CN102367168B - Method and apparatus for decomposing gypsum with plasma - Google Patents
Method and apparatus for decomposing gypsum with plasma Download PDFInfo
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- CN102367168B CN102367168B CN201110301279.3A CN201110301279A CN102367168B CN 102367168 B CN102367168 B CN 102367168B CN 201110301279 A CN201110301279 A CN 201110301279A CN 102367168 B CN102367168 B CN 102367168B
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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 processing method that a kind of gypsum decomposes sulfuric acid processed 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, the Miu Le of Germany and wealthy receiving (Muller Kuhne) exploitation plaster of paris raw material decomposed in rotary kiln and make sulfuric acid and cement technology has been obtained success, have set up pilot plant; Thereafter, Britain, Germany, Poland, Austria, South Africa etc. have been built up in succession take the plaster of paris, anhydrite and phosphogypsum as raw material production sulfuric acid and cement plant, owing to decompose SO
2The low investment of concentration is large, 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 decomposing gypsum technique, and its upper bed control reducing atmosphere is at a lower temperature with CaSO
4Be decomposed into CaS and SO
2The CaS that decomposes enters lower floor's fluidized-bed, and lower floor's bed control oxidizing 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, for the manufacture of sulfuric acid.70-eighties of last century, USSR (Union of Soviet Socialist Republics) was released the technique in same fluidized-bed control reduction, two kinds of atmosphere of oxidation, and its principle is similar to 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
2Control oxidizing 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, prospect of the application is good, but suitability for industrialized production not.German Lurgi company had released Circulating Fluidized Bed Process in 1985, had finished the interim test of day processing 10 t gypsum, had obtained abundant testing data.Have developed U.S.'s scientific exploration company and the nineties in last century on this basis the flash fluidized-bed process, its significant parameter fluidizing velocity is high, and specification of equipment is little.U.S. associating mineral company in 1991 has announced and has adopted the construction of fluidised bed decomposition phosphogypsum to produce the integrated mill of 2,500,000 t sulfuric acid per year, and progress is reported but so far there are no.In recent years, the technician of the states such as India, Morocco, Tunisia also had new achievement in research in this field, but without quantum jump very.
China is on the basis of summing up domestic and international technology, 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 large, power consumption is large, 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 producing sulfuric acid and jointly cement processed " country " eight or five " key research project in the nineties in last century.Nineteen ninety has been finished 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.Built up the commerical test device of 150t/d sulfuric acid at the beginning of 1993 on the basis of hot-die test.Examination is burnt more than a year, has consumed a large 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 qualified product and stops.
China at present only the industrial gypsum annual emissions surpassed 9,000 ten thousand tons, and increase year after year.Owing to contain objectionable impurities in the industry by-product gypsum, discharging can cause serious environmental pollution arbitrarily; The stockyard is set, and not only occupation of land is many, investment is large, the slag expense is high, and high to the Geological Condition Requirement in stockyard, and for a long time accumulation can cause surface water and groundwater pollution.If gypsum is decomposited lime and SO
2, its purposes is more extensive, and benefit is higher.Although the invention of the patent No. 200810068831 can change the problems referred to above and since pyrolytic decomposition easily 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 deficiencies in the prior art, a kind of method of decomposing gypsum with plasma is provided, the desulfurization of adopting plasma technology to carry out gypsum is processed, 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 method of decomposing gypsum with plasma may further comprise the steps: at first, take terra alba and coal dust as the preparation of raw material raw meal powder, and the quality proportion of coal dust in raw meal powder is no more than 30%; Then, the raw meal powder that wind is carried carries out the gas solid separation processing of plasma pyrolysis, secondary plasma cracking and a cyclonic separator successively, so that SO in the gas of cyclonic separator air outlet output
2Volume fraction is not less than 15%.
