CN112250051B - Method for co-producing phosphoric acid and cement clinker by absorbing phosphogypsum roasting smoke by phosphorite slurry - Google Patents
Method for co-producing phosphoric acid and cement clinker by absorbing phosphogypsum roasting smoke by phosphorite slurry Download PDFInfo
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- CN112250051B CN112250051B CN202011111716.0A CN202011111716A CN112250051B CN 112250051 B CN112250051 B CN 112250051B CN 202011111716 A CN202011111716 A CN 202011111716A CN 112250051 B CN112250051 B CN 112250051B
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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
- 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
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/24—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
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/36—Manufacture of hydraulic cements in general
- C04B7/38—Preparing or treating the raw materials individually or as batches, e.g. mixing with fuel
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/36—Manufacture of hydraulic cements in general
- C04B7/43—Heat treatment, e.g. precalcining, burning, melting; Cooling
- C04B7/432—Preheating without addition of fuel
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/36—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
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- 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
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- 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)
- Combustion & Propulsion (AREA)
- Processing Of Solid Wastes (AREA)
- Treating Waste Gases (AREA)
Abstract
The invention discloses a method for co-producing phosphoric acid and cement clinker by absorbing phosphogypsum roasting smoke by phosphorite slurry, which comprises the following steps: 1) Drying; 2) Homogenizing; 3) High temperature decomposition to obtain SO-containing material 2 Phosphogypsum roasting smoke and residues, and cooling the residues to obtain cement clinker; 4) And (3) decomposing phosphorite: will contain SO 2 And (3) introducing phosphogypsum roasting flue gas into the phosphogypsum pulp, decomposing the phosphorite, fully reacting for solid-liquid separation, taking phosphogypsum as filter residue, returning to the step (1) as raw material, and taking filtrate as dilute phosphoric acid and discharging gas. The invention uses the phosphorite slurry to absorb phosphogypsum roasting flue gas to co-produce phosphoric acid and cement clinker, not only can realize phosphogypsum recycling harmless treatment, but also does not need a flue gas acid making system after phosphogypsum is decomposed, sulfur dioxide flue gas is directly introduced into the phosphogypsum slurry and is decomposed after being absorbed to produce phosphogypsum and phosphoric acid, phosphogypsum returns to a roasting working section to realize cyclic treatment, and the treated flue gas can be directly discharged without waste discharge and harmful gas generation in the whole process.
Description
Technical Field
The invention belongs to the technical field of phosphogypsum recycling harmless treatment, and particularly relates to a method for co-producing phosphoric acid and cement clinker by absorbing phosphogypsum roasting smoke by using phosphorite slurry.
Background
Phosphogypsum is a solid waste generated in the wet-process phosphoric acid process, and the component of phosphogypsum is mainly calcium sulfate dihydrate. Phosphoric acid is produced by adopting a wet process, and 4.5-5 t phosphogypsum is produced every time 1 t phosphoric acid is produced. The random discharge and accumulation of phosphogypsum seriously damages the ecological environment, not only pollutes the underground water resource, but also causes the waste of land resource.
In the prior art, based on the basic principle of phosphogypsum pyrolysis, the technology for preparing sulfuric acid by using phosphogypsum has been reported, but various problems exist, such as that a large-scale national phosphate fertilizer enterprise in Yunnan builds a production line for producing 7 ten thousand tons of sulfuric acid and 10 ten thousand tons of cement in the first year in 1986, and after the production operation, the phosphogypsum acid preparation is stopped due to the over high production cost, and the cement production is changed into limestone; another production enterprise in Yunnan province also adopts the technology of phosphogypsum decomposition to prepare acid, but from the source of acid preparation raw materials, phosphogypsum only occupies a part of the whole dosage, and other main sources are natural gypsum and sulfur.
The high-silicon phosphogypsum of Yunnan is used for producing sulfuric acid and co-producing cement, and has certain technical difficulty. First, a high silicon content results in a clinker with a low lime saturation coefficient (i.e. KH value), C 3 S is less, C 2 S is more, the early strength of clinker is low and the clinker is easy to pulverize; siO (SiO) 2 The high content can cause the problems of high silica content and silicic acid ratio, too little liquid phase amount, difficult calcination and the like. To reduce SiO in phosphogypsum, i.e. raw material 2 The content of the raw materials must be proportioned, which in turn tends to reduce the SO in the raw materials 3 The content is as follows. However, according to the report of the related data, SO in the raw meal 3 The content is reduced by 1 percent, SO in kiln gas 2 Concentration change 0.37%; when the kiln gas concentration is changed by 1%, the investment cost for 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 are required to be mixed and homogenized by phosphogypsum and calcareous raw materials, so that the subsequent reaction can be carried out after the CaO of the mixture reaches 39-43%, the reaction temperature is up to 1400 ℃, the energy consumption is high, and the problems of high acid making difficulty and high cost of the subsequent sulfur dioxide gas are also caused. Chinese patent CN102530886a discloses a method for preparing sulfuric acid and cement from phosphogypsum, CN106431031a discloses a method for preparing sulphoaluminate cement and co-producing sulfuric acid by using phosphogypsum, but firstly, the phosphogypsum has low silicon content and low difficulty in producing cement; in addition, the existing method for preparing the sulfuric acid co-production cement by phosphogypsum mostly has the problems of low sulfur dioxide concentration, high difficulty in preparing acid and high cost, and is not beneficial to industrial expansion application.
