sulfide, and the reaction principle is shown in the following equation:
2C + CaSO 4 ＝ CaS + 2CO 2 (1)
4C + CaSO 4 ＝ CaS + 4CO (2)
4CO+ CaSO 4 ＝ CaS + 4CO 2 (3)
as a preferred embodiment of the present invention, the industrial by-product gypsum in the step (1) comprises phosphogypsum and/or desulfurized gypsum.
Preferably, the mass ratio of the industrial by-product gypsum to the water is 1 (3-4), for example, 1:3, 1:3.2, 1:3.4, 1:3.6, 1:3.8 or 1:4, but the industrial by-product gypsum and the industrial by-product water are not limited to the listed values, and other non-listed values in the numerical range are applicable.
Preferably, the mass ratio of the industrial byproduct gypsum to the reducing agent is (4-6): 1, for example, 4:1, 4.4:1, 4.8:1, 5.2:1, 5.6:1 or 6:1, but the industrial byproduct gypsum and the reducing agent are not limited to the listed values, and other values which are not listed in the numerical range are applicable.
According to the invention, industrial byproduct gypsum, water and a reducing agent are mixed according to a certain mass ratio, wherein the excessive addition of the reducing agent can cause incomplete consumption of the reducing agent and increase of cost; when the amount of calcium sulfate is too low, the reducing atmosphere is weak, the calcium sulfate in gypsum is not completely decomposed, and the amount of calcium sulfide produced is reduced.
The industrial byproduct gypsum in a slurry state is needed to be used in the mixing process, and the method is mainly used for uniformly mixing (slurry mixing) the reducing agent and the gypsum, fully contacting and facilitating the reduction reaction; if the powder or the block gypsum is used, the method is equivalent to solid-solid mixing, has poor contact effect and is unfavorable for reaction.
Preferably, the reducing agent comprises coke breeze and/or coal fines.
Preferably, the fixed carbon content in the coke powder is more than or equal to 80%, for example, 80%, 85%, 90%, 95% or 98%, but is not limited to the recited values, and other non-recited values in the range of values are equally applicable; the silica content is less than 8%, for example, 7%, 6%, 5%, 4%, 3% or 2%, but not limited to the recited values, and other values not recited in the numerical range are equally applicable.
Preferably, the fixed carbon in the pulverized coal is equal to or greater than 70%, for example, 75%, 80%, 85%, 90% or 95%, but is not limited to the recited values, and other non-recited values in the numerical range are equally applicable; ash content below 15%, for example 13%, 11%, 9%, 7% or 5%, but not limited to the values recited, other values not recited in the numerical range are equally applicable.
Preferably, the reducing agent further comprises a process of breaking up.
The reducing agent is crushed to 80-100 meshes before mixing the raw materials, and the crushing aims are as follows: in order to be uniformly mixed with phosphogypsum, the contact area is increased.
It is worth to say that the filter cake is crushed after the filter pressing in the step (1), the average particle diameter after crushing is 8-10mm, the filter cake after filter pressing is large in block shape, and the crushing is mainly used for facilitating subsequent drying and dehydration.
In a preferred embodiment of the present invention, the drying temperature in the step (1) is 150 to 200. DegreeC, for example, 150. DegreeC, 160. DegreeC, 170. DegreeC, 180. DegreeC, 190. DegreeC or 200. DegreeC, but the present invention is not limited to the above-mentioned values, and other values not shown in the above-mentioned value range are applicable.
The drying temperature is 150-200 ℃, the drying temperature is determined according to the temperature provided by the subsequent flue gas, and in principle, the higher the drying temperature is, the better the drying temperature is, the quick dehydration of materials can be realized, and the drying time is shortened. However, the drying temperature cannot be too high, otherwise, the temperature requirement on the drying flue gas is too high, and the calcination temperature of the rotary kiln cannot be ensured; too low a temperature can result in slow cake dewatering and excessive drying times.
Preferably, the drying time in the step (1) is 30 to 60min, for example, 30min, 35min, 40min, 45min, 50min, 55min or 60min, but not limited to the recited values, and other values not recited in the numerical range are equally applicable.
Preferably, the heat source for drying in the step (1) comprises flue gas heated and cooled by an external heating rotary kiln. The cooling process is as follows: the high-temperature flue gas generated by fuel combustion heats the rotary kiln (external heating), the temperature of the rotary kiln is increased to ensure that the calcination temperature is 850-950 ℃, and the high-temperature flue gas is reduced to 400-500 ℃ and discharged to be used as a drying heat source.
