CN115073027A - Method and device for preparing sulfuric acid and co-producing cement clinker from industrial byproduct gypsum - Google Patents
Method and device for preparing sulfuric acid and co-producing cement clinker from industrial byproduct gypsum Download PDFInfo
- Publication number
- CN115073027A CN115073027A CN202210881327.9A CN202210881327A CN115073027A CN 115073027 A CN115073027 A CN 115073027A CN 202210881327 A CN202210881327 A CN 202210881327A CN 115073027 A CN115073027 A CN 115073027A
- Authority
- CN
- China
- Prior art keywords
- cement clinker
- gypsum
- sulfuric acid
- industrial
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000010440 gypsum Substances 0.000 title claims abstract description 84
- 229910052602 gypsum Inorganic materials 0.000 title claims abstract description 84
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 239000004568 cement Substances 0.000 title claims abstract description 71
- 239000006227 byproduct Substances 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 37
- 239000000463 material Substances 0.000 claims abstract description 68
- 230000009467 reduction Effects 0.000 claims abstract description 39
- 238000001354 calcination Methods 0.000 claims abstract description 34
- 238000001816 cooling Methods 0.000 claims abstract description 29
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 27
- 239000002994 raw material Substances 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 21
- 239000011593 sulfur Substances 0.000 claims abstract description 21
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 20
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003546 flue gas Substances 0.000 claims abstract description 19
- 238000000227 grinding Methods 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 238000000465 moulding Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 230000003009 desulfurizing effect Effects 0.000 claims abstract description 6
- 238000006477 desulfuration reaction Methods 0.000 claims description 31
- 230000023556 desulfurization Effects 0.000 claims description 31
- 238000002425 crystallisation Methods 0.000 claims description 19
- 230000008025 crystallization Effects 0.000 claims description 18
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 9
- 239000003245 coal Substances 0.000 claims description 8
- 239000000571 coke Substances 0.000 claims description 7
- 239000002893 slag Substances 0.000 claims description 6
- 239000000446 fuel Substances 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 239000002006 petroleum coke Substances 0.000 claims description 4
- 239000002028 Biomass Substances 0.000 claims description 3
- 229910000831 Steel Inorganic materials 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 239000010881 fly ash Substances 0.000 claims description 3
- 239000005060 rubber Substances 0.000 claims description 3
- 239000010959 steel Substances 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 14
- 239000002918 waste heat Substances 0.000 abstract description 11
- 239000013078 crystal Substances 0.000 abstract description 4
- 238000006722 reduction reaction Methods 0.000 description 33
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 17
- 238000010438 heat treatment Methods 0.000 description 12
- 238000000354 decomposition reaction Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 6
- 230000002829 reductive effect Effects 0.000 description 6
- 239000000292 calcium oxide Substances 0.000 description 5
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 235000019738 Limestone Nutrition 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 206010039509 Scab Diseases 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical group [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- JGIATAMCQXIDNZ-UHFFFAOYSA-N calcium sulfide Chemical compound [Ca]=S JGIATAMCQXIDNZ-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 230000017525 heat dissipation Effects 0.000 description 2
- 239000006028 limestone Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- 239000011573 trace mineral Substances 0.000 description 2
- 235000013619 trace mineral Nutrition 0.000 description 2
- 238000009423 ventilation Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000001174 ascending effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002802 bituminous coal Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust 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
- 239000008187 granular material Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 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
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000011020 pilot scale process Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 1
- 229910052683 pyrite Inorganic materials 0.000 description 1
- 239000011028 pyrite Substances 0.000 description 1
- 238000005978 reductive desulfurization reaction Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
-
- 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
- C04B7/24—Cements from oil shales, residues or waste other than slag
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/74—Preparation
-
- 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
- C04B7/14—Cements containing slag
- C04B7/147—Metallurgical slag
-
- 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
- C04B7/24—Cements from oil shales, residues or waste other than slag
- C04B7/26—Cements from oil shales, residues or waste other than slag from raw materials containing flue dust, i.e. fly ash
-
- 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
- C04B7/36—Manufacture of hydraulic cements in general
-
- 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
- C04B7/36—Manufacture of hydraulic cements in general
- C04B7/43—Heat treatment, e.g. precalcining, burning, melting; Cooling
- C04B7/44—Burning; Melting
- C04B7/4407—Treatment or selection of the fuel therefor, e.g. use of hazardous waste as secondary fuel ; Use of particular energy sources, e.g. waste hot gases from other processes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
- Y02P40/121—Energy efficiency measures, e.g. improving or optimising the production methods
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Inorganic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention belongs to the technical field of comprehensive treatment of industrial byproducts, and particularly discloses a method and a device for preparing sulfuric acid and co-producing cement clinker from industrial byproduct gypsum. The process disclosed by the invention comprises the steps of mixing and grinding the industrial byproduct gypsum, a reducing agent and auxiliary materials to obtain raw materials; then, molding and granulating the raw material to obtain an intermediate material; and then placing the intermediate material in a five-in-one thermal device for reaction to obtain clinker and sulfur-containing flue gas, grinding the clinker and the mixed material to prepare cement, and preparing sulfuric acid from the sulfur-containing flue gas. The invention combines the procedures of preheating raw materials, removing crystal water from gypsum, reducing and desulfurizing, calcining clinker and cooling in a set of device; the integrated equipment is compact in arrangement, the main equipment does not need to rotate, a plurality of sets of equipment are easy to be arranged in parallel under the condition of saving power, the unit capacity occupies small area, and the investment is saved; the invention also has the advantages of direct waste heat utilization, small heat loss, high reduction rate and low reduction temperature.