The desulfurization by the phosphor pulp method uses phosphor pulp as absorbent and SO 2 SO and SO 3 The method replaces sulfuric acid to decompose phosphorite, and simultaneously utilizes the residual oxygen in the flue gas to catalyze and oxidize sulfurous acid in the solution into sulfuric acid, thereby continuously increasing the sulfur capacity of the solution and absorbing SO in the flue gas 2 The generated sulfuric acid and phosphorite further generate chemical reaction to generate phosphogypsum and phosphoric acid, and the purpose of desulfurization is achieved. However, 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 problems, it is necessary to invent a method for absorbing phosphogypsum roasting flue gas by using phosphorite slurry to co-produce phosphoric acid and cement clinker.
Disclosure of Invention
The invention aims to provide a method for co-producing phosphoric acid and cement clinker by absorbing phosphogypsum roasting smoke by phosphorite slurry.
The invention aims to realize the method for co-producing phosphoric acid and cement clinker by absorbing phosphogypsum roasting smoke by using phosphorite slurry, which comprises the following steps:
1) And (3) drying: drying phosphogypsum until the water content is less than 4%;
2) Homogenizing: mixing the dried phosphogypsum with a mineralizer and a reducing agent in proportion for primary homogenization, adding ingredients according to the requirements of cement components, and homogenizing again;
3) High-temperature decomposition: the homogenized material enters a hollow long kiln, and is subjected to heat exchange with hot tail gas from the kiln head to realize preheating; then the preheated material is continuously moved to the kiln head, the temperature of the material is increased to 780-810 ℃, the material enters a decomposition section and is continuously increased to 950-1000 ℃, and the material enters a sintering section; the high-temperature decomposition time of phosphogypsum in the kiln is 30 min-40 min, and SO-containing phosphogypsum is obtained 2 Phosphogypsum roasting smoke and residues, and cooling the residues to obtain cement clinker;
4) And (3) decomposing phosphorite: will contain SO 2 Phosphogypsum of (C)And (3) introducing roasting flue gas into the phosphorus ore pulp, decomposing the phosphorus ore, fully reacting, performing solid-liquid separation, taking phosphogypsum as filter residues, returning the filter residues to the step (1) as raw materials for recycling treatment, and taking filtrate as dilute phosphoric acid and discharging gas.
Compared with the prior art, the invention has the following technical effects:
1. the invention uses the phosphogypsum slurry to absorb phosphogypsum roasting flue gas to co-produce phosphoric acid and cement clinker, not only can realize phosphogypsum recycling harmless treatment, but also does not need a flue gas acid making system after phosphogypsum decomposition, sulfur dioxide flue gas is directly introduced into the phosphogypsum slurry to decompose the phosphogypsum to generate phosphogypsum and phosphoric acid, the phosphogypsum returns to a roasting working section to realize cyclic treatment, and the treated flue gas has extremely low sulfur dioxide concentration and can be directly discharged, so that the whole process has no waste discharge and no harmful gas generation.
2. Unlike available technology, the present invention has phosphate ore slurry to absorb phosphogypsum roasting fume and has no need of considering the sulfur dioxide concentration in the fume, and this can avoid the problem of obvious increase in the cost of preparing acid with low sulfur dioxide concentration in the roasting fume caused by compounding cement component during high-temperature decomposition of high-silicon phosphogypsum.
3. The invention realizes the closed-loop treatment of phosphogypsum generation and decomposition in the wet-process phosphoric acid, and the sulfur dioxide generated by the high-temperature decomposition of the phosphogypsum realizes the decomposition of the phosphorite in the phosphogypsum slurry to generate phosphoric acid products and phosphogypsum, and the phosphogypsum returns to carry out the high-temperature decomposition, thereby solving the problem of accumulation of a large amount of phosphogypsum in the wet-process phosphoric acid, and having 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 below with reference to the accompanying drawings, without limiting the invention in any way, and any alterations or substitutions based on the teachings of the invention are intended to fall within the scope of the invention.
