CN101844748B - Method for preparing high-concentration SO2 flue gas and active CaO by using phosphogypsum and decomposing furnace - Google Patents
Method for preparing high-concentration SO2 flue gas and active CaO by using phosphogypsum and decomposing furnace Download PDFInfo
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- CN101844748B CN101844748B CN2010101745136A CN201010174513A CN101844748B CN 101844748 B CN101844748 B CN 101844748B CN 2010101745136 A CN2010101745136 A CN 2010101745136A CN 201010174513 A CN201010174513 A CN 201010174513A CN 101844748 B CN101844748 B CN 101844748B
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Abstract
The invention relates to a method for preparing high-concentration SO2 flue gas and active CaO by using phosphogypsum and a decomposing furnace, and belongs to the technical fields of comprehensive utilization of resources of building materials and industrial solid rejected materials and chemical industry. The method comprises the following steps of: a, mixing phosphogypsum with flue gas at 700 DEG C in a broken dryer to remove complete free water and part of crystal water, allowing the mixture to stay for 1 to 2 seconds before entering a pneumatic drying device, and performing heat exchange with the flue gas at 700 DEG C to further remove residual crystal water and generate anhydrous gypsum; b, raising the temperature of the anhydrous gypsum at 40 DEG C through a vortex preheating system until the temperature reaches 800 DEG C, and allowing the anhydrous gypsum to enter the bottom of the decomposing furnace, and performing a decomposition reaction in an improved decomposing furnace which contains coke and has the temperature of between 900 and 1,150 DEG C; and forming an external circulation by the decomposing furnace and a fourth-stage vortex preheater through a material distribution valve. Solid materials are cooled by a tubular single-barrel cooler and are conveyed to a line warehouse; the high-concentration SO2 flue gas at 250 to 300 DEG C enters an acid making device; and the decomposing furnace is the improved decomposing furnace. The method and the decomposing furnace have the advantages of short process flow, easy control of reaction atmosphere, low decomposition temperature, high efficiency and high concentration of SO2 flue gas.
Description
Technical field:
The present invention relates to a kind ofly prepare high density SO with phosphogypsum
2The method of flue gas and active CaO and decomposing furnace belong to building materials, industrial solid castoff comprehensive utilization of resources and chemical technology field.
Background technology:
The decomposition relieving haperacidity of calcium sulfate and burning till of cement clinker have just been finished abroad in the forties in 20th century.After entering the mid-80 in last century, the sulphur price descends significantly because the world energy sources price rises significantly and regional cement sluggish market such as Europe, and abroad this type of device is closed successively or stopped production.Do not had phosphogypsum system sulfuric acid industry device at present abroad, the correlation technique exploitation also stays cool.
In the sixties in 20th century, China building materials department has just set up special scientific research institution under the cooperation of relevant departments, has born country's " six or five " tackling of key scientific and technical problems, and the technology of sulfuric acid and cement that gypsum and phosphogypsum are produced is carried out monographic study.It was that raw material is produced 60000 tons of sulfuric acid, 100,000 tons of Cement Production devices of coproduction per year with the phosphogypsum that China designs and built YUNLAN Phosphor Fertilizer Plant voluntarily on the basis of pilot scale and investigation foreign technology in 1986.Through repeatedly test run and trial production modification, change normal operation over to up to system in 1993.Nineteen ninety, Shandong Province's northern Shandong chemical industry is on the basis of study YUNLAN Phosphor Fertilizer Plant phosphogypsum system sulfuric acid, cement technology, and having built with the phosphogypsum is that raw material is produced 40000 tons of sulfuric acid, 60,000 tons of Cement Production devices (being called for short the 4-6 engineering) per year.Sulfuric acid, cement that this device is produced all can reach designed capacity, and product is qualified.Existing technology is because of wanting calcination of cement clinker, has that complex process, investment are big, small scale, production control difficulty, unstable product quality, is difficult to the problem of industrial applications.