Description
Technical Field
The invention relates to the technical field of industrial byproduct comprehensive treatment, in particular to a method and a device for preparing sulfuric acid and co-producing cement clinker from industrial byproduct gypsum.
Background
China is a large resource country and a large industrial country, and a large number of byproducts are generated in the production and processing process of products, and the byproducts which cannot be utilized occupy a large amount of land and pollute the environment. Taking industrial byproduct gypsum as an example, the annual output exceeds 2 hundred million tons, wherein 1.1 million tons of desulfurized gypsum of a power plant are mainly distributed in northChina, northeast and northwest areas, particularly in coal producing areas, most of the desulfurized gypsum cannot be used as cement retarders and gypsum boards and is buried, and the comprehensive utilization rate is less than 60%. About 8000 million tons of phosphogypsum are newly added every year, the phosphogypsum stockpiling amount in China currently exceeds 7 hundred million tons, and the yield is mainly concentrated in the economic zone of Yangtze river. The phosphogypsum has complex components, low utilization rate and most prominent ecological environment problem, and the domestic comprehensive utilization rate is less than 40 percent and the foreign comprehensive utilization rate is less than 20 percent at present. The utilization rate of other by-product gypsum is correspondingly lower, and various environmental risks are formed. The gypsum as the industrial by-product with calcium sulfate as the main component is desulfurized to prepare sulfuric acid, and the remaining main component is calcium oxide which can be used as a calcium raw material necessary for preparing cement clinker. The coproduction process saves pyrite and sulfur which are commonly used for preparing sulfuric acid and limestone for preparing cement; and the emission of carbon dioxide generated by decomposing limestone is reduced while resources are saved, and the resources are saved and carbon is reduced.
However, the maturity of the existing process for preparing sulfuric acid and coproducing clinker from gypsum is not high, the application cases of phosphogypsum and natural anhydrite exist, and the corresponding application reports of desulfurized gypsum and other industrial by-product gypsum are not found. On the basis of domestic pilot-scale tests, a complete set of engineering devices for preparing sulfuric acid and co-producing cement from phosphogypsum is developed, namely 4 ten thousand tons of sulfuric acid and 6 ten thousand tons of cement are produced annually. In the scheme, because the calcium sulfate reduction desulfurization needs a reducing atmosphere, the clinker calcination needs an oxidizing atmosphere, and the rotary kiln has the structural characteristics that the ventilation area is large, a stable reduction zone is difficult to form in a ventilation state, so that the reduction desulfurization is unstable, a large amount of sulfur is carried to a calcination zone, and in addition, the phosphorus and fluorine content in phosphogypsum is high, the melting temperature of the substances is low, each zone of the rotary kiln is easy to melt and enrich in a cylinder, so that the crusting and ring formation are generated, and the normal production cannot be normally caused.
In order to improve the reduction desulfurization efficiency, various processes such as suspension preheating decomposition, fluidized bed decomposition desulfurization and the like are developed, and the reduction desulfurization process is carried out before entering a rotary kiln, so that the aims of improving the sulfur content of flue gas, saving energy consumption, improving the yield of the kiln and the like are fulfilled. But all have the problems of partial energy waste, large occupied area of equipment dispersion and large investment. Most of elements such as phosphorus, fluorine and the like are still brought into the rotary kiln, and the ring formation phenomenon in the rotary kiln cannot be solved because the sulfur cannot be completely removed.
The technical preparation mostly follows the following reaction formula before the clinker is calcined:
in the heated state, when the temperature does not exceed 180 ℃: 2CaSO 4 ·2H 2 O→2CaSO 4 ·1/2H 2 O+3H 2 O
The temperature exceeds 180 ℃, and all crystal water is removed: 2CaSO 4 ·1/2H 2 O→2CaSO 4 +H 2 O
SO removal of calcium sulfate 3 The temperature is required to be more than 1280 ℃, the removal speed is very slow, and the decomposition temperature can be reduced by adding carbon element for reduction through tests to ensure that SO 3 Gasified to SO 2 ：2CaSO 4 +C→2CaO+CO 2 +2SO 2
Because of the slow reduction reaction rate, byproducts such as calcium sulfide are generated in the process, and the required calcium oxide, carbon monoxide and sulfur dioxide are not formed in one step:
CaSO 4 +C→CaS+4CO
CaSO 4 +4CO→CaS+4CO 2
CaSO 4 +2C→CaS+2CO 2
calcium sulfide can be produced and oxidized into CaO and CaSO in oxidizing atmosphere 4 ：8CaS+7O 2 →6CaO+2CaSO 4 。
If the integration of drying (including preheating and dewatering), desulfurizing, calcining and cooling is realized, the site can be saved, and the previous process is finishedThe waste heat of the next procedure is fully utilized, and energy conservation is realized. At the same time, SO in the flue gas 2 The content is the key of the absorption efficiency of the sulfuric acid, and the process of separate arrangement is not beneficial to sealing and is easy to cause air leakage to cause the SO in the flue gas 2 The content is reduced, and the prior art calcining equipment mainly adopts a rotary kiln and is easy to leak air; the centralized integrated equipment can greatly reduce the air leakage coefficient and ensure the flue gas SO 2 And (4) content.
