CN112250051A - Method for absorbing phosphogypsum roasting smoke and co-producing phosphoric acid and cement clinker by phosphate rock slurry - Google Patents
Method for absorbing phosphogypsum roasting smoke and co-producing phosphoric acid and cement clinker by phosphate rock slurry Download PDFInfo
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- CN112250051A CN112250051A CN202011111716.0A CN202011111716A CN112250051A CN 112250051 A CN112250051 A CN 112250051A CN 202011111716 A CN202011111716 A CN 202011111716A CN 112250051 A CN112250051 A CN 112250051A
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- phosphogypsum
- phosphoric acid
- roasting
- flue gas
- phosphorite
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- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 title claims abstract description 100
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 239000002367 phosphate rock Substances 0.000 title claims abstract description 46
- 239000004568 cement Substances 0.000 title claims abstract description 40
- 229910000147 aluminium phosphate Inorganic materials 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 33
- 239000002002 slurry Substances 0.000 title claims abstract description 29
- 239000000779 smoke Substances 0.000 title claims abstract description 18
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000003546 flue gas Substances 0.000 claims abstract description 28
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 21
- 239000007789 gas Substances 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 239000000706 filtrate Substances 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 239000010452 phosphate Substances 0.000 claims abstract description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 7
- 238000000926 separation method Methods 0.000 claims abstract description 7
- 238000007599 discharging Methods 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 25
- 239000003638 chemical reducing agent Substances 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000000197 pyrolysis Methods 0.000 claims description 7
- 238000000265 homogenisation Methods 0.000 claims description 6
- 239000004615 ingredient Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000005245 sintering Methods 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 239000000571 coke Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 229910052681 coesite Inorganic materials 0.000 claims 1
- 229910052906 cristobalite Inorganic materials 0.000 claims 1
- 229910052682 stishovite Inorganic materials 0.000 claims 1
- 229910052905 tridymite Inorganic materials 0.000 claims 1
- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulfur dioxide Inorganic materials O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 abstract description 27
- 239000002253 acid Substances 0.000 abstract description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 3
- 239000011574 phosphorus Substances 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 20
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 238000009825 accumulation Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002686 phosphate fertilizer Substances 0.000 description 1
- 238000007613 slurry method Methods 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/18—Phosphoric acid
- C01B25/22—Preparation by reacting phosphate-containing material with an acid, e.g. wet process
- C01B25/222—Preparation by reacting phosphate-containing material with an acid, e.g. wet process with sulfuric acid, a mixture of acids mainly consisting of sulfuric acid or a mixture of compounds forming it in situ, e.g. a mixture of sulfur dioxide, water and oxygen
-
- 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
- C04B7/28—Cements from oil shales, residues or waste other than slag from combustion residues, e.g. ashes or slags from waste incineration
-
- 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
- C04B7/38—Preparing or treating the raw materials individually or as batches, e.g. mixing with fuel
-
- 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
- C04B7/432—Preheating without addition of fuel
-
- 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
- C04B7/47—Cooling ; Waste heat management
- C04B7/475—Cooling ; Waste heat management using the waste heat, e.g. of the cooled clinker, in an other way than by simple heat exchange in the cement production line, e.g. for generating steam
-
- 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
Abstract
The invention discloses a method for absorbing phosphogypsum roasting smoke and co-producing phosphoric acid and cement clinker by phosphorite slurry, which comprises the following steps: 1) drying; 2) homogenizing; 3) high temperature decomposition to obtain SO2Roasting flue gas and residues by using the phosphogypsum, and cooling the residues to obtain cement clinker; 4) decomposing phosphate ore: will contain SO2Introducing the phosphogypsum roasting flue gas into the phosphorite slurry to decompose phosphorite, fully reacting, performing solid-liquid separation, returning filter residue which is phosphogypsum to the step (1) as a raw material, wherein the filtrate is dilute phosphoric acid, and discharging gas. The invention uses the phosphorus ore pulp to absorb the phosphogypsum roasting smoke to co-produce phosphoric acid and cement clinker, not only can realize the recycling harmless treatment of the phosphogypsum,and the phosphogypsum does not need a flue gas acid making system after being decomposed, sulfur dioxide flue gas is directly introduced into the phosphorite pulp and is absorbed to decompose phosphorite to generate phosphogypsum and phosphoric acid, the phosphogypsum returns to a roasting working section to realize circular treatment, the treated flue gas can be directly discharged, and the whole process has no waste discharge and no harmful gas generation.