In a preferred embodiment of the present invention, the calcination temperature in the step (2) is 850 to 950 ℃, and may be 850 ℃, 870 ℃, 890 ℃, 910 ℃,930 ℃, or 950 ℃, for example, but the present invention is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned value range are equally applicable.
The calcining temperature of the invention is 850-950 ℃. In theory, the higher the temperature is, the better the reaction speed is, but the higher the temperature is, the energy consumption is increased, and the materials are easy to be melted at high temperature, scar and adhere to the wall, so that the reaction operation is affected; when the temperature is too low, the conversion rate of calcium sulfate decreases, and the productivity of calcium sulfide decreases.
Preferably, the calcination time in the step (2) is 90 to 120min, for example, 90min, 95min, 100min, 105min, 110min or 115min, but not limited to the recited values, and other values not recited in the range of values are equally applicable.
Preferably, the reducing atmosphere in the step (2) is derived from the gas generated after the reaction in the external heat rotary kiln, and accounts for 30-50 vol%, such as 30vol%, 35vol%, 40vol%, 45vol% or 50vol%, of the total gas, but the reducing atmosphere is not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
In the invention, a part of gas generated after the reaction in the external heat rotary kiln is used as a reducing atmosphere so as to facilitate the calcination process, and the other part of gas is used as a heat source for drying in the step (1).
As a preferable technical scheme of the invention, the method further comprises a dust removal and desulfurization process for the dry gas obtained in the step (1) in sequence;
preferably, the content of calcium sulfide in the step (2) is 85-90%, for example, 85%, 86%, 87%, 88%, 89% or 90%, but not limited to the recited values, and other values not recited in the numerical range are equally applicable.
In addition to calcium sulfide, the calcined product of the invention contains unconverted calcium sulfate, silicon, aluminum and other impurities, wherein the content of the calcium sulfide is 85-90%.
The numerical ranges recited herein include not only the above-listed point values, but also any point values between the above-listed numerical ranges that are not listed, and are limited in space and for the sake of brevity, the present invention is not intended to be exhaustive of the specific point values that the stated ranges include.
Compared with the prior art, the invention has the following beneficial effects:
(1) The device system provided by the invention utilizes equipment such as an external heating rotary kiln and a spin flash dryer to carry out process coupling, and utilizes the characteristics that an external heating rotary kiln heating medium is isolated from reaction materials, the generated gas quantity is very small, reaction dust is prevented from being raised by high-temperature flue gas, and the dust quantity is small;
(2) The invention can effectively solve the problem of high Wen Jieba of the equipment by utilizing the knocking hammer arranged outside the external heating rotary kiln;
(3) The invention uses the clean high-temperature flue gas externally heated by the external heating rotary kiln as the heat source of the spin flash dryer, thereby greatly improving the utilization rate of heat;
(4) The method provided by the invention can realize the recycling of industrial byproduct gypsum and eliminate the hidden environmental trouble.
Drawings
FIG. 1 is a process flow diagram of a method for preparing calcium sulfide by utilizing industrial byproduct gypsum;
FIG. 2 is a schematic diagram of the system for preparing calcium sulfide by using industrial by-product gypsum;
wherein 1 is a reducing agent crusher, 2 is a slurry mixing tank, 3 is a mixing tank discharge pump, 4 is a filter press, 5 is a filter cake crusher, 6 is a rotary dryer, 7 is a cyclone receiver, 8 is a cloth bag dust remover, 9 is a conveyor, 10 is a desulfurizing tower, 11 is a desulfurizing circulating pump, 12 is a drying induced draft fan, 13 is an external heating rotary kiln reaction cylinder, 14 is an external heating rotary kiln external heating chamber, 15 is a reaction gas secondary combustion chamber, 16 is an external heating burner, 17 is a reaction cylinder knocking hammer, 18 is a high-temperature metal dust remover, and 19 is a high-temperature flue gas fan.
Detailed Description
The technical scheme of the invention is further described below by the specific embodiments with reference to the accompanying drawings. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
In one specific embodiment, the invention provides a device system for preparing calcium sulfide by utilizing industrial byproduct gypsum, which comprises a reaction unit, a drying and dedusting unit and an external heat calcination unit which are sequentially connected, as shown in fig. 2;
the reaction unit comprises a reducing agent crusher 1, a slurry mixing tank 2, a filter press 4 and a filter cake crusher 5 which are sequentially connected;
the drying and dedusting unit comprises a rotary dryer 6, a cyclone collector 7 and a gas treatment device which are sequentially connected;
the solid inlet of the rotary dryer 6 is connected with the filter cake crusher 5;
the external heat calcination unit comprises an external heat type rotary kiln reaction cylinder 13, an external heat type rotary kiln external heating chamber 14 and a reaction gas secondary combustion chamber 15, wherein the external heat type rotary kiln external heating chamber 14 and the reaction gas secondary combustion chamber 15 are arranged on the periphery of the external heat type rotary kiln reaction cylinder;
the solid outlet of the cyclone receiver 7 is connected with the solid inlet of the externally heated rotary kiln reaction cylinder 13; the gas outlet of the external heating chamber 14 of the external heating rotary kiln is connected with the gas inlet of the rotary dryer 6.