The core of the whole process is reductive desulfurization, and the stronger the reducing atmosphere, the lower the temperature required for reduction and the faster the reduction speed, and coke is generally used as a reducing agent for achieving the effect. The coke has the advantages of high fixed carbon and high cost; if a process capable of using low-fixed-carbon raw coal as a reducing agent is developed, the cost is greatly reduced, and the process for preparing sulfuric acid and cement clinker by industrial byproduct gypsum is promoted.
Therefore, how to provide a method and a device for preparing sulfuric acid and co-producing cement clinker by using industrial by-product gypsum, reduce the air leakage coefficient and ensure the SO in flue gas 2 The content, the processing cost and the occupied area are difficult problems to be solved urgently in the field.
Disclosure of Invention
In view of the above, the invention provides a method and a device for preparing sulfuric acid and co-producing cement clinker by using industrial by-product gypsum, so as to solve the problems of more required equipment, low process maturity, high treatment cost and few types of treated industrial by-product gypsum in the traditional treatment method for the industrial by-product gypsum; meanwhile, a strong reducing atmosphere is formed in the reaction process, the reducing speed is accelerated, and the reducing temperature is reduced.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing sulfuric acid and cement clinker by industrial by-product gypsum comprises the following steps:
1) mixing and grinding industrial by-product gypsum, a reducing agent and auxiliary materials to obtain a raw material;
2) granulating and molding the raw materials to obtain intermediate materials;
3) and (3) placing the intermediate material in a five-in-one thermal device for reaction to obtain cement clinker and sulfur-containing flue gas, grinding the cement clinker and the mixed material to prepare cement, and preparing sulfuric acid from the sulfur-containing flue gas.
Preferably, the industrial byproduct gypsum comprises one or more of phosphogypsum, desulfurized gypsum, titanium gypsum and chlor-alkali gypsum;
the adding mass ratio of the industrial byproduct gypsum to the reducing agent to the auxiliary materials is 80-99: 1-20: 1 to 19.
Preferably, the reducing agent comprises one or more of coke, coal, biomass fuel, petroleum coke and rubber.
Preferably, the auxiliary materials comprise one or more of sandstone, loess, iron ore tailings and steel slag.
Preferably, the particle size of the raw material in the step 1) is 100-400 meshes.
Preferably, the granulating and forming in the step 2) comprises granulating and forming by a granulator or a forming machine;
the particle size of the intermediate material is 5-15 mm.
Preferably, the reaction in the step 3) comprises preheating the intermediate material, removing crystal water from by-product gypsum, reducing and desulfurizing, calcining cement clinker and cooling in sequence;
the preheating is to raise the temperature from room temperature to 140-160 ℃, and the raising time is 5-15 min;
the temperature of the byproduct gypsum crystallization water is increased from the final preheating temperature to 580-620 ℃, and the temperature rising time is 10-30 min;
in the step of reduction desulfurization, the temperature is raised from the final temperature of byproduct gypsum crystallization water to 1230-1280 ℃, and the temperature rise time is 25-60 min;
calcining the cement clinker until the temperature is increased to 1430-1480 ℃ from the final temperature of reduction desulfurization, wherein the temperature-increasing time is 20-40 min;
and the cooling is to reduce the temperature from the final temperature of the cement clinker calcination to 70-90 ℃, and the temperature reduction time is 40-80 min.
Preferably, the mixed material in the step 3) comprises one or more of natural gypsum, blast furnace slag and fly ash.
The invention also aims to provide a five-in-one thermal device for preparing sulfuric acid and cement clinker from industrial by-product gypsum, which comprises an intermediate material preheating chamber (2), a by-product gypsum crystallization water removing chamber (3), a reduction desulfurization chamber (4), a cement clinker calcining chamber (5) and a cooling chamber (6) which are sequentially communicated.
Preferably, the device also comprises 2-10 balance air pipes (7), a crusher (8), a blower (9), a blanking cylinder (10) and an air pipe (11);
the upper end of the balance air pipe (7) is communicated with the reduction desulfurization chamber (4), the lower end of the balance air pipe is communicated with the cement clinker calcining chamber (5), the crusher (8) is positioned on one side of the cooling chamber (6) far away from the cement clinker calcining chamber (5), the blower (9) is positioned on one side of the crusher (8) far away from the cooling chamber (6), the lower charging barrel (10) is communicated with the crusher (8), and the air pipe (11) is communicated with the intermediate material preheating chamber (2).