A described plasma pyrolysis is: raw meal powder ionization, thermally splitting that the plasma body that adopts plasma generator to produce is come wind are decomposed, to obtain the cracking head product one time, this cracking head product comprises uncracked raw meal powder and split product SO
2, lime; Described secondary plasma is cracked into: a cracking head product that adopts first wind step (2) to obtain, and with uncracked raw meal powder and split product SO
2, the lime initial gross separation, so that raw meal powder is suspended state, and the sedimentation of split product lime is collected, then again adopt plasma body that plasma generator produces that wind to the raw meal powder of suspended state is carried out the secondary plasma cracking, obtain the second pyrolysis product, this second pyrolysis product comprises uncracked raw meal 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 processed, and the pulverulent solids of this cyclonic separator discharge port output is collected coarse particles after the wind refrigerated separation, and fine particle is processed through the secondary plasma cracking again.
The granular size of described raw meal powder is between 20-100um; Described terra alba is selected from two water, half water or the anhydrous powder gypsum of the plaster of paris, industry by-product gypsum or free-water＜5%; Described 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 decomposing gypsum with plasma method, comprises plasma feeder, the second plasma generator, decomposing furnace, cyclonic separator and water cooler; Described decomposing furnace is vertical setting, and the bottom of decomposing furnace arranges 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 described plasma feeder, the opening for feed of water cooler, cyclonic separator, the discharge port of cyclonic separator and the 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 described water cooler is connected with the secondary air transport pipe, the air outlet of water cooler then is connected with plasma feeder, the second plasma generator by two connecting tubes respectively, and on the connecting tube between water cooler and plasma feeder, the second plasma generator variable valve is installed all; The connection site of described the 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 the 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 described 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.
Described plasma feeder comprises feeder and the first plasma generator, the plasma spout of described the first plasma generator is near the discharge port setting of feeder, and the axis of the plasma spout of the first plasma generator is vertical with the discharge port axis of feeder.
Each decomposing furnace is equipped with 2-4 plasma feeder, and each plasma feeder evenly distributes at 1/4 At The Height of decomposing furnace; Each decomposing furnace is equipped with 2-4 plasma generator simultaneously, and each plasma generator evenly distributes at 3/4 At The Height of decomposing furnace.
Described 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. generate lime after raw material decompose, purposes is more extensive, reduces 30-40% than decompose cement hear rate processed in rotary kiln.
3. this method technique is simple, invest low, the obstruction that do not scab, simple to operate.
Description of drawings
Fig. 1 is the decomposing gypsum with plasma 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; The second ion generator 6 such as the second grade; Variable valve 7.
Embodiment
Accompanying drawing discloses the structural representation of preferred embodiment involved in the present invention without limitation; Explain technical scheme of the present invention below with reference to accompanying drawing.
As shown in Figure 1, it provides a kind of device of realizing decomposing gypsum with plasma method of the present invention, comprises plasma feeder, the second plasma generator, decomposing furnace, cyclonic separator and water cooler; Described decomposing furnace is vertical setting, and the bottom of decomposing furnace arranges 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 described plasma feeder, the opening for feed of water cooler, cyclonic separator, the discharge port of cyclonic separator and the 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 described water cooler is connected with the secondary air transport pipe, the air outlet of water cooler then is connected with plasma feeder, the second plasma generator by two connecting tubes respectively, and on the connecting tube between water cooler and plasma feeder, the second plasma generator variable valve is installed all; The connection site of described the 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 the 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 described 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.Described plasma feeder comprises feeder and the first plasma generator, the plasma spout of described the first plasma generator is near the discharge port setting of feeder, and the axis of the plasma spout of the first plasma generator is vertical with the discharge port axis of feeder.Each decomposing furnace is equipped with 2-4 plasma feeder, and each plasma feeder evenly distributes at 1/4 At The Height of decomposing furnace; Each decomposing furnace is equipped with 2-4 plasma generator simultaneously, and each plasma generator evenly distributes at 3/4 At The Height of decomposing furnace.Described decomposing furnace is installed air distribution plate near decomposing furnace blast inlet place.
