CN102367168A - Method and apparatus for decomposing gypsum with plasma - Google Patents
Method and apparatus for decomposing gypsum with plasma Download PDFInfo
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- CN102367168A CN102367168A CN2011103012793A CN201110301279A CN102367168A CN 102367168 A CN102367168 A CN 102367168A CN 2011103012793 A CN2011103012793 A CN 2011103012793A CN 201110301279 A CN201110301279 A CN 201110301279A CN 102367168 A CN102367168 A CN 102367168A
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Abstract
The invention discloses a method and an apparatus for decomposing gypsum with plasma. The method comprises the following steps: raw powder is prepared by treating gypsum powder and coal powder as raw materials, wherein the mass ratio of the coal powder in the raw powder is not more than 30%; and the raw powder conveyed by wind is successively subjected to primary plasma cracking, secondary plasma cracking, and gas-solid separation processing by a cyclone separator to make the volume fraction of SO2 in a gas output from the gas outlet of the cyclone separator be not less than 15%. The apparatus comprises plasma feeders, one or more second plasma generators, a decomposing furnace, the cyclone separator and a cooler. So the method of the invention, which adopts a plasma technology to carry out desulphurization processing on gypsum, has the advantages of wide raw material selection, low energy consumption, less investment, high operation ratio and high decomposition rate.
Description
Technical field
The present invention relates to the process method that a kind of gypsum decomposes system sulfuric acid and lime, belong to production technology and the comprehensive utilization of industry by-product gypsum residue resource and the enviromental protection and improvement field of chemical industry, building material industry.
Background technology
The research of gypsum decomposition technique started from for 20 beginnings of the century.1916, Miu Le and wealthy receiving (Muller Kuhne) the exploitation plaster of paris raw material of Germany decomposed in rotary kiln and make sulfuric acid and cement technology has been obtained success, have set up pilot plant; Thereafter, it is raw material production sulfuric acid and cement plant that Britain, Germany, Poland, Austria, South Africa etc. have been built up with the plaster of paris, anhydrite and phosphogypsum in succession, owing to decompose SO
2The low investment of concentration is big, hear rate is high, operation factor is low, the reason of deficiency in economic performance, successively stops production in the seventies in last century.
Nineteen sixty-eight American I owA university has developed two-stage fluidized and has decomposed plastering, and its upper bed control reducing atmosphere is at a lower temperature with CaSO
4Be decomposed into CaS and SO
2The CaS that decomposes gets into lower floor's fluidized-bed, and lower floor's bed controlled oxidation atmosphere is oxidized to CaO and SO with CaS
2The CaO that decomposes can be sintered into cement, also can do white lime and use; SO
2Gas concentration is higher, is used to make sulfuric acid.70-eighties of last century, the FSU released the technology in same fluidized-bed control reduction, two kinds of atmosphere of oxidation, and its principle is similar with IowA university, and the bottom adds gypsum and controls reducing atmosphere at a lower temperature with CaSO in the fluidized-bed of certain altitude
4Be decomposed into CaS and SO
2Controlled oxidation atmosphere is oxidized to CaO and SO with CaS on fluidized-bed top
2More than two kinds of methods carry out in fluidization, decompose SO
2High, low, the less investment of hear rate of concentration, the use prospect is good, but suitability for industrialized production not.German Lurgi company had released ciculation fluidized bed process in 1985, had accomplished the semipilot of day handling 10 t gypsum, had obtained abundant testing data.Have developed the U.S.'s scientific exploration company and the nineties in last century the flash fluidized-bed process on this basis, its significant parameter fluidizing velocity is high, and specification of equipment is little.The U.S. in 1991 associating mineral company has announced that the construction of employing fluidised bed decomposition phosphogypsum produces 2500000 t vitriolic integrated mills per year, but does not see the progress report so far.In recent years, the technician of states such as India, Morocco, Tunisia also had new achievement in research in this field, but did not have very quantum jump.