According to the technical scheme, compared with the prior art, the invention has the following beneficial effects:
1. the suspension preheating decomposition method reduces the whole place due to the reducing atmosphere: the reducing agent is oxidized and then distributed in the whole space to form a reducing atmosphere, the space is large, the concentration is naturally low, the reducing strength is low, the consumption of the reducing agent is increased in order to reach the concentration of the reducing atmosphere, the consumption of the reducing agent is large, and the cost is high. The reducing agent and the industrial by-product gypsum (the main component is calcium sulfate) are mixed, granulated and molded, so that the reducing agent is oxidized to form a high-concentration reducing atmosphere in granules, and the reducing agent is converted into gas from solid and then forcibly permeates the periphery and the surface, so that the contact between the reducing gas and the calcium sulfate is accelerated. According to the principle of reduction desulfurization, the higher the concentration of the reducing atmosphere, the lower the reduction temperature, and the faster the reduction desulfurization speed. The high-concentration and strong-contact reducing atmosphere greatly accelerates the decomposition and desulfurization of calcium sulfate and reduces the desulfurization temperature.
2. The suspension preheating decomposition method is used for decomposing and desulfurizing, calcining clinker and cooling clinker, and has the advantages of large occupied area, large equipment surface area, more heat dissipation and energy conservation. The invention has compact equipment, small heat dissipation area and easy external heat preservation, does not rotate the main body of the equipment and is beneficial to energy saving.
3. The clinker calcination stage by the suspension preheating decomposition method is carried out in a rotary kiln, because industrial byproduct gypsum contains more trace elements, incomplete desulfurization can also bring higher sulfur into the rotary kiln, the trace elements and the sulfur are easy to melt under the condition of being lower than the clinker calcination temperature, and the clinker is enriched and generates crusts in the kiln, so that the normal operation of the production cannot be carried out in severe time. The material falls by self gravity, and the material is granulated and molded to obtain a molded body, so that the material is not easy to melt and crust with the kiln wall, and the continuous production is further ensured.
4. The desulfurizer of the suspension preheating decomposition method selects coke, and the clinker is calcined by high-quality bituminous coal or natural gas, so that the cost is high. The reducing agent and the calcining material can use low-heat value raw coal or high-sulfur coal, have low cost and fully utilize inferior resources.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is a process flow diagram of the present invention for preparing sulfuric acid and cement clinker from industrial by-product gypsum;
FIG. 2 is a flow chart of the reaction in the five-in-one thermal apparatus of the present invention;
FIG. 3 is a schematic view of the reduction principle of the present invention, wherein a is a schematic view of material distribution, and b is a schematic view of diffusion of a reducing agent after oxidation;
FIG. 4 is a diagram of a five-in-one thermal apparatus according to the present invention;
wherein, 2 is an intermediate material preheating chamber, 3 is a byproduct gypsum crystallization water removing chamber, 4 is a reduction desulfurization chamber, 5 is a cement clinker calcining chamber, 6 is a cooling chamber, 7 is a balance air pipe, 8 is a crusher, 9 is a blower, 10 is a charging barrel, and 11 is an air pipe.
Detailed Description
The invention provides a method for preparing sulfuric acid and cement clinker by industrial by-product gypsum, which comprises the following steps:
1) mixing and grinding industrial by-product gypsum, a reducing agent and auxiliary materials to obtain a raw material;
2) granulating and molding the raw materials to obtain intermediate materials;
3) and (3) placing the intermediate material in a five-in-one thermal device for reaction to obtain clinker and sulfur-containing flue gas, grinding the clinker and the mixed material to prepare cement, and preparing sulfuric acid from the sulfur-containing flue gas.
In the invention, the industrial byproduct gypsum comprises one or more of phosphogypsum, desulfurized gypsum, titanium gypsum and chlor-alkali gypsum;
the adding mass ratio of the industrial byproduct gypsum to the reducing agent to the auxiliary materials is 80-99: 1-20: 1 to 19, preferably 82 to 95: 5-18: 5-15, more preferably 90: 10: 10.
in the invention, the reducing agent comprises one or more of coke, coal, biomass fuel, petroleum coke and rubber.
In the invention, the auxiliary materials comprise one or more of sandstone, loess, iron ore tailings and steel slag.
In the present invention, the particle size of the raw material in the step 1) is 100 to 400 mesh, preferably 200 to 300 mesh, and more preferably 250 mesh.
In the invention, the granulating and forming in the step 2) comprises granulating and forming by a granulator or a forming machine;
the particle size of the intermediate material is 5-15 mm, preferably 8-12 mm, and further preferably 10 mm.
