CN1562847A - Method for producing phosphoric acid and cement from phosphate ore by hot process - Google Patents
Method for producing phosphoric acid and cement from phosphate ore by hot process Download PDFInfo
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- CN1562847A CN1562847A CN 200410034577 CN200410034577A CN1562847A CN 1562847 A CN1562847 A CN 1562847A CN 200410034577 CN200410034577 CN 200410034577 CN 200410034577 A CN200410034577 A CN 200410034577A CN 1562847 A CN1562847 A CN 1562847A
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- phosphoric acid
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Abstract
Phosphate ore, coal, silica and bauxite are processed by drying, grinding, prilling and drying, then to be send into rotary kiln to be roasted, reacted furnace gas is processed by dedusting, hydration absorbing and purifying to produce phosphate product, roasted reacted furnace dregs can be used to produce cement by adding calcined gypsum and shell the being grinded to powder.
Description
The technical field is as follows: the invention relates to a novel environment-friendly process method for producing phosphoric acid and co-producing cement
Secondly, background art: at present, the main domestic process methods for producing phosphoric acid comprise: the phosphoric acid is prepared by using electric furnace yellow phosphorus product as raw material, through thermal method of preparing phosphoric acid product by combustion oxidation and hydration, and by using inorganic acid (sulfuric acid, hydrochloric acid, etc.) to react with powdered rock phosphate, the phosphoric acid and phosphogypsum waste residue are displaced, and the wet-process phosphoric acid is obtained after phosphogypsum is separated.The yellow phosphorus thermal method is characterized in that: the phosphoric acid product has good quality and high content, but consumes a large amount of electric energy, has high production cost, and produces a large amount of waste residue pollution sources (namely, the waste residue amount generated by each ton of phosphoric acid is about 4 tons) when the electric furnace is used for preparing the phosphorus. The wet method for preparing phosphoric acid is characterized in that: the production cost of the phosphoric acid is low; but the product quality is poor, the content is low, the product is generally used for producing fertilizers, the acid quality requirement of industrial phosphate cannot be met, and a large amount of phosphogypsum pollution sources (about 6 tons of waste residues are generated per ton of standard phosphoric acid) are generated in the acid production process; and a large amount of sulfur resources are wasted. The invention relates to a method for producing phosphoric acid by directly reducing phosphate ore, which is invented by institute of Long Sand mining and metallurgy of the department of metallurgical industry, and has the following patent numbers: 931114470: the patent is characterized in that the production cost is lower, and P in phosphorite2O5The utilization rate reaches 80 percent; but there are a number of sources of slag contamination.
The object of the invention isIn order to overcome the defects of the prior art, the calcination of cement clinker, the reduction of phosphate ore and the oxidation of phosphorus steam are completed in the same rotary kiln at one time, so that the combination of phosphoric acid and cement production is realized; compared with the prior art, the method can greatly reduce the production cost of phosphoric acid and cement, and completely return furnace gas dust and residues for purifying phosphoric acid into the ingredients to ensure that P in the phosphorite2O5The utilization rate of the method reaches more than 90 percent, and the generation of waste residue and waste water pollution sources is avoided. The quality of the phosphoric acid obtained by the method meets the national standard GB 2091-92; the quality of cement products can reach over 325 grades. The method of the invention fully utilizes the heat release of the chemical reaction and the process waste heat, and has very obvious economic benefit, environmental protection benefit and social benefit.