China is summing up on the technological both at home and abroad basis; Obtain and in rotary kiln, utilize salt gypsum, phosphogypsum, the plaster of paris, desulfurated plaster to decompose the success of making sulfuric acid and cement; And build 8 in last century Mo and overlap production equipments, the maximum scale that reaches 300,000 tons of cement of annual output 200000 tons of producing sulfuric acid and jointlies of phosphogypsum system.Investment is high, hear rate is big, power consumption is big, the shortcoming of deficiency in economic performance, so the stopping production that has but each device all exists.Carry out " produced by decomposition of phosphorous gypsum in circulating fluid bed system producing sulfuric acid and jointly cement " country " eight or five " key research project in the nineties in last century.Nineteen ninety has been accomplished theoretical investigation, builds up the cold model test device in 1991 and tests.Building up processing power in 1992 is the produced by decomposition of phosphorous gypsum in circulating fluid bed hot test device of 24t/d.On the basis of hot-die test, built up 150t/d vitriolic commerical test device at the beginning of 1993.Examination is burnt more than a year, has consumed great amount of manpower and financial resources and has obtained certain data, has proved the feasibility that the gypsum raw material use at cyclone preheater.Running period is very undesirable, does not go out specification product and stops.
China at present only the industrial gypsum annual emissions surpassed 9,000 ten thousand tons, and increase year by year.Owing to contain objectionable impurities in the industry by-product gypsum, discharging can cause serious environmental to pollute arbitrarily; The stockyard is set, and not only occupation of land is many, investment is big, the slag expense is high, and the geologic condition in stockyard is required height, and long-term accumulation can cause surface water and phreatic pollution.If gypsum is decomposited lime and SO
2, its purposes is more extensive, and benefit is higher.Though the invention of the patent No. 200810068831 can change the problems referred to above and since pyrolytic decomposition be prone to scab obstructions, rate of decomposition is low, operation factor is low, energy consumption is high, also fail the application.
Summary of the invention
The present invention is directed to the deficiency of prior art, the method that provides a kind of plasma to decompose gypsum, the desulfurization of adopting plasma technology to carry out gypsum is handled, and has raw material and draws materials extensively, and energy consumption is low, less investment, the advantage that operation factor is high, rate of decomposition is high.
For realizing above technical purpose, the present invention will take following technical scheme:
A kind of plasma decomposes the method for gypsum, may further comprise the steps: at first, be preparation of raw material raw material powder with terra alba and coal dust, and the quality proportion of coal dust in the raw material powder is no more than 30%; Then, the raw material powder that wind is carried carries out the gas solid separation of plasma pyrolysis, secondary plasma cracking and a cyclonic separator successively to be handled, and makes SO in the gas of cyclonic separator air outlet output
2Volume(tric)fraction is not less than 15%.
A described plasma pyrolysis is: the raw material powder ionization that the plasma body that adopts plasma generator to produce is come wind, thermally splitting are decomposed; To obtain the cracking head product one time, this cracking head product comprises uncracked raw material powder and split product SO
2, lime; Described secondary plasma is cracked into: a cracking head product that earlier adopts wind step (2) to obtain, and with uncracked raw material powder and split product SO
2, the lime initial gross separation; Make the raw material powder be suspended state; And the sedimentation of split product lime is collected; Then adopt plasma body that plasma generator produces that the raw material powder of wind to suspended state is carried out the secondary plasma cracking once more, obtain the second pyrolysis product, this second pyrolysis product comprises uncracked raw material powder and split product SO
2, lime, and the secondary plasma cracking temperature is between 1100 ℃-1200 ℃; Described cyclonic separator is made gas solid separation with the second pyrolysis product and is handled, and the pulverulent solids of this cyclonic separator discharge port output is collected coarse particles after the wind refrigerated separation, and fine particle is handled through the secondary plasma cracking once more.
The particle size of said raw material powder is between 20-100um; Said terra alba is selected from the plaster of paris, industry by-product gypsum or free-water < 5% two water, half water or anhydrous powder gypsum; Said coal dust is industrial bituminous coal or hard coal, and the calorific value of coal dust is greater than 16000 KJ/>Kg.