A mixing tank discharging pump 3 is arranged between the slurry mixing tank 2 and the filter press 4.
The gas treatment device comprises a bag-type dust collector 8, a desulfurizing tower 10 and a drying induced draft fan 12 which are sequentially connected; a desulfurization circulating pump 11 is arranged on the desulfurization tower 10; the gas outlet of the desulfurizing tower 10 is connected with the drying induced draft fan 12; the liquid outlet of the desulfurizing tower 10 is divided into two branches, one branch is connected with the desulfurizing circulation pump 11, and the other branch is connected with the inlet of the slurry mixing tank 3.
A conveyor 9 is arranged between the solid outlet of the cyclone receiver 7 and the solid inlet of the externally heated rotary kiln reaction cylinder 13; the head part and the tail part of the externally heated rotary kiln reaction cylinder 13 are respectively and independently provided with a reaction cylinder knocking hammer 17; the gas outlet of the externally heated rotary kiln reaction cylinder 13 is sequentially connected with a high-temperature metal dust remover 18 and a high-temperature flue gas fan 19;
the outlet of the high-temperature flue gas fan 18 is respectively connected with the gas inlet of the externally-heated rotary kiln reaction cylinder 13 and the gas inlet of the reaction gas secondary combustion chamber 15;
the outlet of the reaction gas secondary combustion chamber 15 is connected with the inlet of the external heating chamber 14 of the external heating rotary kiln.
The external heating rotary kiln cylinder 13 is made of high-temperature resistant alloy;
the reaction gas secondary combustion chamber 15 and the external heating chamber 14 of the external heating rotary kiln are respectively and independently provided with at least one external heating burner 16.
In another embodiment, the invention provides a method for preparing calcium sulfide by utilizing industrial byproduct gypsum by adopting the device system, as shown in fig. 1, comprising the following steps:
(1) Mixing industrial byproduct gypsum in a slurry state, water and crushed reducing agent in a slurry mixing tank, and then sequentially carrying out filter pressing, crushing and drying at 150-200 ℃ for 30-60 min to obtain dry solids and dry flue gas;
wherein, the mass ratio of the industrial by-product gypsum to the water is 1 (3-4), and the mass ratio of the industrial by-product gypsum to the reducing agent is (4-6) 1; the dry heat source comprises flue gas heated and cooled by an external heating rotary kiln;
(2) Calcining the dried solid obtained in the step (1) at 850-950 ℃ in a reducing atmosphere for 90-120 min to obtain calcium sulfide;
wherein the reducing atmosphere is from gas generated after the reaction in the external heating rotary kiln, and accounts for 30-50 vol% of the total gas amount;
(3) A dust removal and desulfurization process is sequentially carried out on the dry gas obtained in the step (1);
wherein, the desulfurization process is carried out in a desulfurization tower, and lime milk is adopted for desulfurization and then discharged; the desulfurization slurry is returned to the slurry mixing tank in the step (1).
Some of the component sources in the following examples and comparative examples are as follows:
the main components of phosphogypsum adopted by the invention are shown in table 1; the main components of the desulfurized gypsum are shown in Table 2; the main components of the coke are shown in table 3; the main components of the pulverized coal are shown in table 4.