Thirdly, the invention content: the content of the invention is as follows: mixing and evenly mixing phosphate ore and coal with silica and bauxite in a ratio of 1: 0.35-0.45: 0.35-0.65: 0.20-0.35 (calculated according to the dry weight ratio), and grinding the evenly mixed materials into powder in a grinding mill, wherein the fineness requires that the 180-mesh passing rate is 60-70%; or respectively grinding the materials into powder, and then mixing the materials according to the proportion. The milled and mixed material was fed into a pan granulator and about 20% of the material was fed below the granulator for the dusting cycle. And (2) starting the granulator, and spraying clay slurry (the clay slurry consists of dispersing agents such as clay, water and pentasodium, the specific gravity of the slurry is 1.3-1.4, the pH value is 6.5-10, the solid content is about 45%, the solid fineness is less than 1mm, and the pentasodium content is 0.5% of the total amount of the slurry) into the granulator for granulation. Control the ball diameterThe diameter is 6-20 mm, and the water content of the material balls is 10-15%. The prepared pellets fall into the dry powder below the granulator for powder coating so as to prevent the pellets from adhering to each other. And conveying the pellets and the dry powder after powder coating into a drying screening machine for drying, separating thepowder and fine particles with the particle size less than 6mm, returning the powder and the fine particles into a granulator, and conveying the pellets with the particle size more than 6mm into a feeding hopper of a rotary kiln for later use. The diameter of the rotary kiln is more than 1.5m, the length of the rotary kiln is more than 30m, the thickness of the lining heat-insulating layer is required to be 20cm, and the thickness of the fire-resistant layer is more than or equal to 10 cm; the inclination of the kiln is 3-6 degrees (horizontal included angle). The pellets are added from the exhaust end of the rotary kiln and pass through a drying section,The pre-reaction section and the reaction section complete the whole process of the calcination reaction. Controlling the retention time of the material balls added into the furnace slag to be discharged to be 3-6 hours; the deslagging temperature of the rotary kiln is 800-1000 ℃; the exhaust temperature of the rotary kiln is 500-800 ℃, and the rotation speed of the rotary kiln is 2-6 r/min. According to the temperature condition of the rotary kiln, coal powder and hot air are intermittently or continuously sprayed into the kiln to maintain the normal temperature of 1300-1450 ℃ in the reaction section of the rotary kiln (the coal spraying and slag discharging end of the rotary kiln is about 10m to the kiln as the reaction section, the middle part of the rotary kiln is generally called as a pre-reaction section, and the exhaust end of the rotary kiln is about 10m as the drying section). And discharging the slag after the calcination reaction into an air heat exchanger for heat exchange and cooling, adding calcined gypsum and quick lime into the cooled slag, crushing the slag into 325 meshes, and obtaining the cement product after inspection and packaging, wherein the pass rate is more than 90%. The ratio of the slag to the calcined gypsum to the quicklime is 1: 0.1-0.35: 0.1-0.3 (calculated by dry weight ratio). The furnace gas in the rotary kiln is led intoa four-stage cyclone dust collector for dust collection treatment, and the collected dust and the residue of purified phosphoric acid are returned to a granulation section for use. Controlling inlet air temperature of the first cycloneThe temperature of the fourth cyclone dust collector is 500-800 ℃, and the temperature of the outlet air of the fourth cyclone dust collector is 250-350 ℃. Introducing the furnace gas after dust removal treatment into a hydration absorption tower, and circularly spraying and absorbing P in the furnace gas by using dilute phosphoric acid2O5Let P stand2O5The gas hydrates to phosphoric acid. And (4) after the concentration of the circulating acid meets the requirement, pumping the circulating acid into a settling pond or a filter for purification treatment, and obtaining the finished product phosphoric acid through inspection and quantitative packaging. And (3) washing the residual gas after acid preparation by using a two-stage alkaline aqueous solution, introducing the residual gas into a waste heat recovery device to combust carbon monoxide gas in the waste heat recovery device, and recovering heat energy. In the implementation process of the invention, the pollution sources of waste residues and waste water are eliminated, and P in phosphorite is utilized2O5The utilization rate is improved to more than 90%. The chemical reaction equation is as follows:
1. the main reaction formula of the rotary kiln for calcining materials is as follows:
2. reaction of phosphorus vapor with hot air in a rotary kiln:
3. the reaction formula of the synthetic phosphoric acid in the hydration absorption tower is as follows:
4. the reaction formula among the main components in the cement is as follows:
the technological process of the invention is shown in the attached drawing of the specification
Fourth, example
Take the production of 3000 tons of 85% phosphoric acid and 12000 tons of cement in a production device for production. The main equipment is as follows:
1. raymond mill: three sets of the air separation and dust collection device are provided, and the production capacity of the air separation and dust collection device is 8-10T/hour.
2. A disc granulator: one set, diameter of the granulating pan: phi 3.2m, side height: 400 mm. Rotating speed: 10 revolutions per minute.
3. Rotating the calcining kiln: diameter phi of 1.9m multiplied by length 30 m; the rotating speed is 2-6 r/min; horizontal slope of 5 degrees.
4. Hydration circulation absorption tower: two, diameter phi 1.2m is multiplied by height 8 m; and a 50mm graphite plate is lined.
5. Tail gas washing tower: two, diameter phi m is multiplied by 5m, and the carbon steel is internally anticorrosive.
6. A slurry preparation tank: two, capacity 20m3Each provided with a stirring device.
7. Double helix compounding device: two sets, production capacity 30m3And (4) setting the time per hour.
8. Cement packaging line: one line, 6 tons/hour of production capacity.
9. An ore coarse crusher: one, the production capacity is 50T/h, and the crushing fineness is less than or equal to 6 mm.