Another technical purpose of the present invention provides a kind of device of realizing above-mentioned plasma decomposition gypsum method, comprises plasma feeder, second plasma generator, decomposing furnace, cyclonic separator and water cooler; Said decomposing furnace is vertical setting, and the bottom of decomposing furnace is provided with the decomposing furnace blast inlet, and the decomposing furnace blast inlet is connected with a wind transport pipe simultaneously; The plasma body outlet of the opening for feed of the discharge port of said plasma feeder, the opening for feed of water cooler, cyclonic separator, the discharge port of cyclonic separator and second plasma generator all connects with decomposing furnace and is connected, and on the discharge port of cyclonic separator and the feeding pipe between the decomposing furnace air valve is installed; The blast inlet of said water cooler is connected with the secondary air transport pipe; The air outlet of water cooler then is connected with plasma feeder, second plasma generator through two connecting tubes respectively, and equal install adjustment valve on the connecting tube between water cooler and plasma feeder, second plasma generator; The connection site of said second plasma generator and decomposing furnace is higher than the connection site of plasma feeder and decomposing furnace; The connection site of water cooler and decomposing furnace is lower than the connection site of plasma feeder and decomposing furnace; The opening for feed of cyclonic separator and the connection site of decomposing furnace are higher than the connection site of second plasma generator and decomposing furnace, and the connection site of the discharge port of cyclonic separator and decomposing furnace is lower than the connection site of plasma feeder and decomposing furnace.
The top of said decomposing furnace is cylindric, and the bottom then is the inverted cone shape setting; And the height of the circular cylinder shaped portion of decomposing furnace and inverted cone shape part equates.
Said plasma feeder comprises the feeder and first plasma generator; The plasma spout of said first plasma generator is near the discharge port setting of feeder, and the discharge port axis normal of the axis of the plasma spout of first plasma generator and feeder.
Each decomposing furnace is equipped with 2-4 plasma feeder, and each plasma feeder is highly located uniform distribution at 1/4 of decomposing furnace; Each decomposing furnace is equipped with 2-4 plasma generator simultaneously, and each plasma generator is highly located uniform distribution at 3/4 of decomposing furnace.
Said decomposing furnace is installed air distribution plate near decomposing furnace blast inlet place.
According to above technical scheme, can realize following beneficial effect:
1, gypsum adopts the plasma decomposition technique, rate of decomposition is reached more than 98%, gas SO
2Concentration reaches more than 15%, has improved 50% more than than present decomposition technique.
2. raw material decompose back generation lime, and purposes is more extensive, reduce 30-40% than in rotary kiln, decomposing system cement hear rate.
3. this method technology is simple, invest low, the obstruction that do not scab, simple to operate.
Description of drawings
Fig. 1 is the plasma decomposition gypsum method flow synoptic diagram that is of the present invention;
Among the figure: decomposing furnace 1; Cyclonic separator 2; Air valve 3; Water cooler 4; Plasma feeder 5; Second ion generator 6 such as second grade; Variable valve 7.
Embodiment
Accompanying drawing discloses the structural representation of preferred embodiment involved in the present invention without limitation; Below will combine accompanying drawing that technical scheme of the present invention at length is described.
