CN106145073B - A kind of method of fluidized calcination rock phosphate in powder production yellow phosphorus - Google Patents
A kind of method of fluidized calcination rock phosphate in powder production yellow phosphorus Download PDFInfo
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- CN106145073B CN106145073B CN201610718662.1A CN201610718662A CN106145073B CN 106145073 B CN106145073 B CN 106145073B CN 201610718662 A CN201610718662 A CN 201610718662A CN 106145073 B CN106145073 B CN 106145073B
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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
- C01B25/02—Preparation of phosphorus
- C01B25/027—Preparation of phosphorus of yellow phosphorus
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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
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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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
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
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Abstract
The invention discloses a kind of fluidized calcination rock phosphate in powder production yellow phosphorus method, including：Rock phosphate in powder is processed into 300~500 μm and obtains ground phosphate rock, ground phosphate rock is preheated to 400~600 DEG C, enter from the feed inlet of fluidized-bed kiln, 300~500 DEG C of air enter from the bottom of fluidized-bed kiln, fully burning generates 1500 DEG C or more high temperature to fuel in fluidized-bed kiln, and the calcium in ground phosphate rock, the P elements moment in 1~2 second is made to resolve into phosphorus steam and clinker；Phosphorus steam, flue gas and the clinker that fluidized-bed kiln comes enter high-temperature gas-solid separator and are separated, enter miberal powder preheater after ground phosphate rock is heated in heat exchanger from the phosphorus steam and flue gas that high-temperature gas-solid separator is separated, after being cooled to 200~250 DEG C after being preheated to ground phosphate rock gas solid separation is carried out into gas-solid separator, phosphorus steam separates the phosphorus steam and flue gas separated with flue gas after washed absorption again, phosphorus steam becomes yellow phosphorus, flue gas discharge.Resource consumption of the present invention is few, energy saving, safety and environmental protection.
Description
Technical field
The production method of existing yellow phosphorus mainly has blast furnace process, electric furnace process, hydro carbons reduction method and kiln method, wherein grinding
That studies carefully has：Hydro carbons reduction method in the presence of silica, is obtained with methane reduction rock phosphate in powder；Kiln method, rock phosphate in powder and silica
Calcium pyrophosphate is generated at 1200 DEG C and resolves into calcium phosphate and P at 1000 DEG C2O5, then with coke (anthracite) reduce P2O5And it obtains.
Comparative maturity has：Blast furnace process, reduction reaction carry out under the hot conditions in blast furnace.Since blast furnace process has phosphorus in furnace gas
Many shortcomings such as content is low, furnace volume is excessive, calorific value of gas is low, the rate of recovery of phosphorus is low, thus blast furnace process progressively by
It eliminates.Electric furnace process；Reduction reaction in electric current at a high temperature of studied.Electric liter method.Electric furnace has product for some reason
Quality is good（Purity reaches 99.9%）, the advantages of productivity is high, at low cost, therefore, producing yellow Phosphorus by electric oven is current industrial metaplasia
The unique method of production, advantage seems especially prominent in the area of supply of electric power abundance, but electric furnace process has the following disadvantages：
（1）In terms of resource consumption：Need a large amount of silicas and coke；
（2）In terms of energy consumption：One ton of yellow phosphorus of production needs the electric energy of 13500~15000kwh；
（3）Energy saving aspect：For high temperature deslagging at 1200~1300 DEG C, energy waste amount is big；
（4）Environmentally friendly aspect：One ton of yellow phosphorus of production needs 7~9 tons of high temperature furnace slags of deslagging, and environmental pollution influences big；
（5）Secure context：Deslagging temperature high safety hidden danger is big；
（6）In terms of fire-fighting：System is operation under positive pressure, flame phenomenon often occurs, and fire hazard is big.
The content of the invention
Few, energy saving, safety and environmental protection the boiling of a kind of resource consumption that it is an object of the invention to overcome disadvantages mentioned above and provide
The method for rising calcining rock phosphate in powder production yellow phosphorus.
A kind of method of fluidized calcination rock phosphate in powder production yellow phosphorus of the present invention, comprises the following steps：
（1）It is prepared by ground phosphate rock；Rock phosphate in powder is homogenized after being crushed to 15~20mm, is ground to 300~500 μm and is obtained ground phosphate rock, into
Miberal powder warehouse stores；
（2）Raw material preheating：The phosphorus steam and flue gas of heat exchanger discharge preheat ground phosphate rock in miberal powder preheater；
（3）Gas solid separation：The ground phosphate rock after 150~250 DEG C is preheating to carry out together with the mixture of phosphorus steam and flue gas
Gas solid separation, ground phosphate rock enters heat exchanger and continues to heat after gas solid separation, until 400~600 DEG C；
（4）Fluidized calcination：400~600 DEG C of ground phosphate rock enters from the feed inlet of fluidized-bed kiln, and air is through air preheat
Device, which is preheating to after 300~500 DEG C from the bottom of fluidized-bed kiln, to be entered, and fully burning generates 1500 to fuel in fluidized-bed kiln
DEG C or more high temperature, the calcium in ground phosphate rock, the P elements moment in 1~2 second is made to resolve into phosphorus steam and clinker；
（5）High-temperature gas-solid separates：Phosphorus steam, flue gas and the clinker that fluidized-bed kiln comes enter the progress of high-temperature gas-solid separator
Separation enters miberal powder after ground phosphate rock is heated in heat exchanger from the phosphorus steam and flue gas that high-temperature gas-solid separator is separated and preheats
Device carries out gas solid separation after being cooled to 200~250 DEG C after being preheated to ground phosphate rock into gas-solid separator, and the phosphorus separated steams
Phosphorus steam is separated with flue gas after washed absorption again for vapour and flue gas, and phosphorus steam becomes yellow phosphorus, flue gas discharge.