A. Preparing materials: mixing phosphorus ore (P)2O5The content is more than or equal to 28 percent); white coal (carbon content is more than or equal to 70%), silica (SiO-containing)2More than or equal to 95 percent); bauxite (containing Al)2O3Not less than 60 percent) of the raw materials are respectively dried according to the ratio of the phosphate ore to the white coal to the silica oreBauxite equal to 1: 0.4: 0.5: 0.25The raw materials are mixed according to the proportion, and are sent into a Raymond mill for crushing (for example, the raw ore with the ore particle size larger than 10mm is coarsely crushed to be less than 6mm before being sent into the Raymond mill), and the air inlet pressure of the Raymond mill and the passing rate of collected powder are preferably controlled to be 60-70% of 180-mesh passing rate.
B. Preparing slurry: selecting clay for pottery, adding water, stirring into slurry, and controlling the specific gravity of the slurry to be 1.30-1.35; the solid content is about 45 percent; the particle size of the solid is less than or equal to 1 mm. In order to prevent the mud from precipitating and improve the wettability and the fluidity of the mud, sodium tripolyphosphate (pentasodium) is added into the mud according to 0.5 percent of the weight of the mud, and the PH value is controlled as follows: 6.5 to 7.5.
C. Granulating and drying: and conveying the ground mixed material to a granulating disc of a disc granulator, and spraying slurry into the granulating disc. The material is moistened and bonded into particles in a rolling way, the particle size is gradually increased and the particles fall into the dry powder under the plate for powder coating, so that the pellets are prevented from being adhered to each other. The spherical particles coated with the powder and the dry powder are sent into a dryer to be dried, the dried material balls and the dry powder are screened by a 6mm sieve mesh machine, and the granules and the dry powder smaller than 6mm return to a granulator to be granulated; and feeding the granules larger than 6mm into the air outlet end of the rotary kiln through a feeder for calcination reaction. The qualified material particles with the diameter of 10-20 mm account for more than 60%.
D. Calcining reaction and furnace gas hydration for preparing acid:
firstly, spraying diesel oil and air into the rotary kiln for combustion, heating the reaction section to about 500 ℃, then spraying pulverized coal and hot air into the rotary kiln, and adding the material particles into the rotary kiln when the air outlet temperature of the rotary kiln reaches 500-600 ℃. Controlling the material particles to rotateThe residence time in the rotary kiln is 4-5 hours, the deslagging temperature is controlled to be 900-1000 ℃, and the maximum feeding speed is 4000 kg/hour. When the slag discharging temperature is lower than 800 ℃, the speed of coal powder spraying and hot air is increased, the feeding speed is reduced, and when the slag discharging temperature reaches 950 ℃, the quantity of the coal powder spraying and the hot air can be stopped or reduced. The furnace gas of the calcination reaction is subjected to dust collection treatment by a four-stage series cyclone dust collector, and the outlet temperature of a fourth cyclone dust collector is controlled as follows: 250 to 350 ℃. Furnace gas after dust removal treatmentAnd introducing into a hydration absorption tower. Injecting P in circulating phosphoric acid absorption furnace gas into the upper part of the hydration tower2O5The gas becomes phosphoric acid. When the content of the circulating phosphoric acid reaches over 86 percent, the circulating phosphoric acid can be pumped into a settling pond or a filter for purification treatment. And (4) checking the purified phosphoric acid to be qualified, and quantitatively packaging to obtain the finished phosphoric acid. Absorbing residual gas after acid production, and introducing sodium carbonate aqueous solution (Na)2CO3Content 20%) in the spray washing tower, circularly spraying and washing. And introducing the washed residual gas into a lime kiln, burning the carbon monoxide gas in the lime kiln and utilizing the heat energy of the carbon monoxide gas. The dust collected by the cyclone dust collector and the residue after phosphoric acid purification are combined and returned to the particle separator.
E. Production of cement: and (4) calcining the reacted slag in the rotary kiln, and discharging the slag into an air heat exchange device for heat exchange. The heated air is sent into a rotary kiln for pulverized coal spraying; cooling the heat-exchanged furnace slag to below 100 ℃, adding calcined gypsum and quicklime according to the weight ratio of the furnace slag to the calcined gypsum to the quicklime being equal to 1: 0.15: 0.1, uniformly mixing, then sending into a Raymond mill for crushing, wherein the pass rate of 325 meshes is required to be more than 90%, and inspecting, packaging, warehousing and aging the ground cement material to obtain the cement product.