In the invention, the reaction in the step 3) comprises preheating the intermediate material, removing crystallization water from the byproduct gypsum, reducing and desulfurizing, calcining cement clinker and cooling in sequence;
the preheating is to raise the temperature from room temperature to 140-160 ℃, preferably 145-155 ℃, and further preferably 150 ℃; the temperature rise time is 5-15 min, preferably 7-12 min, and more preferably 10 min;
the temperature of the byproduct gypsum crystallization water is increased from the final preheating temperature to 580-620 ℃, preferably 590-610 ℃, and more preferably 600 ℃; the temperature rise time is 10-30 min, preferably 15-25 min, and more preferably 20 min;
the reduction desulfurization is to raise the temperature from the final temperature of byproduct gypsum crystallization water to 1230-1280 ℃, preferably 1240-1260 ℃, and more preferably 1250 ℃; the temperature rise time is 25-60 min, preferably 30-50 min, and more preferably 40 min;
the cement clinker is calcined until the temperature is increased from the reduction desulfurization final temperature to 1430-1480 ℃, preferably 1440-1460 ℃ and more preferably 1450 ℃; the temperature rise time is 20-40 min, preferably 25-35 min, and more preferably 30 min;
the cooling is to reduce the temperature from the final temperature of the calcination of the cement clinker to 70-90 ℃, preferably 75-85 ℃, and further preferably 80 ℃; the cooling time is 40-80 min, preferably 50-70 min, and more preferably 60 min.
In the invention, the mixed materials in the step 3) are natural gypsum, blast furnace slag, fly ash and other mixed materials which meet the relevant cement standards;
in the invention, the mass ratio of the clinker to the mixed material is required to meet the corresponding cement standard, and preferably is 25-95: 75-5.
In the invention, the process flow chart of the co-production of sulfuric acid and cement clinker by byproduct gypsum is shown in figure 1.
The invention also provides a five-in-one thermal device for preparing sulfuric acid and cement clinker from industrial by-product gypsum, which comprises an intermediate material preheating chamber (2), a by-product gypsum crystallization water removing chamber (3), a reduction desulfurization chamber (4), a cement clinker calcining chamber (5) and a cooling chamber (6) which are sequentially communicated, and is shown in figure 4.
In the invention, the granulator or the forming machine (1) is positioned at one end of the five-in-one thermal equipment, which is far away from the feeding barrel.
In the invention, the five-in-one thermal device also comprises 2-10 balance air pipes (7), a crusher (8), a blower (9), a blanking cylinder (10) and an air pipe (11); the number of the balance air pipes (7) is preferably 4-8, and more preferably 6.
In the invention, the charging barrel (10) is a sealed charging barrel.
The upper end of the balance air pipe (7) is communicated with the reduction desulfurization chamber (4), the lower end of the balance air pipe is communicated with the cement clinker calcining chamber (5), the crusher (8) is positioned on one side of the cooling chamber (6) far away from the cement clinker calcining chamber (5), the blower (9) is positioned on one side of the crusher (8) far away from the cooling chamber (6), the lower charging barrel (10) is communicated with the crusher (8), and the air pipe (11) is communicated with the intermediate material preheating chamber (2).
In the invention, the material flow and the airflow flow are as follows: granulating and forming the raw materials in a granulator or a forming machine (1), feeding the raw materials into a five-in-one device, and sequentially completing preheating and attached water removal in an intermediate material preheating chamber (2) by utilizing waste heat from bottom to top; crystal water removal is completed in a byproduct gypsum crystallization water removal chamber (3); reducing agent is oxidized in the reduction desulfurization chamber (4) to form a reducing atmosphere, calcium sulfate is decomposed in the reducing atmosphere to decompose SO 2 The schematic diagram of the reduction principle of gas and CaO is shown in fig. 3, fig. 3a shows that the reducing agent, the auxiliary material and the calcium sulfate are uniformly distributed, and fig. 3b shows that the oxycarbide generated after the reducing agent is oxidized diffuses to the outer wall; in the cement clinker calcining chamber (5), unburned reducing agent is combusted in the gradually formed oxidizing atmosphere (the lower part is provided with a cold cutting fan for air supply), CaO and SiO in auxiliary materials 2 、Al 2 O 3 、Fe 2 O 3 The components are subjected to chemical reaction to generate cement clinker; the clinker moves downwards under the action of gravity, cooling air blown by an air blower (9) is received in a cooling chamber (6) to finish cooling of the clinker, and the cooled clinker is crushed in a crusher (8) and then enters a sealed blanking cylinder (10) to finish preparation of the clinker. In order to balance the oxidizing atmosphere and the reducing atmosphere, a balance air pipe (7) is additionally arranged in the middle of the equipment; the equipment is a closed device, decomposed SO 2 Gas, water vapor and other waste gases enter the links of dust removal and acid preparation along the air pipe (11). The specific reaction flow and the waste heat trend are shown in fig. 2, fig. 2 shows that the reducing agent is combusted in the reduction desulfurization stage, because the reducing agent is incompletely combusted in the reduction atmosphere, the reducing agent is continuously combusted in the oxidation atmosphere after entering the clinker calcination stage to generate clinker, sensible heat of the clinker is absorbed by bottom cooling air after entering the cooling stage, the temperature of the cooling air is increased to be more than 800 ℃ from room temperature, the fuel combustion in the clinker calcination stage is accelerated, and one-time waste heat utilization is completed; in the clinker calcining stage, because the fuel combustion temperature can reach about 1450 ℃, in the wind ascending process, the waste heat enters the reduction desulfurization stage to complete the primary waste heat utilization; is composed ofThe excessive residual oxygen is prevented from entering the reduction desulfurization section, and part of residual heat enters the crystallization dehydration section through the balance air pipe, so that the primary residual heat utilization is completed; the waste heat of the reduction desulfurization stage enters a crystallization water removal stage, and primary waste heat utilization is also completed; and the waste heat in the crystallization water removal stage is moved upwards to the raw material preheating stage, so that the primary waste heat utilization is completed.