As shown in Figure 1, it provides a kind of and has realized that plasma according to the invention decomposes the device of gypsum method, comprises plasma feeder, second plasma generator, decomposing furnace, cyclonic separator and water cooler; Said decomposing furnace is vertical setting, and the bottom of decomposing furnace is provided with the decomposing furnace blast inlet, and the decomposing furnace blast inlet is connected with a wind transport pipe simultaneously; The plasma body outlet of the opening for feed of the discharge port of said plasma feeder, the opening for feed of water cooler, cyclonic separator, the discharge port of cyclonic separator and second plasma generator all connects with decomposing furnace and is connected, and on the discharge port of cyclonic separator and the feeding pipe between the decomposing furnace air valve is installed; The blast inlet of said water cooler is connected with the secondary air transport pipe; The air outlet of water cooler then is connected with plasma feeder, second plasma generator through two connecting tubes respectively, and equal install adjustment valve on the connecting tube between water cooler and plasma feeder, second plasma generator; The connection site of said second plasma generator and decomposing furnace is higher than the connection site of plasma feeder and decomposing furnace; The connection site of water cooler and decomposing furnace is lower than the connection site of plasma feeder and decomposing furnace; The opening for feed of cyclonic separator and the connection site of decomposing furnace are higher than the connection site of second plasma generator and decomposing furnace, and the connection site of the discharge port of cyclonic separator and decomposing furnace is lower than the connection site of plasma feeder and decomposing furnace.The top of said decomposing furnace is cylindric, and the bottom then is the inverted cone shape setting; And the height of the circular cylinder shaped portion of decomposing furnace and inverted cone shape part equates.Said plasma feeder comprises the feeder and first plasma generator; The plasma spout of said first plasma generator is near the discharge port setting of feeder, and the discharge port axis normal of the axis of the plasma spout of first plasma generator and feeder.Each decomposing furnace is equipped with 2-4 plasma feeder, and each plasma feeder is highly located uniform distribution at 1/4 of decomposing furnace; Each decomposing furnace is equipped with 2-4 plasma generator simultaneously, and each plasma generator is highly located uniform distribution at 3/4 of decomposing furnace.Said decomposing furnace is installed air distribution plate near decomposing furnace blast inlet place.
Hence one can see that, and the principle of work that above-mentioned realization plasma decomposes the device of gypsum method is:
Plasma generator arcing success on the plasma feeder 5 and produce low-temperature plasma after, the plasma temperature in plasma generator exit reaches 4000～5000 ℃, in the terminal high-temperature activation district that forms of feeder.Secondary air is carried the raw material powder that gypsum and coal process and is got into plasma feeder 5, and through the ionization rapidly under the physics chemical action of plasma body of high-temperature activation district, thermally splitting is decomposed; Coal dust is gasified obtains more gas fuel burning, promotes raw material to decompose, and mixes high temperature gas flow (800 ℃) and gets into decomposing furnace 1 bottom; Rise and the maintenance certain temperature at the moving low suspension of a wind; Arrive the plasma body of second ion generator, 6 generations such as top runs into, undecomposed raw material continue to decompose, and make the decomposing furnace head temperature reach 1100 ℃-1200 ℃; Raw material are fully decomposed, and generate high density SO
2And lime, degradation production flows out decomposing furnace with hot gas flow (900 ℃) and gets in the cyclonic separator 2, and high-speed rotational is with lime particle and high density SO
2Carry out gas solid separation, Han>15% high volumetric concentration SO
2Gas is got into by the separator top with hot gas (550 ℃) and makes sulfate system; Isolating lime returns decomposing furnace 1 bottom; The resolvent pellet density increases; Get into water cooler 4 after discharge secondary air cooling back, undecomposed fine particle gets into decomposing furnace 1 top and decomposes, and rate of decomposition is reached more than 98%.Variable valve 7 is to regulate decomposing furnace temperature and decomposition effect usefulness up and down.Air valve 3 guarantees not leak out bottom the separator.
Hence one can see that: the raw material that the present invention adopts is gypsum and coal, and green powder (gypsum and coal) particle size is all at 20-100um; Described gypsum can be the plaster of paris or industry by-product gypsum, contains free-water < 5% two water, half water or anhydrous powder gypsum; Coal is 0-30% at the content of raw material.Coal is industrial bituminous coal or hard coal, and calorific value is greater than 16000 KJ/>Kg.Secondary air is decomposed the raw material powder of gypsum and coal preparation through the rapid ionization in plasma high-temperature region of activation, the thermally splitting of plasma feeder 5; Get in the decomposing furnace 1; Under a wind effect, be the suspended state rising and run into the plasma body that plasma generator 6 produces; Continue thermally splitting and decompose, make the decomposing furnace upper temp reach 1100 ℃-1200 ℃, raw material fully are decomposed into SO
2And lime, and the cross section gas of decomposing furnace speed top is 6-8m/s, the bottom is 7-10m/s.Contain high density SO
2Gas separate through cyclonic separator 2 with resolvent lime, gas can be made sulfuric acid; Resolvent returns decomposing furnace through air valve 3 to be got rid of through water cooler 4, and resolvent lime CaO content is high, can make industrial lime and use.Adopt the plasma decomposition technique, the gypsum wide material sources can be the plaster of paris or industry by-product gypsum, and free water content is less than 5% two water, half water or anhydrous powder gypsum, and the coal of use is industrial bituminous coal or hard coal, and calorific value gets final product greater than 16000 KJ/Kg.