（6）Cooling of furnace slag is discharged；Clinker after high-temperature gas-solid separation separation enters air preheater to carry out with combustion air
The postcooling that exchanges heat is discharged to 200~250 DEG C.
A kind of method of above-mentioned fluidized calcination rock phosphate in powder production yellow phosphorus, wherein：200~250 DEG C of clinkers are again through lag cooler
It is recycled and packaged after 70~80 DEG C are cooled to after being cooled down indirectly with water（Calcium oxide）.
A kind of method of above-mentioned fluidized calcination rock phosphate in powder production yellow phosphorus, wherein：The coke of supplying 5~10% in ground phosphate rock
Charcoal.
A kind of method of above-mentioned fluidized calcination rock phosphate in powder production yellow phosphorus, wherein：Increase air amount of allocating makes high-temperature calcination
The phosphorus steam separated in stove from ground phosphate rock is completely oxidized to phosphorus pentoxide by enough high temperature airs and carrys out preparing phosphoric acid.
Compared with prior art, the present invention with apparent advantageous effect, it was found from upper technical solution；
（1）In terms of resource consumption；A large amount of silicas and coke is not required in the present invention.
（2）In terms of energy consumption；A large amount of electric energy are not required in the present invention, directly carry out boiling to rock phosphate in powder using combustion gas and forge
It burns, one ton of rock phosphate in powder of calcining needs oil liquefied gas in 150~200Nm3（8000kcol/Nm3）.
（3）Energy saving aspect；The present invention exchanges heat deslagging temperature 70~80 using flue gas and miberal powder heat exchange, air and clinker
DEG C, energy waste is few.
（4）Environmentally friendly aspect；Clinker of the present invention is calcium oxide, is common construction material and industrial chemicals, is production process
In by-product.Clinker stockyard is not required, environmental pollution is without influence.
（5）Secure context；Deslagging temperature lower security hidden danger is small.
（6）In terms of fire-fighting；System is run for negative pressure, does not have flame phenomenon, no fire hazard.
Description of the drawings
Fig. 1 is the process flow chart of the present invention.
Specific embodiment
Embodiment 1：
A kind of method of fluidized calcination rock phosphate in powder production yellow phosphorus, comprises the following steps：
（1）It is prepared by ground phosphate rock；Rock phosphate in powder is homogenized after being crushed to 15~20mm, is ground to 300~500 μm and is obtained ground phosphate rock, into
Miberal powder warehouse stores；
（2）Raw material preheating：The phosphorus steam and flue gas of heat exchanger discharge preheat ground phosphate rock in miberal powder preheater；
（3）Gas solid separation：The ground phosphate rock after 150~250 DEG C is preheating to carry out together with the mixture of phosphorus steam and flue gas
Gas solid separation, ground phosphate rock enters heat exchanger and continues to heat after gas solid separation, until 400~600 DEG C；
（4）Fluidized calcination：400~600 DEG C of ground phosphate rock enters from the feed inlet of fluidized-bed kiln, and air is through air preheat
Device, which is preheating to after 300~500 DEG C from the bottom of fluidized-bed kiln, to be entered, and fully burning generates 1500 to fuel in fluidized-bed kiln
DEG C or more high temperature, the calcium in ground phosphate rock, the P elements moment in 1~2 second is made to resolve into phosphorus steam and clinker（Main ingredient oxygen
Change calcium）；
（5）High-temperature gas-solid separates：Phosphorus steam, flue gas and the clinker that fluidized-bed kiln comes enter the progress of high-temperature gas-solid separator
Separation enters miberal powder after ground phosphate rock is heated in heat exchanger from the phosphorus steam and flue gas that high-temperature gas-solid separator is separated and preheats
Device carries out gas solid separation after being cooled to 200~250 DEG C after being preheated to ground phosphate rock into gas-solid separator, and the phosphorus separated steams
Phosphorus steam is separated with flue gas after washed absorption again for vapour and flue gas, and phosphorus steam becomes yellow phosphorus, flue gas discharge.
（6）Cooling of furnace slag is discharged；Clinker after high-temperature gas-solid separation separation enters air preheater to carry out with combustion air
The postcooling that exchanges heat is discharged to 200~250 DEG C.Recycling bag is carried out after cooling to 70~80 DEG C after lag cooler and water indirectly cooling again
Dress（Calcium oxide）.
When the present invention can be incorporated 5~10% coke in ground phosphate rock, protected with ensureing to produce carbonic oxide in gaseous mixture
Phosphorus steam is not oxidized to produce yellow phosphorus.