Claims (3)
1. A method for preparing phosphorus and cement by phosphorite thermal method comprises drying phosphorite, coal, silica and bauxite, grinding, granulating, drying, calcining in rotary kiln, dedusting reaction furnace gas, hydrating, absorbing, and purifying to obtain phosphoric acid product; calcined slag is added with calcined gypsum and quicklime and ground to obtain a cement product.
2. The method for producing phosphorus and cement by the hot method for the phosphorite according to claim 1, characterized in that: the ratio of phosphorus ore to coal to silica to bauxite is 1: 0.35-0.45: 0.35-0.65: 0.20-0.35 (calculated by dry weight ratio).
3. The method for producing phosphorus and cement by the hot method for the phosphorite according to claim 1, characterized in that: the ratio of the slag to the calcined gypsum after the calcination reaction to the quicklime is equal to 1: 0.1-0.35: 0.1-0.3 (calculated according to the dry weight ratio).
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| CN 200410034577 CN1243687C (en) | 2004-04-20 | 2004-04-20 | Method for producing phosphoric acid and cement from phosphate ore by hot process |
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| CN 200410034577 CN1243687C (en) | 2004-04-20 | 2004-04-20 | Method for producing phosphoric acid and cement from phosphate ore by hot process |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7910080B2 (en) | 2004-06-04 | 2011-03-22 | Jdcphosphate, Inc. | Phosphorous pentoxide producing methods |
| US8734749B2 (en) | 2011-11-29 | 2014-05-27 | Jdcphosphate, Inc. | Phosphorous pentoxide producing methods and phosphate ore feed agglomerates |
| WO2014194571A1 (en) * | 2013-06-04 | 2014-12-11 | 四川玖长科技有限公司 | Raw material pre-treatment process and raw material pre-treatment process system suitable for kiln process for production of phosphoric acid |
| CN106186776A (en) * | 2016-06-30 | 2016-12-07 | 湖北理工新型材料有限公司 | A kind of composite mineral powder and its preparation method and application |
| US9783419B2 (en) | 2014-09-26 | 2017-10-10 | Jdcphosphate, Inc. | Phosphorous pentoxide producing methods and systems with increased agglomerate compression strength |
| US11858811B2 (en) | 2019-06-30 | 2024-01-02 | Novaphos Inc. | Phosphorus production methods and systems and methods for producing a reduction product |
-
2004
- 2004-04-20 CN CN 200410034577 patent/CN1243687C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7910080B2 (en) | 2004-06-04 | 2011-03-22 | Jdcphosphate, Inc. | Phosphorous pentoxide producing methods |
| US8734749B2 (en) | 2011-11-29 | 2014-05-27 | Jdcphosphate, Inc. | Phosphorous pentoxide producing methods and phosphate ore feed agglomerates |
| WO2014194571A1 (en) * | 2013-06-04 | 2014-12-11 | 四川玖长科技有限公司 | Raw material pre-treatment process and raw material pre-treatment process system suitable for kiln process for production of phosphoric acid |
| CN104211034A (en) * | 2013-06-04 | 2014-12-17 | 四川玖长科技有限公司 | Raw material pretreatment method and raw material pretreatment process system suitable for kiln method phosphoric acid technology |
| RU2637909C2 (en) * | 2013-06-04 | 2017-12-07 | Сычуань Ко Чанг Технолоджи Ко., Лтд | Initial material preparing process and technological process developed for burning in furnace when receiving phosphoric acid |
| US10744512B2 (en) | 2013-06-04 | 2020-08-18 | Sichuan Ko Chang Technology Co., Ltd. | Raw material pre-treatment method and raw material pre-treatment process system suitable for kiln phosphoric acid process |
| US9783419B2 (en) | 2014-09-26 | 2017-10-10 | Jdcphosphate, Inc. | Phosphorous pentoxide producing methods and systems with increased agglomerate compression strength |
| CN106186776A (en) * | 2016-06-30 | 2016-12-07 | 湖北理工新型材料有限公司 | A kind of composite mineral powder and its preparation method and application |
| US11858811B2 (en) | 2019-06-30 | 2024-01-02 | Novaphos Inc. | Phosphorus production methods and systems and methods for producing a reduction product |
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