Description
Technical Field
The invention belongs to the technical field of phosphogypsum recycling and harmless treatment, and particularly relates to a method for absorbing phosphogypsum roasting smoke and co-producing phosphoric acid and cement clinker by phosphate rock slurry.
Background
Phosphogypsum is a solid waste produced in a wet-process phosphoric acid process, and the components of the phosphogypsum are mainly calcium sulfate dihydrate. The phosphoric acid is produced by a wet process, and 4.5-5 t of phosphogypsum is produced every 1 t of phosphoric acid is produced. The random discharge and accumulation of the phosphogypsum seriously damage the ecological environment, not only pollutes underground water resources, but also causes the waste of land resources.
In the prior art, based on the basic principle of phosphogypsum pyrolysis, the technology of preparing sulfuric acid by using phosphogypsum has been reported, but a plurality of problems exist, for example, a large national phosphate fertilizer enterprise in Yunnan builds a first domestic production line for producing 7 ten thousand tons of sulfuric acid and 10 ten thousand tons of cement every year in 1986, after production operation, the production of acid by phosphogypsum is stopped due to overhigh production cost, and the cement production is changed into the production of acid by limestone; another production enterprise in Yunnan province also adopts the technology of 'decomposing phosphogypsum to prepare acid', but from the source of acid preparation raw materials, the phosphogypsum only accounts for a part of the whole dosage, and other main sources are natural gypsum and sulfur.
The high silicon phosphogypsum in Yunnan is used for producing sulfuric acid and co-producing cement, and has certain technical difficulty. Firstly, a high silicon content leads to a low lime saturation factor (i.e. KH value), C of the clinker3S less, C2S is more, the early strength of the clinker is low and the clinker is easy to pulverize; SiO 22High content of silica causes problems such as too high silica ratio, too small amount of liquid phase, and difficulty in calcination. To reduce phosphogypsum, the production is carried out immediatelySiO in the material2The content of the raw material must be proportioned, which must reduce SO in the raw material3And (4) content. However, according to the data report, SO in the raw meal3The SO content in the kiln gas is reduced by 1 percent2The concentration was changed by 0.37%; when the concentration of the kiln gas is changed by 1%, the investment cost of acid making construction is increased by 10%.
Chinese patent CN100513341A discloses a method for producing cement and sulfuric acid by using high-silicon phosphogypsum, but the raw materials of the method are required to be phosphogypsum and calcareous raw materials which are mixed and homogenized, so that the subsequent reaction can be carried out only after the CaO of the mixture reaches 39-43 percent, the reaction temperature is as high as 1400 ℃, the energy consumption is high, and the problems of high difficulty and high cost of the subsequent preparation of acid by sulfur dioxide gas exist. Chinese patent CN102530886A discloses a method for preparing sulfuric acid and cement by using phosphogypsum, and CN106431031A discloses a method for preparing sulphoaluminate cement and co-producing sulfuric acid by using phosphogypsum, but firstly, the phosphogypsum has lower silicon content and low difficulty in producing cement; and most of the existing methods for preparing sulfuric acid and co-producing cement by using phosphogypsum have the problems of low sulfur dioxide concentration, high difficulty in acid preparation, high cost and difficulty in industrial expansion and application.
The phosphorite slurry method desulfurization takes phosphorite slurry as an absorbent and SO2And SO3The method replaces sulfuric acid to decompose phosphorite, simultaneously utilizes residual oxygen in the flue gas to catalytically oxidize the sulfurous acid in the solution into sulfuric acid, continuously increases the sulfur capacity of the solution and absorbs SO in the flue gas2The generated sulfuric acid and phosphorite further undergo chemical reaction to generate phosphogypsum and phosphoric acid, and the aim of desulfurization is fulfilled. But the method has the defect that the problem of accumulation of a large amount of phosphogypsum in the existing wet-process phosphoric acid process is not solved.