Report with phosphogypsum system sulfuric acid is existing in the Chinese patent literature.Publication number [CN 101318632A] discloses and has a kind ofly prepared the method for producing sulfuric acid and jointly lime with the suspended state decomposing phosphogypsum, sends into decomposing furnace after this method utilizes the hammer drying crusher with the phosphogypsum oven dry and decomposes and produce SO
2Gas.But the hot blast of hammer drying crusher derives from gas cooler 150-250 ℃ cooling hot blast, and temperature is low, and duration of contact is short, is difficult to remove fully crystal water and free-water in the phosphogypsum.Phosphogypsum directly enters decomposing furnace without preheating, has increased the thermal load of decomposing furnace, has shortened the reaction times of material in decomposing furnace, and decomposition efficiency is lower, unit product hear rate height.First and second grade cyclone preheater has only played isolating effect, does not play the effect of heat exchange.This technology is under the situation that does not add coke, and temperature phosphogypsum more than 1200 ℃ the time just begins to decompose in the decomposing furnace, and molten state appears in phosphogypsum easily under this temperature, ties base in decomposing furnace, stops the continuation of phosphogypsum to be decomposed.
China is the deficient relatively country of a sulphur resource, utilizes phosphate fertilizer plant's by product phosphogypsum to produce the deficiency that sulfuric acid not only can remedy China's sulfuric acid raw material reserved resources; Phosphogypsum land occupation, problem of environment pollution caused have been solved simultaneously; Sulfuric acid can be used for phosphate fertilizer plant again and produces phosphoric acid, has constituted benign cycle; Have remarkable social benefit and economic benefit.
Summary of the invention:
The objective of the invention is to overcome the defective in the existing phosphogypsum relieving haperacidity technology, provide that a kind of technical process is short, reaction atmosphere is easy to control, ardealite decomposition temperature is low, decomposition efficiency is high, SO
2What flue gas concentration was high prepares high density SO with phosphogypsum
2The method of flue gas and active CaO and decomposing furnace.
The present invention is optimized innovation with present manufacture of cement modern technique, is applied to phosphogypsum and handles, and particularly utilizes the precal cination technique in the manufacture of cement, effective reduction phosphogypsum system sulfuric acid energy consumption and resolution problem.
Of the present inventionly prepare high density SO with phosphogypsum
2The method of flue gas and active CaO comprises drying and dehydrating, pre-thermolysis and lime refrigerating work procedure, and concrete steps are:
A. drying and dehydrating: the raw material phosphogypsum is quantitatively delivered to broken dryer by getting the material conveyor, from the temperature of hotblast stove is that 700 ℃ hot flue gas mixes with phosphogypsum at this, when breaing up, phosphogypsum removed whole free-waters and partial crystallization water by hot flue gas heating, taken out of broken dryer by hot flue gas after stopping 1-2s, enter the tubular type Pneumatic drying device, this with from 700 ℃ hot flue gas heat exchange of hotblast stove, generate dehydrated gyp-after removing whole crystal water; Store 2-4 hour by sending into steady feed bin after cyclonic separator and the bag filter collection;
B. pre-thermolysis: reduce to through the temperature after the steady feed bin storage and to enter preheating decomposition system from the one-level cyclone preheater with the airduct that is connected of secondary cyclone preheater after 40 ℃ dehydrated gyp-claims accurate measurement by belt, successively through one-level, secondary, three grades of cyclone preheaters, enter the decomposing furnace bottom after temperature risen to 800 ℃, in 900～1150 ℃ the environment that coke exists decomposition reaction takes place, wherein coke sprays into bottom, decomposing furnace reduction zone according to 0.5～0.75 metering of C/S mol ratio; The decomposing furnace middle and upper part feeds warm air, constitutes weak oxide atmosphere, and the generation and the CaS that suppress elemental sulfur are remaining, material is the self-forming internal recycling in decomposing furnace, mean air flow speed is 5m/s in the decomposing furnace, and the dehydrated gyp-residence time is 2～3s, and decomposition reaction is: 2CaSO
4+ C → 2CaO+2SO
2↑+CO
2↑; Material after the decomposition is brought reaction of fourth stage cyclone preheater and gas solid separation into by 900 ℃ hot flue gas, and decomposing furnace and fourth stage cyclone preheater constitute outer loop by material distributing valve; 250～300 ℃ contain high density SO
2Flue gas up flow successively pre-heating system and enter sulphuric acid plant;
C. lime cooling: the temperature that goes out decomposing system is that 900 ℃ active CaO is sent into lime bin after the tubular type single cylinder cooling machine is cooled to 85 ℃; Active CaO is sent into decomposing furnace through the cooling hot blast of 500～600 ℃ of tubular type single cylinder cooling machine cooling backs through the metering adjusting and is made full use of.