Described plasma feeder is at terminal one to two the high-power plasma generator of radial arrangement (300KW) of common feeder; After plasma generator arcing success and producing low-temperature plasma; The plasma temperature in plasma generator exit reaches 4000～5000 ℃, in the terminal high-temperature activation district that forms of feeder.Secondary air is carried green powder and is got into decomposing furnace 1 and produce heat cracking reaction through the high-temperature activation district, and simultaneously with chemical reaction and physical reaction, coal dust is gasified obtains more gas fuel burning, promotes raw material to decompose.
Said plasma body contains a large amount of chemically active particles, like atom (C, H, O), atomic group (OH, H
2, O
2), ion (O
2 -, H
2 -, OH
-, O
-, H
+) and electronics etc., can quicken the thermochemistry conversion, promote the green powder combustion decomposition.
A described wind makes the interior material of decomposing furnace at suspended state, gets into plasma feeder and plasma generator respectively behind the secondary air cooling resolvent.
Claims (8)
1. the method that plasma decomposes gypsum is characterized in that, may further comprise the steps: at first, be preparation of raw material raw material powder with terra alba and coal dust, and the quality proportion of coal dust in the raw material powder is no more than 30%; Then, the raw material powder that wind is carried carries out the gas solid separation of plasma pyrolysis, secondary plasma cracking and a cyclonic separator successively to be handled, and makes SO in the gas of cyclonic separator air outlet output
2Volume(tric)fraction is not less than 15%.
2. the method for decomposing gypsum according to the said plasma of claim 1; It is characterized in that; A described plasma pyrolysis is: the raw material powder ionization that the plasma body that adopts plasma generator to produce is come wind, thermally splitting are decomposed; To obtain the cracking head product one time, this cracking head product comprises uncracked raw material powder and split product SO
2, lime; Described secondary plasma is cracked into: a cracking head product that earlier adopts wind step (2) to obtain, and with uncracked raw material powder and split product SO
2, the lime initial gross separation; Make the raw material powder be suspended state; And the sedimentation of split product lime is collected; Then adopt plasma body that plasma generator produces that the raw material powder of wind to suspended state is carried out the secondary plasma cracking once more, obtain the second pyrolysis product, this second pyrolysis product comprises uncracked raw material powder and split product SO
2, lime, and the secondary plasma cracking temperature is between 1100 ℃-1200 ℃; Described cyclonic separator is made gas solid separation with the second pyrolysis product and is handled, and the pulverulent solids of this cyclonic separator discharge port output is collected coarse particles after the wind refrigerated separation, and fine particle is handled through the secondary plasma cracking once more.
3. the method for decomposing gypsum according to the said plasma of claim 1 is characterized in that the particle size of said raw material powder is between 20-100um; Said terra alba is selected from the plaster of paris, industry by-product gypsum or free-water < 5% two water, half water or anhydrous powder gypsum; Said coal dust is industrial bituminous coal or hard coal, and the calorific value of coal dust is greater than 16000 KJ/>Kg.
4. realize that the said plasma of claim 1 decomposes the device of gypsum method for one kind, it is characterized in that, comprise plasma feeder, second plasma generator, decomposing furnace, cyclonic separator and water cooler; Said decomposing furnace is vertical setting, and the bottom of decomposing furnace is provided with the decomposing furnace blast inlet, and the decomposing furnace blast inlet is connected with a wind transport pipe simultaneously; The plasma body outlet of the opening for feed of the discharge port of said plasma feeder, the opening for feed of water cooler, cyclonic separator, the discharge port of cyclonic separator and second plasma generator all connects with decomposing furnace and is connected, and on the discharge port of cyclonic separator and the feeding pipe between the decomposing furnace air valve is installed; The blast inlet of said water cooler is connected with the secondary air transport pipe; The air outlet of water cooler then is connected with plasma feeder, second plasma generator through two connecting tubes respectively, and equal install adjustment valve on the connecting tube between water cooler and plasma feeder, second plasma generator; The connection site of said second plasma generator and decomposing furnace is higher than the connection site of plasma feeder and decomposing furnace; The connection site of water cooler and decomposing furnace is lower than the connection site of plasma feeder and decomposing furnace; The opening for feed of cyclonic separator and the connection site of decomposing furnace are higher than the connection site of second plasma generator and decomposing furnace, and the connection site of the discharge port of cyclonic separator and decomposing furnace is lower than the connection site of plasma feeder and decomposing furnace.