TABLE 1
| Composition of the composition | H 2 O | CaO | SO 3 | SiO 2 | P 2 O 5 | Al 2 O 3 | Fe 2 O 3 | MgO |
| Content/wt% | 35-40 | 23-25 | 33-36 | 1.4-1.5 | 0.8-0.9 | 0.35-0.4 | 0.3-0.4 | 0.1-0.15 |
TABLE 2
| Composition of the composition | H 2 O | CaO | SO 3 | SiO 2 | Al 2 O 3 | Fe 2 O 3 | MgO |
| Content/wt% | 33-38 | 24-26 | 31-33 | 0.7-0.9 | 0.4-0.45 | 0.1-0.2 | 1.4-1.5 |
TABLE 3 Table 3
| Composition of the components | W f | V f | A f | C f | Others |
| Content/wt% | 1.2 | 3.8 | 11.5 (wherein SiO 2 ≤8.0) | 82.7 | 0.8 |
TABLE 4 Table 4
| Composition of the components | M ad | V daf | A d | FC ad | Others |
| Content/wt% | 2.03 | 14.50 | 12.36 | 71.28 | 0.6 |
Example 1
The embodiment provides a device system for preparing calcium sulfide by utilizing industrial byproduct gypsum, which comprises a reaction unit, a drying and dedusting unit and an external heat calcination unit which are sequentially connected;
the reaction unit comprises a reducing agent crusher 1, a slurry mixing tank 2, a filter press 4 and a filter cake crusher 5 which are sequentially connected;
the drying and dedusting unit comprises a rotary dryer 6, a cyclone collector 7 and a gas treatment device which are sequentially connected;
the solid inlet of the rotary dryer 6 is connected with the filter cake crusher 5;
the external heat calcination unit comprises an external heat type rotary kiln reaction cylinder 13, an external heat type rotary kiln external heating chamber 14 and a reaction gas secondary combustion chamber 15, wherein the external heat type rotary kiln external heating chamber 14 and the reaction gas secondary combustion chamber 15 are arranged on the periphery of the external heat type rotary kiln reaction cylinder;
the solid outlet of the cyclone receiver 7 is connected with the solid inlet of the externally heated rotary kiln reaction cylinder 13; the gas outlet of the external heating chamber 14 of the external heating rotary kiln is connected with the gas inlet of the rotary dryer 6.
A mixing tank discharging pump 3 is arranged between the slurry mixing tank 2 and the filter press 4.
The gas treatment device comprises a bag-type dust collector 8, a desulfurizing tower 10 and a drying induced draft fan 12 which are sequentially connected; a desulfurization circulating pump 11 is arranged on the desulfurization tower 10; the gas outlet of the desulfurizing tower 10 is connected with the drying induced draft fan 12; the liquid outlet of the desulfurizing tower 10 is divided into two branches, one branch is connected with the desulfurizing circulation pump 11, and the other branch is connected with the inlet of the slurry mixing tank 3.
A conveyor 9 is arranged between the solid outlet of the cyclone receiver 7 and the solid inlet of the externally heated rotary kiln reaction cylinder 13; the head part and the tail part of the externally heated rotary kiln reaction cylinder 13 are respectively and independently provided with a reaction cylinder knocking hammer 17; the gas outlet of the externally heated rotary kiln reaction cylinder 13 is sequentially connected with a high-temperature metal dust remover 18 and a high-temperature flue gas fan 19;
the outlet of the high-temperature flue gas fan 18 is respectively connected with the gas inlet of the externally-heated rotary kiln reaction cylinder 13 and the gas inlet of the reaction gas secondary combustion chamber 15;
the outlet of the reaction gas secondary combustion chamber 15 is connected with the inlet of the external heating chamber 14 of the external heating rotary kiln.
The external heating rotary kiln cylinder 13 is made of high-temperature resistant alloy;
the reaction gas secondary combustion chamber 15 is provided with an external heating burner 16; the external heating chamber 14 of the external heating rotary kiln is provided with three external heating burners 16.
Example 2
This example provides a system of apparatus for producing calcium sulfide using industrial by-product gypsum, which differs from example 1 only in that: the present embodiment omits the reaction cylinder knocking hammers 17 provided at the head and tail of the externally heated rotary kiln reaction cylinder 13.
Comparative example 1
This comparative example provides an apparatus system for preparing calcium sulfide using industrial by-product gypsum, which differs from example 1 only in that: the comparative example modifies the device in the external heat calcination unit into an internal heat rotary kiln.
Application example 1
The application example provides a method for preparing calcium sulfide by utilizing industrial byproduct gypsum by adopting the device system provided in the embodiment 1, which comprises the following steps:
(1) Mixing 1000kg of phosphogypsum containing 40% of water in a slurry state, 2000kg of water and 100kg of crushed coke in a slurry mixing tank, and sequentially performing filter pressing, crushing and drying at 200 ℃ for 30min to obtain 700kg of dry solids and dry flue gas;
wherein, the mass ratio of the industrial byproduct gypsum to the water is 1:4, and the mass ratio of the industrial byproduct gypsum to the reducing agent is 6:1; the dry heat source comprises flue gas (500 ℃) which is heated and cooled by an external heating rotary kiln;
(2) Calcining the dried solid obtained in the step (1) at 950 ℃ in a reducing atmosphere for 90min to obtain 330kg of calcium sulfide with the content of 90%;
wherein the reducing atmosphere is from gas generated after the reaction in the external heating rotary kiln, and accounts for 30vol% of the total gas amount;
(3) A dust removal and desulfurization process is sequentially carried out on the dry gas obtained in the step (1);
wherein, the desulfurization process is carried out in a desulfurization tower, and lime milk is adopted for desulfurization and then discharged; the desulfurization slurry is returned to the slurry mixing tank in the step (1).