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Weighing 85 parts of desulfurized gypsum, 12 parts of coal and 3 parts of sandstone, mixing and grinding the desulfurized gypsum and the sandstone to the grain size of 100-300 meshes to obtain a raw material, putting the raw material into a granulator, granulating and molding to obtain an intermediate material with the grain size of 10mm, feeding the molded intermediate material into a five-in-one thermal tool, heating the intermediate material to 150 ℃ from room temperature under 15min to complete preheating, heating the intermediate material to 600 ℃ after 20min to complete gypsum crystallization water removal, heating the intermediate material to 1250 ℃ after 40min to complete reduction desulfurization, heating the intermediate material to 1450 ℃ after 30min to complete cement clinker calcination, cooling the intermediate material to 80 ℃ under 60min to obtain cement clinker and sulfur-containing flue gas, grinding the cement clinker, the natural gypsum, the industrial byproduct gypsum and various mixed materials meeting relevant standards together to prepare cement, and preparing sulfuric acid from the sulfur-containing flue gas.
Example 2
Weighing 87.5 parts of phosphogypsum, 11 parts of petroleum coke and 1.5 parts of loess, mixing and grinding the mixture to a particle size of 250-400 meshes to obtain a raw material, putting the raw material into a granulator for granulation and molding to obtain an intermediate material with the particle size of 15mm, feeding the molded intermediate material into a five-in-one thermal tool, heating the raw material to 140 ℃ from room temperature for 5min to complete preheating, heating the raw material to 580 ℃ after 10min to complete de-crystallization water as a byproduct of gypsum, heating the raw material to 1230 ℃ after 25min to complete reduction desulfurization, heating the raw material to 1430 ℃ after 20min to complete cement clinker calcination, cooling the raw material to 90 ℃ after 40min to obtain cement clinker and sulfur-containing flue gas, and respectively grinding the cement clinker, the natural gypsum, the industrial byproduct gypsum and various mixed materials meeting relevant standards to prepare cement and sulfuric acid from the sulfur-containing flue gas.
Example 3
Weighing 98 parts of phosphogypsum, 5 parts of coke and 15 parts of iron ore, mixing and grinding the mixture to a particle size of 200-350 meshes to obtain a raw material, putting the raw material into a granulator, granulating and forming to obtain an intermediate material with the particle size of 5mm, feeding the formed intermediate material into a five-in-one thermal device, heating the intermediate material to 160 ℃ from room temperature for 12min to complete preheating, heating the intermediate material to 620 ℃ after 30min to complete by-product gypsum crystallization water removal, heating the intermediate material to 1280 ℃ after 60min to complete reduction desulfurization, heating the intermediate material to 1480 ℃ after 40min to complete cement clinker calcination, cooling the intermediate material to 70 ℃ after 80min to obtain cement clinker and sulfur-containing flue gas, and grinding the cement clinker, natural gypsum, industrial by-product gypsum and various mixed materials meeting relevant standards together to obtain cement, and preparing sulfuric acid from the sulfur-containing flue gas.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A method for preparing sulfuric acid and cement clinker by industrial by-product gypsum is characterized by comprising the following steps:
1) mixing and grinding industrial by-product gypsum, a reducing agent and auxiliary materials to obtain a raw material;
2) granulating and molding the raw materials to obtain intermediate materials;
3) and (3) placing the intermediate material in a five-in-one thermal device for reaction to obtain cement clinker and sulfur-containing flue gas, grinding the cement clinker and the mixed material to prepare cement, and preparing sulfuric acid from the sulfur-containing flue gas.
2. The method for preparing sulfuric acid and co-producing cement clinker by using the industrial byproduct gypsum according to claim 1, wherein the industrial byproduct gypsum comprises one or more of phosphogypsum, desulfurized gypsum, titanium gypsum and chlor-alkali gypsum;
the adding mass ratio of the industrial byproduct gypsum to the reducing agent to the auxiliary materials is 80-99: 1-20: 1 to 19.
3. The method for preparing sulfuric acid and co-producing cement clinker from industrial byproduct gypsum according to claim 2, wherein the reducing agent comprises one or more of coke, coal, biomass fuel, petroleum coke and rubber.
4. The method for preparing sulfuric acid and co-producing cement clinker from industrial byproduct gypsum according to claim 3, wherein the auxiliary materials comprise one or more of sandstone, loess, iron ore tailings and steel slag.
5. The method for preparing sulfuric acid and co-producing cement clinker from industrial by-product gypsum according to any one of claims 1 to 4, wherein the particle size of the raw material in the step 1) is 100 to 400 meshes.
6. The method for preparing sulfuric acid and cement clinker from industrial byproduct gypsum according to claim 5, wherein the granulation molding in the step 2) comprises molding by a granulator or a molding machine;
the particle size of the intermediate material is 5-15 mm.