Based on the above problems, it is necessary to invent a method for absorbing the phosphogypsum roasting smoke and co-producing phosphoric acid and cement clinker by using phosphorite slurry.
Disclosure of Invention
The invention aims to provide a method for absorbing phosphogypsum roasting smoke and co-producing phosphoric acid and cement clinker by phosphorite slurry.
The invention aims to realize the method for absorbing the phosphogypsum roasting smoke and co-producing phosphoric acid and cement clinker by the phosphorite slurry, which comprises the following steps:
1) drying: drying the phosphogypsum until the moisture content is less than 4%;
2) homogenizing: mixing the dried phosphogypsum with a mineralizer and a reducing agent in proportion for primary homogenization, then adding the ingredients according to the requirements of cement components, and homogenizing again;
3) and (3) pyrolysis: the homogenized material enters a hollow long kiln and exchanges heat with hot tail gas from a kiln head to realize preheating; then, continuously moving the preheated material to the kiln head, raising the temperature of the material to 780-810 ℃, entering a decomposition section, continuously raising the temperature to 950-1000 ℃, and entering a sintering section; the high-temperature decomposition time of the phosphogypsum in the kiln is 30 min-40 min, and the SO-containing phosphogypsum is obtained2Roasting flue gas and residues by using the phosphogypsum, and cooling the residues to obtain cement clinker;
4) decomposing phosphate ore: will contain SO2Introducing the phosphogypsum roasting flue gas into the phosphorite slurry to decompose phosphorite, performing solid-liquid separation after full reaction, returning filter residue which is phosphogypsum to the step (1) as a raw material for circular treatment, wherein the filtrate is dilute phosphoric acid, and discharging gas.
Compared with the prior art, the invention has the following technical effects:
1. the invention uses the phosphorus ore pulp to absorb the phosphogypsum roasting smoke to co-produce phosphoric acid and cement clinker, not only can realize the recycling harmless treatment of the phosphogypsum, but also does not need a smoke acid making system after the phosphogypsum is decomposed, sulfur dioxide smoke is directly introduced into the phosphorus ore pulp to decompose phosphorite to generate the phosphogypsum and the phosphoric acid, the phosphogypsum returns to a roasting section to realize the circulating treatment, the concentration of the sulfur dioxide in the treated smoke is extremely low, the smoke can be directly discharged, and the whole process has no waste discharge and no harmful gas generation.
2. Compared with the prior art that the high requirement of the phosphogypsum roasting flue gas acid production on the concentration of sulfur dioxide is different, the method adopts the phosphorite slurry to absorb the phosphogypsum roasting flue gas without considering the concentration of sulfur dioxide in the flue gas, and effectively avoids the problem that the cost for producing acid is obviously increased due to the low concentration of sulfur dioxide in the roasting flue gas after the high-silicon phosphogypsum is mixed according to cement components during high-temperature decomposition.
3. The invention realizes the closed-loop treatment of the production and decomposition of the phosphogypsum in the wet-process phosphoric acid, realizes the decomposition of the phosphorite in the phosphorite slurry by the sulfur dioxide generated by the high-temperature decomposition of the phosphogypsum to generate the phosphoric acid product and the phosphogypsum, returns the phosphogypsum for high-temperature decomposition, solves the problem of the accumulation of a large amount of the phosphogypsum in the wet-process phosphoric acid, and has low operation cost and simple flow.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The invention is further described with reference to the accompanying drawings, but the invention is not limited in any way, and any alterations or substitutions based on the teaching of the invention are within the scope of the invention.