In the gypsum decomposition process in the application example, a reaction cylinder knocking hammer arranged at an inlet and an outlet of the rotary kiln performs timing action, so that scab is avoided; and (3) allowing gas generated by the reaction in the rotary kiln to enter a high-temperature metal dust remover for purification under the action of a high-temperature flue gas fan, and then entering a reaction gas secondary combustion chamber and an external heating chamber for secondary combustion to generate heat.
Application example 2
The application example provides a method for preparing calcium sulfide by utilizing industrial byproduct gypsum by adopting the device system provided in the embodiment 1, which comprises the following steps:
(1) Mixing 1000kg of phosphogypsum containing 35% of water in a slurry state, 1600kg of water and 130kg of crushed coal dust in a slurry mixing tank, and sequentially carrying out filter pressing, crushing and drying at 150 ℃ for 60min to obtain 780kg of dry solids and dry flue gas;
wherein, the mass ratio of phosphogypsum to water is 1:3, and the mass ratio of phosphogypsum to reducing agent is 5:1; the dry heat source comprises flue gas (400 ℃) which is heated and cooled by an external heating rotary kiln;
(2) Calcining the dried solid obtained in the step (1) at 850 ℃ in a reducing atmosphere for 120min to obtain 360kg of calcium sulfide with 85 percent of content;
wherein the reducing atmosphere is from gas generated after the reaction in the external heating rotary kiln, and accounts for 50vol% of the total gas amount;
(3) A dust removal and desulfurization process is sequentially carried out on the dry gas obtained in the step (1);
wherein, the desulfurization process is carried out in a desulfurization tower, and lime milk is adopted for desulfurization and then discharged; the desulfurization slurry is returned to the slurry mixing tank in the step (1).
In the gypsum decomposition process in the application example, a reaction cylinder knocking hammer arranged at an inlet and an outlet of the rotary kiln performs timing action, so that scab is avoided; and (3) allowing gas generated by the reaction in the rotary kiln to enter a high-temperature metal dust remover for purification under the action of a high-temperature flue gas fan, and then entering a reaction gas secondary combustion chamber and an external heating chamber for secondary combustion to generate heat.
Application example 3
The application example provides a method for preparing calcium sulfide by utilizing industrial byproduct gypsum by adopting the device system provided in the embodiment 1, which comprises the following steps:
(1) 1000kg of desulfurized gypsum which contains 33% of water and is in a slurry state, 2082kg of water and 168kg of crushed coke are mixed in a slurry mixing tank, and then are subjected to filter pressing, crushing and drying at 180 ℃ for 50min to obtain 780kg of dry solids and dry flue gas;
wherein the mass ratio of the desulfurized gypsum to the water is 1:3.6, and the mass ratio of the desulfurized gypsum to the reducing agent is 4:1; the dry heat source comprises flue gas (450 ℃) which is heated and cooled by an external heating rotary kiln;
(2) Calcining the dried solid obtained in the step (1) at 900 ℃ in a reducing atmosphere for 110min to obtain 350kg of calcium sulfide with 87 percent of content;
wherein the reducing atmosphere is from gas generated after the reaction in the external heating rotary kiln, and accounts for 45vol% of the total gas amount;
(3) A dust removal and desulfurization process is sequentially carried out on the dry gas obtained in the step (1);
wherein, the desulfurization process is carried out in a desulfurization tower, and lime milk is adopted for desulfurization and then discharged; the desulfurization slurry is returned to the slurry mixing tank in the step (1).
In the gypsum decomposition process in the application example, a reaction cylinder knocking hammer arranged at an inlet and an outlet of the rotary kiln performs timing action, so that scab is avoided; and (3) allowing gas generated by the reaction in the rotary kiln to enter a high-temperature metal dust remover for purification under the action of a high-temperature flue gas fan, and then entering a reaction gas secondary combustion chamber and an external heating chamber for secondary combustion to generate heat.