5. decompose the device of gypsum method according to the said realization plasma of claim 4, it is characterized in that the top of said decomposing furnace is cylindric, the bottom then is the inverted cone shape setting; And the height of the circular cylinder shaped portion of decomposing furnace and inverted cone shape part equates.
6. decompose the device of gypsum method according to the said realization plasma of claim 4; It is characterized in that; Said plasma feeder comprises the feeder and first plasma generator; The plasma spout of said first plasma generator is near the discharge port setting of feeder, and the discharge port axis normal of the axis of the plasma spout of first plasma generator and feeder.
7. decompose the device of gypsum method according to the said realization plasma of claim 4, it is characterized in that, each decomposing furnace is equipped with 2-4 plasma feeder, and each plasma feeder is highly located uniform distribution at 1/4 of decomposing furnace; Each decomposing furnace is equipped with 2-4 plasma generator simultaneously, and each plasma generator is highly located uniform distribution at 3/4 of decomposing furnace.
8. decompose the device of gypsum method according to the said realization plasma of claim 4, it is characterized in that, said decomposing furnace is installed air distribution plate near decomposing furnace blast inlet place.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109665507A (en) * | 2018-10-12 | 2019-04-23 | 四川大学 | Utilize the method and its implementing device of plasma-based Traffic Decomposition sulphur phosphorus system material |
| CN109663555A (en) * | 2019-01-27 | 2019-04-23 | 浙江大学 | The system and method for pulse jet plasma body cooperative conversion greenhouse gases and charcoal |
| CN112984784A (en) * | 2021-02-05 | 2021-06-18 | 陕西翼飞航智能科技有限公司 | Based on SO2And O2CaSO of plasma hot blast stove4Decomposition and decomposed gas recovery system and method |
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| CN1340456A (en) * | 2000-09-01 | 2002-03-20 | 山东鲁北企业集团总公司 | Process and equipment for decomposing gypsum |
| CN201261720Y (en) * | 2008-07-07 | 2009-06-24 | 昆明理工大学 | Integrated apparatus for utilizing phosphogypsum decomposition circulating fluid bed residual heat |
| CN101531346A (en) * | 2008-03-14 | 2009-09-16 | 张智新 | Method for converting and decomposing gypsum to produce sulfuric acid |
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2011
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1340456A (en) * | 2000-09-01 | 2002-03-20 | 山东鲁北企业集团总公司 | Process and equipment for decomposing gypsum |
| CN101531346A (en) * | 2008-03-14 | 2009-09-16 | 张智新 | Method for converting and decomposing gypsum to produce sulfuric acid |
| CN201261720Y (en) * | 2008-07-07 | 2009-06-24 | 昆明理工大学 | Integrated apparatus for utilizing phosphogypsum decomposition circulating fluid bed residual heat |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109665507A (en) * | 2018-10-12 | 2019-04-23 | 四川大学 | Utilize the method and its implementing device of plasma-based Traffic Decomposition sulphur phosphorus system material |
| CN109663555A (en) * | 2019-01-27 | 2019-04-23 | 浙江大学 | The system and method for pulse jet plasma body cooperative conversion greenhouse gases and charcoal |
| CN112984784A (en) * | 2021-02-05 | 2021-06-18 | 陕西翼飞航智能科技有限公司 | Based on SO2And O2CaSO of plasma hot blast stove4Decomposition and decomposed gas recovery system and method |
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