Be used for aforesaid method decomposing furnace, constitute by upper, middle, and lower part; It is characterized in that: decomposing furnace (12) top is provided with degradation production outlet (23) and the first hot blast import (24); Decomposing furnace (12) middle part is provided with fuel inlet (25), coke import (28) and material inlet (29); Decomposing furnace (12) bottom is provided with the second hot blast import (26) and cold high pressure wind inlet (27).
Equipment used is except that decomposing furnace is improvement in present method, and all the other equipment are that market is bought or self-control.
The present invention has that technical process is short, reaction atmosphere is easy to control, ardealite decomposition temperature is low, decomposition efficiency is high, SO
2The advantage that flue gas concentration is high.Through high temperature burn the CaO that can be directly as commodity selling or make building material product and sell.
Description of drawings:
Fig. 1 is a process flow sheet synoptic diagram of the present invention.Mark among the figure:
1, weighing belt; 2, broken dryer; 3, Pneumatic drying device; 4, cyclone; 5, induced draft fan; 6, sack cleaner; 7, steady feed bin; 8, weighing belt; 9, one-level cyclone preheater; 10, secondary cyclone preheater; 11, three grades of cyclone preheaters; 12, decomposing furnace; 13, Category Four cyclone preheater; 14, material distributing valve; 15, cooler; 16, lime bin; 17, coke bin; 18, disk weigher; 19, Pulverized Coal Bin; 20, disk weighing balance; 21, induced draft fan; 22, electric precipitator.
Fig. 2 is the structural representation of the used decomposing furnace of technology of the present invention.Mark among the figure:
12, decomposing furnace; 23, degradation production (material or gas) outlet; 24, the first hot blast import; 25, fuel inlet; 26, the second hot blast import; 27, cold high pressure wind inlet; 28, coke import; 29, material inlet.
Embodiment:
The present invention is further illustrated below in conjunction with accompanying drawing, but be not limited only to embodiment.Equipment used is except that decomposing furnace is improvement in the present embodiment, and all the other equipment are that market is bought.
The technological process of present method is:
The phosphogypsum of heap in the canopy directly added in the broken dryer 2 after metering, mix, stop and enter tubular type Pneumatic drying device 3 after 1～2 second, instantaneous free-water and the crystal water of removing with 700 ℃ hot flue gas from hotblast stove.All enter through cyclone 4 and solid materials after sack cleaner 6 separates and to enter decomposing furnace 12 from material inlet 29 after Category Four cyclone preheater 9,10,11,13 is preheated to 800 ℃.Coal dust sprays into decomposing furnace 12 from fuel inlet 25, and high pressure cold wind enters decomposing furnace 12 from import 27, and the cooling hot blast enters decomposing furnace 12 from the second hot blast import 26.Dehydrated gyp-decomposes under 900 or 1000 or 1150 ℃ temperature and obtains SO
2Flue gas and CaO solid.Wherein coke sprays into coke import 28 according to C/S mol ratio 0.5 or 0.65 or 0.75 metering; The cooling hot blast that decomposing furnace 12 tops, the first hot blast import 24 feeds from cooler 15 constitutes weak oxide atmosphere, and the generation and the CaS that suppress elemental sulfur are remaining.Material is the self-forming internal recycling in decomposing furnace 12, and the mean air flow speed are 5m/s in the decomposing furnace 12, and the dehydrated gyp-residence time is 2 or 3s, and decomposition reaction is: 2CaSO
4+ C → 2CaO+2SO
2↑+CO
2↑.Material after the decomposition is brought fourth stage cyclone preheater 13 reaction and gas solid separation into by 900 ℃ hot flue gas, and decomposing furnace 12 constitutes outer loop with fourth stage cyclone preheater 13 by material distributing valve 14.Temperature is that 250 or 300 ℃ volume content is greater than 12% SO after the gas solid separation
2Flue gas up enters sulphuric acid plant from degradation production outlet 23 pre-heating system that flows successively; Temperature is that 900 ℃ CaO solid goes out pre-heating system after tubular type single cylinder cooling machine 15 is directly sent into lime bin 16 after being cooled to 85 ℃ of temperature from degradation production outlet 23.Active CaO is sent into decomposing furnace through the cooling hot blast of 500 or 600 ℃ of tubular type single cylinder cooling machine cooling backs through the metering adjusting and is made full use of.