Embodiment 2：
Increase air amount of allocating makes the phosphorus steam separated in high-temperature calcination stove from ground phosphate rock empty by enough high temperature
Gas is completely oxidized to phosphorus pentoxide and carrys out preparing phosphoric acid.Remaining is the same as embodiment 1.
The above described is only a preferred embodiment of the present invention, not making limitation in any form to the present invention, appoint
Without departing from technical solution of the present invention content, technical spirit according to the invention any is simply repaiied to what above example was made for what
Change, equivalent variations and modification, in the range of still falling within technical solution of the present invention.
Claims (4)
1. a kind of method of fluidized calcination rock phosphate in powder production yellow phosphorus, comprises the following steps：
（1）It is prepared by ground phosphate rock；Rock phosphate in powder is homogenized after being crushed to 15~20mm, is ground to 300~500 μm and is obtained ground phosphate rock, into miberal powder
Warehouse stores；
（2）Raw material preheating：The phosphorus steam and flue gas of heat exchanger discharge preheat ground phosphate rock in miberal powder preheater；
（3）Gas solid separation：The mixture for being preheating to the ground phosphate rock after 150~250 DEG C and phosphorus steam and flue gas carries out gas-solid together
It separates, ground phosphate rock enters heat exchanger and continues to heat after gas solid separation, until 400~600 DEG C；
（4）Fluidized calcination：400~600 DEG C of ground phosphate rock enters from the feed inlet of fluidized-bed kiln, and air is pre- through air preheater
Heat enters to after 300~500 DEG C from the bottom of fluidized-bed kiln, fuel in fluidized-bed kiln fully burning generate 1500 DEG C with
Upper high temperature makes the calcium in ground phosphate rock, the P elements moment in 1~2 second resolve into phosphorus steam and clinker；
（5）High-temperature gas-solid separates：Phosphorus steam, flue gas and the clinker that fluidized-bed kiln comes enter high-temperature gas-solid separator and are divided
From, from the phosphorus steam and flue gas that high-temperature gas-solid separator is separated ground phosphate rock is heated in heat exchanger after into miberal powder preheat
Device carries out gas solid separation after being cooled to 200~250 DEG C after being preheated to ground phosphate rock into gas-solid separator, and the phosphorus separated steams
Phosphorus steam is separated with flue gas after washed absorption again for vapour and flue gas, and phosphorus steam becomes yellow phosphorus, flue gas discharge；
（6）Cooling of furnace slag is discharged；Clinker after high-temperature gas-solid separation separation enters air preheater and exchanges heat with combustion air
Postcooling is discharged to 200~250 DEG C.
2. a kind of method of fluidized calcination rock phosphate in powder production yellow phosphorus as described in claim 1, wherein：200~250 DEG C of clinkers are again
Through lag cooler with being recycled and packaged after cooling to 70~80 DEG C after water indirectly cooling（Calcium oxide）.
3. a kind of method of fluidized calcination rock phosphate in powder production yellow phosphorus as claimed in claim 1 or 2, wherein：Match somebody with somebody in ground phosphate rock
Enter 5~10% coke.
4. a kind of method of fluidized calcination rock phosphate in powder production yellow phosphorus as claimed in claim 3, wherein：Increase air amount of allocating makes
The phosphorus steam separated in high-temperature calcination stove from ground phosphate rock is completely oxidized to phosphorus pentoxide to make by enough high temperature airs
Take phosphoric acid.
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| CN108314069A (en) * | 2018-05-08 | 2018-07-24 | 杨光华 | A kind of method of dry sintering dissolution aluminium oxide |
| CN108408705B (en) * | 2018-06-01 | 2021-07-13 | 雷波明信实业发展有限公司 | Phosphoric acid production device and method based on multistage fluidized bed |
| CN109467067B (en) * | 2019-01-16 | 2020-04-24 | 中州新材料(杭州)有限公司 | Preparation process of high-purity phosphorus pentoxide |
| CN115594158A (en) * | 2022-12-01 | 2023-01-13 | 云南布兰特化工有限公司（Cn） | Method for preparing yellow phosphorus from phosphate by using silicothermic reduction and application |
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| DE3826981A1 (en) * | 1988-08-09 | 1990-02-15 | Hoechst Ag | METHOD FOR PROCESSING DUST WHICH ARISES IN ELECTROTHERMAL PHOSPHORUS PRODUCTION |
| CN201463541U (en) * | 2009-08-12 | 2010-05-12 | 李竟川 | Boiling and calcining furnace |
| CN101774553B (en) * | 2010-03-26 | 2012-01-11 | 成都高威节能科技有限公司 | Method for calcining raw materials in furnace in yellow phosphorus production |
| CN102674274B (en) * | 2012-05-25 | 2015-06-24 | 葛振华 | Yellow phosphorus ore processing technology |
| CN105197901B (en) * | 2015-09-16 | 2017-12-22 | 黄钰雪 | Phosphorus ore containing potassium prepares the power-economizing method of yellow phosphorus, sylvite, sodium carbonate and aluminum oxide |
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