Application example 4
The application example provides a method for preparing calcium sulfide by utilizing industrial byproduct gypsum by adopting the device system provided in the embodiment 1, which comprises the following steps:
(1) 1000kg of desulfurized gypsum in slurry state and containing 38% of water, 1976kg of water and 138kg of crushed coal dust are mixed in a slurry mixing tank, and then, filter pressing, crushing and drying at 190 ℃ are sequentially carried out for 40min to obtain 760kg of dry solids and dry flue gas;
wherein the mass ratio of the desulfurized gypsum to the water is 1:3.8, and the mass ratio of the desulfurized gypsum to the reducing agent is 4.5:1; the dry heat source comprises flue gas (480 ℃) which is heated and cooled by an external heating rotary kiln;
(2) Calcining the dried solid obtained in the step (1) at 930 ℃ in a reducing atmosphere for 100min to obtain 340kg of calcium sulfide with 89 percent of content;
wherein the reducing atmosphere is from gas generated after the reaction in the external heating rotary kiln, and accounts for 35vol% of the total gas amount;
(3) A dust removal and desulfurization process is sequentially carried out on the dry gas obtained in the step (1);
wherein, the desulfurization process is carried out in a desulfurization tower, and lime milk is adopted for desulfurization and then discharged; the desulfurization slurry is returned to the slurry mixing tank in the step (1).
In the gypsum decomposition process in the application example, a reaction cylinder knocking hammer arranged at an inlet and an outlet of the rotary kiln performs timing action, so that scab is avoided; and (3) allowing gas generated by the reaction in the rotary kiln to enter a high-temperature metal dust remover for purification under the action of a high-temperature flue gas fan, and then entering a reaction gas secondary combustion chamber and an external heating chamber for secondary combustion to generate heat.
Application example 5
The application example provides a method for preparing calcium sulfide by utilizing industrial byproduct gypsum by adopting the device system provided in the embodiment 1, which comprises the following steps:
(1) Mixing 500kg of phosphogypsum with 35% of water, 500kg of desulfurized gypsum with 35% of water, 2250kg of water and 130kg of crushed coke in a slurry mixing tank, and sequentially performing filter pressing, crushing and drying at 180 ℃ for 50min to obtain 780kg of dry solids and dry flue gas;
wherein, the mass ratio of the gypsum to the water is 1:4, and the mass ratio of the gypsum to the reducing agent is 5:1; the dry heat source comprises flue gas (470 ℃) which is heated and cooled by an external heating rotary kiln;
(2) Calcining the dried solid obtained in the step (1) at 920 ℃ in a reducing atmosphere for 120min to obtain 360kg of calcium sulfide with 88 percent of content;
wherein the reducing atmosphere is from gas generated after the reaction in the external heating rotary kiln, and accounts for 40vol% of the total gas amount;
(3) A dust removal and desulfurization process is sequentially carried out on the dry gas obtained in the step (1);
wherein, the desulfurization process is carried out in a desulfurization tower, and lime milk is adopted for desulfurization and then discharged; the desulfurization slurry is returned to the slurry mixing tank in the step (1).
In the gypsum decomposition process in the application example, a reaction cylinder knocking hammer arranged at an inlet and an outlet of the rotary kiln performs timing action, so that scab is avoided; and (3) allowing gas generated by the reaction in the rotary kiln to enter a high-temperature metal dust remover for purification under the action of a high-temperature flue gas fan, and then entering a reaction gas secondary combustion chamber and an external heating chamber for secondary combustion to generate heat.
Application example 6
The present application example provides a method for producing calcium sulfide using industrial by-product gypsum using the apparatus system provided in example 2, which is the same as that of application example 1.
In the gypsum decomposition process in the application example, a knocking hammer is not arranged on the reaction cylinder body at the inlet and outlet of the rotary kiln, so that the problem of equipment height Wen Jieba cannot be solved.
Comparative application example 1
The application example provides a method for preparing calcium sulfide by utilizing industrial byproduct gypsum by adopting the device system provided in the comparative example 1, which comprises the following steps:
(1) Mixing 1000kg of phosphogypsum containing 40% of water in a slurry state, 2000kg of water and 100kg of crushed coke in a slurry mixing tank, and sequentially performing filter pressing, crushing and drying at 200 ℃ for 30min to obtain 700kg of dry solids and dry flue gas;
wherein, the mass ratio of the industrial byproduct gypsum to the water is 1:4, and the mass ratio of the industrial byproduct gypsum to the reducing agent is 6:1; the dry heat source comprises flue gas (500 ℃) which is heated and cooled by an internal heating rotary kiln;
(2) Calcining the dried solid obtained in the step (1) at 950 ℃ in a reducing atmosphere for 90min to obtain 330kg of calcium sulfide with the content of 90%;
wherein the reducing atmosphere is from gas generated after reaction in the internal heating rotary kiln, and accounts for 80vol% of the total gas amount;
(3) A dust removal and desulfurization process is sequentially carried out on the dry gas obtained in the step (1);
wherein, the desulfurization process is carried out in a desulfurization tower, and lime milk is adopted for desulfurization and then discharged; the desulfurization slurry is returned to the slurry mixing tank in the step (1).