As shown in fig. 1, the method for co-producing phosphoric acid and cement clinker by absorbing phosphogypsum roasting smoke by using phosphorite slurry comprises the following steps:
1) And (3) drying: drying phosphogypsum until the water content is less than 4%;
2) Homogenizing: mixing the dried phosphogypsum with a mineralizer and a reducing agent in proportion for primary homogenization, adding ingredients according to the requirements of cement components, and homogenizing again;
3) High-temperature decomposition: the homogenized material enters a hollow long kiln, and is subjected to heat exchange with hot tail gas from the kiln head to realize preheating; then the preheated material is continuously moved to the kiln head, the temperature of the material is increased to 780-810 ℃, the material enters a decomposition section and is continuously increased to 950-1000 ℃, and the material enters a sintering section; the high-temperature decomposition time of phosphogypsum in the kiln is 30 min-40 min, and SO-containing phosphogypsum is obtained 2 Phosphogypsum roasting smoke and residues, and cooling the residues to obtain cement clinker;
4) And (3) decomposing phosphorite: will contain SO 2 And (2) introducing phosphogypsum roasting flue gas into the phosphogypsum pulp, decomposing the phosphorite, fully reacting, carrying out solid-liquid separation, taking phosphogypsum as filter residue, returning to the step (1) as a raw material for recycling treatment, and taking filtrate as dilute phosphoric acid and discharging gas.
Preferably, the reducing agent is a carbon reducing agent, and the carbon reducing agent is coke.
Preferably, siO in the phosphogypsum 2 The content of (2) 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% after passing through 100 meshes.
Example 1
A method for co-producing phosphoric acid and cement clinker by absorbing phosphogypsum roasting smoke by phosphorite slurry comprises the following steps:
1) And (3) drying: drying 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, adding ingredients according to the requirements of cement components, and homogenizing again;
3) High-temperature decomposition: the homogenized material enters a hollow long kiln, and is subjected to heat exchange with hot tail gas from the kiln head to realize preheating; the preheated material is then continued toMoving the kiln head, increasing the temperature of the materials to 780 ℃, entering a decomposition section, continuously increasing the temperature to 950 ℃, and entering a sintering section; the high-temperature decomposition time of phosphogypsum in the kiln is 30min, and SO-containing phosphogypsum is obtained 2 Phosphogypsum roasting smoke and residues, and cooling the residues to obtain cement clinker; the decomposition rate reaches 85%;
4) And (3) decomposing phosphorite: will contain SO 2 And (2) introducing phosphogypsum roasting flue gas into the phosphogypsum pulp to decompose the phosphorite, fully reacting, carrying out solid-liquid separation, taking phosphogypsum as filter residue, returning to the step (1) as raw material for recycling treatment, and taking filtrate as dilute phosphoric acid, wherein the gas meets the emission standard and is directly discharged.
Example 2
A method for co-producing phosphoric acid and cement clinker by absorbing phosphogypsum roasting smoke by phosphorite slurry comprises the following steps:
1) And (3) drying: drying 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, adding ingredients according to the requirements of cement components, and homogenizing again;
3) High-temperature decomposition: the homogenized material enters a hollow long kiln, and is subjected to heat exchange with hot tail gas from the kiln head 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 and is continuously increased to 980 ℃, and the material enters a firing section; the high-temperature decomposition time of phosphogypsum in the kiln is 35min, and SO-containing phosphogypsum is obtained 2 Phosphogypsum roasting smoke and residues, and cooling the residues to obtain cement clinker; the decomposition rate reaches 90%;
4) And (3) decomposing phosphorite: will contain SO 2 And (2) introducing phosphogypsum roasting flue gas into the phosphogypsum pulp to decompose the phosphorite, fully reacting, carrying out solid-liquid separation, taking phosphogypsum as filter residue, returning to the step (1) as raw material for recycling treatment, and taking filtrate as dilute phosphoric acid, wherein the gas meets the emission standard and is directly discharged.
Example 3
A method for co-producing phosphoric acid and cement clinker by absorbing phosphogypsum roasting smoke by phosphorite slurry comprises the following steps:
1) And (3) drying: drying phosphogypsum until the water content is less than 4%;
2) Homogenizing: mixing the dried phosphogypsum with a mineralizer and a reducing agent in proportion for primary homogenization, adding ingredients according to the requirements of cement components, and homogenizing again;
3) High-temperature decomposition: the homogenized material enters a hollow long kiln, and is subjected to heat exchange with hot tail gas from the kiln head to realize preheating; then the preheated material is continuously moved to the kiln head, the temperature of the material is increased to 810 ℃, the material enters a decomposition section and is continuously increased to 1000 ℃, and the material enters a sintering section; the high-temperature decomposition time of phosphogypsum in the kiln is 40min, and SO-containing phosphogypsum is obtained 2 Phosphogypsum roasting smoke and residues, and cooling the residues to obtain cement clinker; the decomposition rate reaches 95%;
4) And (3) decomposing phosphorite: will contain SO 2 And (2) introducing phosphogypsum roasting flue gas into the phosphogypsum pulp to decompose the phosphorite, fully reacting, carrying out solid-liquid separation, taking phosphogypsum as filter residue, returning to the step (1) as raw material for recycling treatment, and taking filtrate as dilute phosphoric acid, wherein the gas meets the emission standard and is directly discharged.