7. The method for preparing sulfuric acid and cement clinker from industrial by-product gypsum according to claim 6, wherein the reaction in the step 3) comprises preheating the intermediate material, removing crystallization water from the by-product gypsum, reducing and desulfurizing, calcining the cement clinker, and cooling in sequence;
the preheating is to raise the temperature from room temperature to 140-160 ℃, and the raising time is 5-15 min;
the temperature of the byproduct gypsum crystallization water is increased from the final preheating temperature to 580-620 ℃, and the temperature rising time is 10-30 min;
in the step of reduction desulfurization, the temperature is raised from the final temperature of byproduct gypsum crystallization water to 1230-1280 ℃, and the temperature rise time is 25-60 min;
calcining the cement clinker until the temperature is increased to 1430-1480 ℃ from the final temperature of reduction desulfurization, wherein the temperature-increasing time is 20-40 min;
and the cooling is to reduce the temperature from the final temperature of the cement clinker calcination to 70-90 ℃, and the temperature reduction time is 40-80 min.
8. The method for preparing sulfuric acid and co-producing cement clinker by using industrial by-product gypsum according to claim 6 or 7, wherein the mixed material in the step 3) comprises one or more of natural gypsum, blast furnace slag and fly ash.
9. The five-in-one thermal device for preparing sulfuric acid and co-producing cement clinker from industrial byproduct gypsum is characterized by comprising an intermediate material preheating chamber (2), a byproduct gypsum crystallization water removing chamber (3), a reduction desulfurization chamber (4), a cement clinker calcining chamber (5) and a cooling chamber (6) which are communicated in sequence.
10. The five-in-one thermal device for preparing sulfuric acid and co-producing cement clinker from industrial by-product gypsum according to claim 9, further comprising 2-10 balance air pipes (7), a crusher (8), a blower (9), a blanking cylinder (10) and an air pipe (11);
the upper end of the balance air pipe (7) is communicated with the reduction desulfurization chamber (4), the lower end of the balance air pipe is communicated with the cement clinker calcining chamber (5), the crusher (8) is positioned on one side of the cooling chamber (6) far away from the cement clinker calcining chamber (5), the blower (9) is positioned on one side of the crusher (8) far away from the cooling chamber (6), the lower charging barrel (10) is communicated with the crusher (8), and the air pipe (11) is communicated with the intermediate material preheating chamber (2).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210881327.9A CN115073027A (en) | 2022-07-26 | 2022-07-26 | Method and device for preparing sulfuric acid and co-producing cement clinker from industrial byproduct gypsum |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210881327.9A CN115073027A (en) | 2022-07-26 | 2022-07-26 | Method and device for preparing sulfuric acid and co-producing cement clinker from industrial byproduct gypsum |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115073027A true CN115073027A (en) | 2022-09-20 |
Family
ID=83243934
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210881327.9A Pending CN115073027A (en) | 2022-07-26 | 2022-07-26 | Method and device for preparing sulfuric acid and co-producing cement clinker from industrial byproduct gypsum |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115073027A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115504692A (en) * | 2022-09-27 | 2022-12-23 | 中冶南方都市环保工程技术股份有限公司 | Method for preparing carbonized cementing material and co-producing sulfuric acid by using semi-dry desulfurized fly ash |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101318631A (en) * | 2008-07-10 | 2008-12-10 | 昆明理工大学 | Method and apparatus for decomposing phosphogypsum to produce sulphuric acid, generating electricity power and cement with quiescent state reduction |
| CN101343047A (en) * | 2008-08-26 | 2009-01-14 | 山东鲁北企业集团总公司 | Improved preparation technique for preparing sulphuric acid and cement with gypsum |
| CN201254457Y (en) * | 2008-07-10 | 2009-06-10 | 昆明理工大学 | Apparatus for decomposing phosphogypsum to produce sulphuric acid, generating electricity power and cement with quiescent state reduction |
| CN102020251A (en) * | 2010-11-08 | 2011-04-20 | 南京创能电力科技开发有限公司 | Improved production process for preparing sulfuric acid and cement from gypsum |
| CN102219413A (en) * | 2010-03-30 | 2011-10-19 | 三菱综合材料株式会社 | Cement clinker manufacturing method |
| CN103496861A (en) * | 2013-09-24 | 2014-01-08 | 龚家竹 | Production method for co-producing cement and sulfuric acid by using gypsum |
| CN103964715A (en) * | 2014-02-27 | 2014-08-06 | 龚家竹 | Energy-saving and cost-reducingmethod for producingcementfromgypsumwith by-product ofsulfuric acid |
| CN107215850A (en) * | 2017-06-09 | 2017-09-29 | 山东鲁北企业集团总公司 | A kind of lithium slag and industry by-product gypsum Sulphuric acid joint product cement process |
| CN111559879A (en) * | 2020-05-18 | 2020-08-21 | 上海三夫工程技术有限公司 | Method for preparing sulphoaluminate cement and co-producing sulfuric acid by reducing gypsum with sulfur gas |