As shown in figure 1, the method for absorbing the phosphogypsum roasting smoke and co-producing phosphoric acid and cement clinker by the phosphorite slurry comprises the following steps:
1) drying: drying the phosphogypsum until the moisture content is less than 4%;
2) homogenizing: mixing the dried phosphogypsum with a mineralizer and a reducing agent in proportion for primary homogenization, then adding the ingredients according to the requirements of cement components, and homogenizing again;
3) and (3) pyrolysis: the homogenized material enters a hollow long kiln and exchanges heat with hot tail gas from a kiln head to realize preheating; then, continuously moving the preheated material to the kiln head, raising the temperature of the material to 780-810 ℃, entering a decomposition section, continuously raising the temperature to 950-1000 ℃, and entering a sintering section; the high-temperature decomposition time of the phosphogypsum in the kiln is 30 min-40 min, and the SO-containing phosphogypsum is obtained2Roasting flue gas and residues by using the phosphogypsum, and cooling the residues to obtain cement clinker;
4) decomposing phosphate ore: will contain SO2Introducing the phosphogypsum roasting flue gas into the phosphorite slurry to decompose phosphorite, performing solid-liquid separation after full reaction, returning filter residue which is phosphogypsum to the step (1) as a raw material for circular treatment, wherein the filtrate is dilute phosphoric acid, and discharging gas.
Preferably, the reducing agent is a carbonaceous reducing agent, and the carbonaceous reducing agent is coke.
Preferably, SiO in the phosphogypsum is2The content of (A) is 5-20%.
Preferably, the solid content of the phosphorite slurry is 50-70%, and the granularity of the phosphorite slurry is not less than 80% when the phosphorite slurry passes through a 100-mesh screen.
Example 1
A method for absorbing phosphogypsum roasting smoke and co-producing phosphoric acid and cement clinker by phosphorite slurry comprises the following steps:
1) drying: drying the phosphogypsum until the water content is 3.5%;
2) homogenizing: mixing the dried phosphogypsum with a mineralizer and a reducing agent in proportion for primary homogenization, then adding the ingredients according to the requirements of cement components, and homogenizing again;
3) and (3) pyrolysis: the homogenized material enters a hollow long kiln and exchanges heat with hot tail gas from a kiln head to realize preheating; then, the preheated material is continuously moved to the kiln head, the temperature of the material is increased to 780 ℃, the material enters a decomposition section, the temperature is continuously increased to 950 ℃, and the material enters a sintering section; the high-temperature decomposition time of the phosphogypsum in the kiln is 30min, SO that SO is obtained2Roasting flue gas and residues by using the phosphogypsum, and cooling the residues to obtain cement clinker; the decomposition rate reaches 85 percent;
4) decomposing phosphate ore: will contain SO2Introducing the phosphogypsum roasting flue gas into the phosphorite pulp to decompose phosphorite, performing solid-liquid separation after full reaction, returning filter residue which is phosphogypsum to the step (1) as a raw material for circular treatment, wherein the filtrate is dilute phosphoric acid, and the gas meets the emission standard and can be directly discharged.
Example 2
A method for absorbing phosphogypsum roasting smoke and co-producing phosphoric acid and cement clinker by phosphorite slurry comprises the following steps:
1) drying: drying the phosphogypsum until the water content is 3%;
2) homogenizing: mixing the dried phosphogypsum with a mineralizer and a reducing agent in proportion for primary homogenization, then adding the ingredients according to the requirements of cement components, and homogenizing again;
3) and (3) pyrolysis: the homogenized material enters a hollow long kiln and is heated with hot tail gas from a kiln headExchanging to realize preheating; then, the preheated material is continuously moved to the kiln head, the temperature of the material is increased to 800 ℃, the material enters a decomposition section, the temperature is continuously increased to 980 ℃, and the material enters a sintering section; the high-temperature decomposition time of the phosphogypsum in the kiln is 35min, SO that SO is obtained2Roasting flue gas and residues by using the phosphogypsum, and cooling the residues to obtain cement clinker; the decomposition rate reaches 90 percent;
4) decomposing phosphate ore: will contain SO2Introducing the phosphogypsum roasting flue gas into the phosphorite pulp to decompose phosphorite, performing solid-liquid separation after full reaction, returning filter residue which is phosphogypsum to the step (1) as a raw material for circular treatment, wherein the filtrate is dilute phosphoric acid, and the gas meets the emission standard and can be directly discharged.