In the comparative example, an internal heating rotary kiln is adopted for calcination treatment, the reaction materials are in direct contact with a calcination heat source in the kiln, and the calcination heat source is provided with reducing gas at the same time; the flue gas generated by the method contains part of reaction materials, so that the content of calcium sulfide obtained by calcination is reduced, and the production of the calcium sulfide is not facilitated; and may cause loss of heat source.
In conclusion, the external heating rotary kiln, the rotary flash dryer and other equipment are coupled in process, industrial byproduct gypsum is decomposed to prepare calcium sulfide, reaction dust is prevented from being lifted by high-temperature flue gas, and the powder yield is low; the problem of equipment height Wen Jieba is effectively solved by utilizing an external knocking hammer; the clean high-temperature flue gas heated by the external heating type rotary kiln is used as a heat source of the rotary flash dryer, so that the heat utilization rate is greatly improved. The invention can realize the resource utilization of industrial byproduct gypsum and eliminate the hidden danger of the environment.
The applicant states that the detailed structural features of the present invention are described by the above embodiments, but the present invention is not limited to the above detailed structural features, i.e. it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be apparent to those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope of the present invention and the scope of the disclosure.
The applicant states that the detailed process flow of the present invention is illustrated by the above examples, but the present invention is not limited to the above detailed process flow, i.e. it does not mean that the present invention must be implemented depending on the above detailed process flow. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (10)
1. The device system for preparing the calcium sulfide by utilizing the industrial byproduct gypsum is characterized by comprising a reaction unit, a drying and dedusting unit and an external heat calcination unit which are sequentially connected;
the reaction unit comprises a reducing agent crusher, a slurry mixing tank, a filter press and a filter cake crusher which are sequentially connected;
the drying and dedusting unit comprises a rotary dryer, a cyclone receiver and a gas treatment device which are sequentially connected;
the solid inlet of the rotary dryer is connected with the filter cake crusher;
the external heat calcination unit comprises an external heat type rotary kiln reaction cylinder body, and an external heat type rotary kiln external heating chamber and a reaction gas secondary combustion chamber which are arranged on the periphery of the external heat type rotary kiln reaction cylinder body;
the solid outlet of the cyclone receiver is connected with the solid inlet of the externally heated rotary kiln reaction cylinder; and a gas outlet of the external heating chamber of the external heating rotary kiln is connected with a gas inlet of the rotary dryer.
2. The apparatus system of claim 1, wherein a mixing tank discharge pump is disposed between the slurry mixing tank and the filter press;
preferably, the gas treatment device comprises a bag-type dust collector, a desulfurizing tower and a drying induced draft fan which are sequentially connected;
preferably, a desulfurization circulating pump is arranged on the desulfurization tower;
preferably, a gas outlet of the desulfurizing tower is connected with the drying induced draft fan;
preferably, the liquid outlet of the desulfurizing tower is divided into two branches, one branch is connected with the desulfurizing circulating pump, and the other branch is connected with the inlet of the slurry mixing tank.
3. The plant system according to claim 1 or 2, characterized in that a conveyor is arranged between the solids outlet of the cyclone collector and the solids inlet of the externally heated rotary kiln reaction cylinder;
preferably, the head part and the tail part of the externally heated rotary kiln reaction cylinder are respectively and independently provided with a reaction cylinder knocking hammer;
preferably, a gas outlet of the externally heated rotary kiln reaction cylinder is sequentially connected with a high-temperature metal dust remover and a high-temperature flue gas fan;
preferably, the outlet of the high-temperature flue gas fan is respectively connected with the gas inlet of the externally-heated rotary kiln reaction cylinder and the gas inlet of the reaction gas secondary combustion chamber;
preferably, the outlet of the reaction gas secondary combustion chamber is connected with the inlet of the external heating chamber of the external heating rotary kiln.
4. A plant system according to any one of claims 1-3, wherein the material of the externally heated rotary kiln cylinder comprises a high temperature resistant alloy;
preferably, the reaction gas secondary combustion chamber and the external heating chamber of the external heating rotary kiln are respectively and independently provided with at least one external heating burner.
5. A method for preparing calcium sulfide by using industrial by-product gypsum, wherein the method is performed by using the device system according to any one of claims 1 to 4.