The phosphogypsum rate of decomposition of present method is greater than 95%, and desulfurization degree is greater than 85%, and CaO content is greater than 75% in the solid product, and wherein active CaO can be directly used in industries such as building materials.
Claims (2)
1. one kind prepares high density SO with phosphogypsum
2The method of flue gas and active CaO is characterized in that: method comprises drying and dehydrating, pre-thermolysis and lime refrigerating work procedure; Specific as follows:
A. drying and dehydrating: the raw material phosphogypsum is quantitatively delivered to broken dryer by getting the material conveyor, from the temperature of hotblast stove is that 700 ℃ hot flue gas mixes with phosphogypsum at this, when breaing up, phosphogypsum removed whole free-waters and partial crystallization water by hot flue gas heating, taken out of broken dryer by hot flue gas after stopping 1-2s, enter the tubular type Pneumatic drying device, this with from 700 ℃ hot flue gas heat exchange of hotblast stove, generate dehydrated gyp-after removing whole crystal water; Store 2-4 hour by sending into steady feed bin after cyclonic separator and the bag filter collection;
B. pre-thermolysis: reduce to through the temperature after the steady feed bin storage and to enter preheating decomposition system from the one-level cyclone preheater with the airduct that is connected of secondary cyclone preheater after 40 ℃ dehydrated gyp-claims accurate measurement by belt, successively through one-level, secondary, three grades of cyclone preheaters, enter the decomposing furnace bottom after temperature risen to 800 ℃, in 900～1150 ℃ the environment that coke exists decomposition reaction takes place, wherein coke sprays into bottom, decomposing furnace reduction zone according to 0.5～0.75 metering of C/S mol ratio; The decomposing furnace middle and upper part feeds warm air, constitutes weak oxide atmosphere, and the generation and the CaS that suppress elemental sulfur are remaining, material is the self-forming internal recycling in decomposing furnace, mean air flow speed is 5m/s in the decomposing furnace, and the dehydrated gyp-residence time is 2～3s, and decomposition reaction is: 2CaSO
4+ C → 2CaO+2SO
2↑+CO
2↑; Material after the decomposition is brought reaction of fourth stage cyclone preheater and gas solid separation into by 900 ℃ hot flue gas, and decomposing furnace and fourth stage cyclone preheater constitute outer loop by material distributing valve; 250～300 ℃ contain high density SO
2Flue gas up flow successively pre-heating system and enter sulphuric acid plant;
C. lime cooling: the temperature that goes out decomposing system is that 900 ℃ active CaO is sent into lime bin after the tubular type single cylinder cooling machine is cooled to 85 ℃; Active CaO is sent into decomposing furnace through the cooling hot blast of 500～600 ℃ of tubular type single cylinder cooling machine cooling backs through the metering adjusting and is made full use of.
2. be used for the described method of claim 1 decomposing furnace, constitute by upper, middle, and lower part; It is characterized in that: decomposing furnace (12) top is provided with degradation production outlet (23) and the first hot blast import (24); Decomposing furnace (12) middle part is provided with fuel inlet (25), coke import (28) and material inlet (29); Decomposing furnace (12) bottom is provided with the second hot blast import (26) and cold high pressure wind inlet (27).