Example 3
A method for absorbing phosphogypsum roasting smoke and co-producing phosphoric acid and cement clinker by phosphorite slurry comprises the following steps:
1) drying: drying the phosphogypsum until the moisture content is less than 4%;
2) homogenizing: mixing the dried phosphogypsum with a mineralizer and a reducing agent in proportion for primary homogenization, then adding the ingredients according to the requirements of cement components, and homogenizing again;
3) and (3) pyrolysis: the homogenized material enters a hollow long kiln and exchanges heat with hot tail gas from a kiln head to realize preheating; then, the preheated material is continuously moved to the kiln head, the temperature of the material is raised to 810 ℃, the material enters a decomposition section, the temperature is continuously raised to 1000 ℃, and the material enters a sintering section; the high-temperature decomposition time of the phosphogypsum in the kiln is 40min to obtain the product containing SO2Roasting flue gas and residues by using the phosphogypsum, and cooling the residues to obtain cement clinker; the decomposition rate reaches 95 percent;
4) decomposing phosphate ore: will contain SO2Introducing the phosphogypsum roasting flue gas into the phosphorite pulp to decompose phosphorite, performing solid-liquid separation after full reaction, returning filter residue which is phosphogypsum to the step (1) as a raw material for circular treatment, wherein the filtrate is dilute phosphoric acid, and the gas meets the emission standard and can be directly discharged.
Claims (5)
1. A method for absorbing phosphogypsum roasting smoke and co-producing phosphoric acid and cement clinker by phosphorite slurry is characterized by comprising the following steps:
1) drying: drying the phosphogypsum until the moisture content is less than 4%;
2) homogenizing: mixing the dried phosphogypsum with a mineralizer and a reducing agent in proportion for primary homogenization, then adding the ingredients according to the requirements of cement components, and homogenizing again;
3) and (3) pyrolysis: the homogenized material enters a hollow long kiln and exchanges heat with hot tail gas from a kiln head to realize preheating; then, continuously moving the preheated material to the kiln head, raising the temperature of the material to 780-810 ℃, entering a decomposition section, continuously raising the temperature to 950-1000 ℃, and entering a sintering section; the high-temperature decomposition time of the phosphogypsum in the kiln is 30 min-40 min, and the SO-containing phosphogypsum is obtained2Roasting flue gas and residues by using the phosphogypsum, and cooling the residues to obtain cement clinker;
4) decomposing phosphate ore: will contain SO2Introducing the phosphogypsum roasting flue gas into the phosphorite slurry to decompose phosphorite, performing solid-liquid separation after full reaction, returning filter residue which is phosphogypsum to the step (1) as a raw material for circular treatment, wherein the filtrate is dilute phosphoric acid, and discharging gas.
2. The method for absorbing the flue gas generated by roasting the phosphogypsum and co-producing the phosphoric acid and the cement clinker by the phosphorite slurry as claimed in claim 1, characterized in that the reducing agent is a carbonaceous reducing agent, and the carbonaceous reducing agent is coke.
3. The method for absorbing the flue gas generated by roasting the phosphogypsum and co-producing the phosphoric acid and the cement clinker by the phosphorite slurry as claimed in claim 1, wherein the SiO in the phosphogypsum is SiO2The content of (A) is 5-20%.
4. The method for co-production of phosphoric acid and cement clinker by absorbing phosphogypsum roasting flue gas through phosphorite slurry according to claim 1, characterized in that the solid content of the phosphorite slurry is 50-70%, and the granularity of the phosphorite slurry is not less than 80% when the phosphorite slurry is passed through a 100-mesh sieve.
5. The method for absorbing the phosphogypsum roasting flue gas and co-producing phosphoric acid and cement clinker by the phosphate rock slurry as claimed in claim 1, characterized in that the concentration of the phosphogypsum roasting flue gas is 5-30%.
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