6. The method according to claim 5, characterized in that it comprises the steps of:
(1) Mixing industrial byproduct gypsum, water and a reducing agent in a slurry state in a slurry mixing tank, and then sequentially carrying out filter pressing, crushing and drying to obtain dry solids and dry flue gas;
(2) Calcining the dried solid obtained in the step (1) in a reducing atmosphere to obtain calcium sulfide.
7. The method of claim 6, wherein the industrial byproduct gypsum of step (1) comprises phosphogypsum and/or desulfurized gypsum;
preferably, the mass ratio of the industrial byproduct gypsum to the water is 1 (3-4);
preferably, the mass ratio of the industrial byproduct gypsum to the reducing agent is (4-6) 1;
preferably, the reducing agent comprises coke breeze and/or coal fines;
preferably, the fixed carbon content in the coke powder is more than or equal to 80 percent, and the silicon oxide content is less than 8 percent;
preferably, the fixed carbon in the pulverized coal is more than or equal to 70%, and the ash content is less than 15%;
preferably, the reducing agent further comprises a process of breaking up.
8. The method according to any one of claims 5 to 7, wherein the drying temperature in step (1) is 150 to 200 ℃;
preferably, the drying time in the step (1) is 30-60 min;
preferably, the heat source for drying in the step (1) comprises flue gas heated and cooled by an external heating rotary kiln.
9. The method of claim 6, wherein the temperature of the calcining of step (2) is 850-950 ℃;
preferably, the calcination time in the step (2) is 90-120 min;
preferably, the reducing atmosphere in the step (2) is from gas generated after the reaction in the external heating rotary kiln, and accounts for 30-50 vol% of the total gas amount.
10. The method according to any one of claims 5 to 9, further comprising a dust removal and desulfurization process performed sequentially on the dry gas obtained in step (1);
preferably, the content of the calcium sulfide in the step (2) is 85-90%.
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| CN202310397840.5A CN116425123A (en) | 2023-04-13 | 2023-04-13 | Device system and method for preparing calcium sulfide by utilizing industrial byproduct gypsum |
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| CN202310397840.5A CN116425123A (en) | 2023-04-13 | 2023-04-13 | Device system and method for preparing calcium sulfide by utilizing industrial byproduct gypsum |
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Citations (7)
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|---|---|---|---|---|
| EP0332709A1 (en) * | 1987-09-03 | 1989-09-20 | Showa Denko Kabushiki Kaisha | Externally heated rotary kiln |
| CN101003365A (en) * | 2007-01-17 | 2007-07-25 | 贵州大学 | New method for producing calcium sulfide by using phosphogypsum |
| CN101428767A (en) * | 2008-12-11 | 2009-05-13 | 贵州大学 | Process for producing calcium sulfide with phosphogypsum or other gypsums |
| CN103072949A (en) * | 2012-12-07 | 2013-05-01 | 云天化集团有限责任公司 | Method for preparing calcium sulfide through reductive decomposition of phosphogypsum by fluidized bed |
| CN114014275A (en) * | 2021-12-03 | 2022-02-08 | 中国科学院过程工程研究所 | Device and method for preparing calcium silicate base material and sulfuric acid from industrial byproduct gypsum |
| KR20230016837A (en) * | 2021-07-27 | 2023-02-03 | 진수곤 | a rotary kiln |
| CN218723057U (en) * | 2022-05-24 | 2023-03-24 | 赣州福默斯科技有限公司 | Rotary kiln |
-
2023
- 2023-04-13 CN CN202310397840.5A patent/CN116425123A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0332709A1 (en) * | 1987-09-03 | 1989-09-20 | Showa Denko Kabushiki Kaisha | Externally heated rotary kiln |
| CN101003365A (en) * | 2007-01-17 | 2007-07-25 | 贵州大学 | New method for producing calcium sulfide by using phosphogypsum |
| CN101428767A (en) * | 2008-12-11 | 2009-05-13 | 贵州大学 | Process for producing calcium sulfide with phosphogypsum or other gypsums |
| CN103072949A (en) * | 2012-12-07 | 2013-05-01 | 云天化集团有限责任公司 | Method for preparing calcium sulfide through reductive decomposition of phosphogypsum by fluidized bed |
| KR20230016837A (en) * | 2021-07-27 | 2023-02-03 | 진수곤 | a rotary kiln |
| CN114014275A (en) * | 2021-12-03 | 2022-02-08 | 中国科学院过程工程研究所 | Device and method for preparing calcium silicate base material and sulfuric acid from industrial byproduct gypsum |
| CN218723057U (en) * | 2022-05-24 | 2023-03-24 | 赣州福默斯科技有限公司 | Rotary kiln |
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