| CN112694067A (en) * | 2020-12-30 | 2021-04-23 | 成都千砺金科技创新有限公司 | Production method for co-producing cement and sulfuric acid by using phosphogypsum |
-
2022
- 2022-07-26 CN CN202210881327.9A patent/CN115073027A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101318631A (en) * | 2008-07-10 | 2008-12-10 | 昆明理工大学 | Method and apparatus for decomposing phosphogypsum to produce sulphuric acid, generating electricity power and cement with quiescent state reduction |
| CN201254457Y (en) * | 2008-07-10 | 2009-06-10 | 昆明理工大学 | Apparatus for decomposing phosphogypsum to produce sulphuric acid, generating electricity power and cement with quiescent state reduction |
| CN101343047A (en) * | 2008-08-26 | 2009-01-14 | 山东鲁北企业集团总公司 | Improved preparation technique for preparing sulphuric acid and cement with gypsum |
| CN102219413A (en) * | 2010-03-30 | 2011-10-19 | 三菱综合材料株式会社 | Cement clinker manufacturing method |
| CN102020251A (en) * | 2010-11-08 | 2011-04-20 | 南京创能电力科技开发有限公司 | Improved production process for preparing sulfuric acid and cement from gypsum |
| CN103496861A (en) * | 2013-09-24 | 2014-01-08 | 龚家竹 | Production method for co-producing cement and sulfuric acid by using gypsum |
| CN103964715A (en) * | 2014-02-27 | 2014-08-06 | 龚家竹 | Energy-saving and cost-reducingmethod for producingcementfromgypsumwith by-product ofsulfuric acid |
| CN107215850A (en) * | 2017-06-09 | 2017-09-29 | 山东鲁北企业集团总公司 | A kind of lithium slag and industry by-product gypsum Sulphuric acid joint product cement process |
| CN111559879A (en) * | 2020-05-18 | 2020-08-21 | 上海三夫工程技术有限公司 | Method for preparing sulphoaluminate cement and co-producing sulfuric acid by reducing gypsum with sulfur gas |
| CN112694067A (en) * | 2020-12-30 | 2021-04-23 | 成都千砺金科技创新有限公司 | Production method for co-producing cement and sulfuric acid by using phosphogypsum |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115504692A (en) * | 2022-09-27 | 2022-12-23 | 中冶南方都市环保工程技术股份有限公司 | Method for preparing carbonized cementing material and co-producing sulfuric acid by using semi-dry desulfurized fly ash |
| CN115504692B (en) * | 2022-09-27 | 2023-09-22 | 中冶南方都市环保工程技术股份有限公司 | Method for preparing carbonized cementing material and co-producing sulfuric acid by using semi-dry desulfurization ash |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111559879B (en) | Method for preparing sulphoaluminate cement and co-producing sulfuric acid by reducing gypsum with sulfur gas | |
| CN201161187Y (en) | Composite cycle fluidized bed apparatus for phosphogypsum decomposition | |
| CN110404936B (en) | Comprehensive treatment method for semi-dry desulfurized fly ash | |
| CN102010924A (en) | Method for producing directly reduced iron from coal | |
| CN101244811B (en) | Method for improving SO2 concentration in acid making technique with decomposition of calcium sulphate | |
| CN105819447A (en) | High-thermal-intensity CaO carbon-containing pellets and preparation method and application thereof | |
| CN115073027A (en) | Method and device for preparing sulfuric acid and co-producing cement clinker from industrial byproduct gypsum | |
| CN111574080B (en) | Method for preparing belite sulphoaluminate cement and co-producing sulfuric acid by reducing gypsum with sulfur gas | |
| CN110844888A (en) | Reduction-oxidation two-stage treatment method for desulfurized fly ash | |
| CN105152141B (en) | A kind of gypsum relieving haperacidity thermal technology and device | |
| CN105217581B (en) | A kind of method of chemical gypsum and carbide slag comprehensive utilization | |
| CN101357773B (en) | Method for reducing ardealite decomposition temperature | |
| CN218561134U (en) | Phosphogypsum comprehensive utilization system | |
| CN115925295B (en) | Phosphogypsum comprehensive utilization method | |
| CN106517120B (en) | A kind of method of kiln legal system phosphoric acid coproduction aglite | |
| CN102320640A (en) | Method for decomposing phosphogypsum through coupling reaction heat and vibration fluidizing | |
| CN112250051B (en) | Method for co-producing phosphoric acid and cement clinker by absorbing phosphogypsum roasting smoke by phosphorite slurry | |
| KR20190081980A (en) | Manufacturing method of direct reduction iron using waste materials | |
| CN212030203U (en) | High-efficient decomposing furnace | |
| CN114804664A (en) | Method for preparing lime balls from wet-process carbide slag | |
| CN105063345B (en) | H in gas is sintered under the conditions of flue gas recirculation at high proportion2O (g) control method | |
| CN110681322B (en) | Green calcining equipment, system and process for producing gel material by utilizing bulk solid wastes | |
| CN113651295A (en) | Method for preparing sulfuric acid by treating semidry desulfurization ash and high-sulfur iron material through sintering process | |
| Zhang et al. | Sulfur migration behavior in sintering and pelletizing processes: A review | |
| CN101941806A (en) | Method for utilizing composite reducing agent to decompose phosphogypsum |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220920 |
|
| RJ01 | Rejection of invention patent application after publication |