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101745136A CN101844748B (en) | 2010-05-18 | 2010-05-18 | Method for preparing high-concentration SO2 flue gas and active CaO by using phosphogypsum and decomposing furnace |
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|---|---|---|---|
| CN2010101745136A CN101844748B (en) | 2010-05-18 | 2010-05-18 | Method for preparing high-concentration SO2 flue gas and active CaO by using phosphogypsum and decomposing furnace |
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| CN101844748A CN101844748A (en) | 2010-09-29 |
| CN101844748B true CN101844748B (en) | 2011-08-24 |
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| CN102815674A (en) * | 2011-06-08 | 2012-12-12 | 甘肃锦世化工有限责任公司 | Heat-exchanging device for kiln-feeding raw material and high-temperature flue gas of roasting rotary kiln for producing acid from gypsum |
| CN102320640A (en) * | 2011-08-17 | 2012-01-18 | 武汉工程大学 | Method for decomposing phosphogypsum through coupling reaction heat and vibration fluidizing |
| CN102936101B (en) * | 2012-11-12 | 2014-10-08 | 石家庄新华能源环保科技股份有限公司 | Method and device for producing lime and sulfuric acid by using gypsum |
| CN103396023B (en) * | 2013-07-30 | 2015-11-25 | 湖南恒光科技股份有限公司 | A kind of preparation technology of inactive anhydrous calcium sulfate |
| CN103539369B (en) * | 2013-11-05 | 2016-08-24 | 大唐国际发电股份有限公司高铝煤炭资源开发利用研发中心 | A kind of Method and system for drying Calcium silicon slag and reducing alkali |
| CN103663388B (en) * | 2013-12-06 | 2015-04-22 | 云南创兴建材新技术有限公司 | Method and reactor for preparing high concentration SO2 flue gas by using phosphogypsum through CaS |
| CN105036170A (en) * | 2015-07-27 | 2015-11-11 | 昆明理工大学 | Method for preparing calcium oxide through phosphogypsum decomposition |
| CN109650345B (en) * | 2018-04-09 | 2022-03-04 | 西南科技大学 | Method for respectively utilizing sulfur and calcium resources in gypsum |
| CN108910836A (en) * | 2018-09-25 | 2018-11-30 | 天津水泥工业设计研究院有限公司 | A kind of technique and device of gypsum Sulphuric acid coproduction lime |
| CN109745842B (en) * | 2019-02-28 | 2023-10-20 | 山东大学 | Heating decomposing furnace for recycling calcium oxide |
| CN109809456B (en) * | 2019-03-13 | 2021-02-26 | 山东大学 | System and method for co-producing calcium oxide and sulfur by coal gasification and gypsum calcination |
| CN115744835B (en) * | 2022-07-07 | 2024-06-14 | 云南云天化环保科技有限公司 | System and method for fused decomposition of phosphogypsum reduction mixture by entrained flow |
| CN117299001A (en) * | 2023-11-28 | 2023-12-29 | 北京中航泰达环保科技股份有限公司 | Desulfurization gypsum treatment carbon emission reduction composite set |
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| US5066474A (en) * | 1988-05-10 | 1991-11-19 | Science Ventures, Inc. | Method for sulfur dioxide production from calcium sulfate by entrained high-temperature slagging reduction |
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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 |
| CN101244811A (en) * | 2008-03-17 | 2008-08-20 | 云南云天化国际化工股份有限公司 | Method for improving SO2 concentration in acid making technique with decomposition of calcium sulphate |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5417399A (en) * | 1977-07-11 | 1979-02-08 | Mitsui Eng & Shipbuild Co Ltd | Thermally decomposing method for guypsum |
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2010
- 2010-05-18 CN CN2010101745136A patent/CN101844748B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5066474A (en) * | 1988-05-10 | 1991-11-19 | Science Ventures, Inc. | Method for sulfur dioxide production from calcium sulfate by entrained high-temperature slagging reduction |
| CN1724338A (en) * | 2005-06-16 | 2006-01-25 | 什邡市鸿升化工有限公司 | Process for producing industrial sulfuric acid using phosphorus gypsum as raw material |
| CN1948131A (en) * | 2006-10-31 | 2007-04-18 | 李光明 | Coproducing cement technological method of producing acid using phosphogypsum and sulfur |
| CN101244811A (en) * | 2008-03-17 | 2008-08-20 | 云南云天化国际化工股份有限公司 | Method for improving SO2 concentration in acid making technique with decomposition of calcium sulphate |
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