Claims (2)
1. The method for co-producing phosphoric acid and cement clinker by absorbing phosphogypsum roasting smoke by using phosphorite slurry is characterized by comprising the following steps:
1) And (3) drying: drying phosphogypsum until the moisture is less than 4%, wherein SiO (silicon dioxide) in phosphogypsum 2 The content of (2) is 5-20%;
2) Homogenizing: mixing the dried phosphogypsum with a mineralizer and a reducing agent in proportion for primary homogenization, adding ingredients according to the requirements of cement components, and homogenizing again;
3) High-temperature decomposition: the homogenized material enters a hollow long kiln, and is subjected to heat exchange with hot tail gas from the kiln head to realize preheating; then the preheated material is continuously moved to the kiln head, the temperature of the material is increased to 780-810 ℃, the material enters a decomposition section and is continuously increased to 950-1000 ℃, and the material enters a sintering section; the high-temperature decomposition time of phosphogypsum in the kiln is 30 min-40 min, and SO-containing phosphogypsum is obtained 2 The phosphogypsum roasting smoke and residues are cooled to obtain cement clinker, wherein the concentration of the phosphogypsum roasting smoke is 5-30%;
4) And (3) decomposing phosphorite: will contain SO 2 And (3) introducing phosphogypsum roasting flue gas into the phosphogypsum slurry, wherein the solid content of the phosphogypsum slurry is 50-70%, the particle size of the phosphogypsum slurry is not less than 80% after passing through 100 meshes, decomposing the phosphogypsum, fully reacting, carrying out solid-liquid separation, filtering residues to obtain phosphogypsum, returning to the step (1) as a raw material for recycling treatment, and discharging the filtrate to obtain diluted phosphoric acid.
2. The method for co-producing phosphoric acid and cement clinker by absorbing phosphogypsum roasting flue gas with phosphorite slurry according to claim 1, wherein the reducing agent is a carbon reducing agent, and the carbon reducing agent is coke.
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| CN1948131A (en) * | 2006-10-31 | 2007-04-18 | 李光明 | Coproducing cement technological method of producing acid using phosphogypsum and sulfur |
| CN101050074A (en) * | 2006-04-04 | 2007-10-10 | 马芸仙 | Method for producing cement and vitriol from high silicon ardealite |
| WO2008043222A1 (en) * | 2006-09-30 | 2008-04-17 | Hubei Sanxin Phosphoric Acid Co. Ltd | Method for directly producing phosphoric acid and several silicate or aluminate byproducts from phosphate ore raw materials |
| CN105836722A (en) * | 2016-04-08 | 2016-08-10 | 龚家竹 | A method of directly using phosphogypsum decomposition gas for wet method phosphoric acid production |
| WO2017173716A1 (en) * | 2016-04-08 | 2017-10-12 | 成都千砺金科技创新有限公司 | Method for joint production of phosphogypsum decomposition gas and wet-process phosphoric acid |
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| CN101050074A (en) * | 2006-04-04 | 2007-10-10 | 马芸仙 | Method for producing cement and vitriol from high silicon ardealite |
| WO2008043222A1 (en) * | 2006-09-30 | 2008-04-17 | Hubei Sanxin Phosphoric Acid Co. Ltd | Method for directly producing phosphoric acid and several silicate or aluminate byproducts from phosphate ore raw materials |
| CN1948131A (en) * | 2006-10-31 | 2007-04-18 | 李光明 | Coproducing cement technological method of producing acid using phosphogypsum and sulfur |
| CN105836722A (en) * | 2016-04-08 | 2016-08-10 | 龚家竹 | A method of directly using phosphogypsum decomposition gas for wet method phosphoric acid production |
| WO2017173716A1 (en) * | 2016-04-08 | 2017-10-12 | 成都千砺金科技创新有限公司 | Method for joint production of phosphogypsum decomposition gas and wet-process phosphoric acid |
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| 工业副产石膏制硫酸联产水泥新技术进展;鲍树涛;硫酸工业(第02期);第51-56页 * |
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