Hence one can see that, and the principle of work of the device of above-mentioned realization decomposing gypsum with plasma 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 meal powder that gypsum and coal make and is entered plasma feeder 5, through the rapidly ionization under the physics chemical action of plasma body of high-temperature activation district, thermally splitting is decomposed, coal dust is vaporized and obtains more gas fuel burning, promote raw material to decompose, mix high temperature gas flow (800 ℃) and enter decomposing furnace 1 bottom, rise and the maintenance certain temperature at the moving low suspension of a wind, arrive the plasma body of the second ion generator 6 generations such as top runs into, undecomposed raw material continue to decompose, 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 enters in the cyclonic separator 2, and high-speed rotational is with lime particle and high density SO
2Carry out gas solid separation, contain 15% high volumetric concentration SO
2Gas enters the manufacturing sulfate system with hot gas (550 ℃) by the separator top, the lime that separates returns decomposing furnace 1 bottom, the resolvent pellet density increases, entering water cooler 4 discharges by the secondary air cooling is rear, undecomposed fine particle enters decomposing furnace 1 top and decomposes, and rate of decomposition is reached more than 98%.Variable valve 7 is to regulate decomposing furnace up and down temperature and decomposition effect usefulness.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) granular size is all at 20-100um; Described gypsum can be the plaster of paris or industry by-product gypsum, contains two water, half water or the anhydrous powder gypsum of free-water＜5%; 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 with the raw meal powder of gypsum and coal preparation through the plasma high-temperature region of activation of plasma feeder 5 ionize rapidly, thermally splitting decomposes, enter 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, continuing thermally splitting decomposes, 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 by 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 entered 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 vaporized and obtains more gas fuel burning, promotes raw material to decompose.
Described plasma body contains a large amount of chemically active particles, such as atom (C, H, O), atomic group (OH, H
2, O
2), ion (O
2 -, H
2 -, OH
-, O
-, H
+) and electronics etc., can accelerate the thermochemistry conversion, promote the green powder combustion decomposition.
A described wind makes the interior material of decomposing furnace at suspended state, enters respectively plasma feeder and plasma generator behind the secondary air cooling resolvent.
Claims (8)
1. the method for a decomposing gypsum with plasma is characterized in that, may further comprise the steps: at first, take terra alba and coal dust as the preparation of raw material raw meal powder, and the quality proportion of coal dust in raw meal powder is no more than 30%; Then, the raw meal powder that wind is carried carries out the gas solid separation processing of plasma pyrolysis, secondary plasma cracking and a cyclonic separator successively, so that SO in the gas of cyclonic separator air outlet output
2Volume fraction is not less than 15%.
2. the method for described decomposing gypsum with plasma according to claim 1, it is characterized in that, a described plasma pyrolysis is: raw meal powder ionization, thermally splitting that the plasma body that adopts plasma generator to produce is come wind are decomposed, to obtain the cracking head product one time, this cracking head product comprises uncracked raw meal powder and split product SO
2, lime; Described secondary plasma is cracked into: a cracking head product that adopts first wind step (2) to obtain, and with uncracked raw meal powder and split product SO
2, the lime initial gross separation, so that raw meal powder is suspended state, and the sedimentation of split product lime is collected, then again adopt plasma body that plasma generator produces that wind to the raw meal powder of suspended state is carried out the secondary plasma cracking, obtain the second pyrolysis product, this second pyrolysis product comprises uncracked raw meal 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 processed, and the pulverulent solids of this cyclonic separator discharge port output is collected coarse particles after the wind refrigerated separation, and fine particle is processed through the secondary plasma cracking again.
3. the method for described decomposing gypsum with plasma according to claim 1 is characterized in that the granular size of described raw meal powder is between 20-100um; Described terra alba is selected from the plaster of paris, industry by-product gypsum; Described coal dust is industrial bituminous coal or hard coal, and the calorific value of coal dust is greater than 16000 KJ/Kg.
4. a device of realizing the described decomposing gypsum with plasma method of claim 1 is characterized in that, comprises plasma feeder, the second plasma generator, decomposing furnace, cyclonic separator and water cooler; Described decomposing furnace is vertical setting, and the bottom of decomposing furnace arranges 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 described plasma feeder, the opening for feed of water cooler, cyclonic separator, the discharge port of cyclonic separator and the 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 described water cooler is connected with the secondary air transport pipe, the air outlet of water cooler then is connected with plasma feeder, the second plasma generator by two connecting tubes respectively, and on the connecting tube between water cooler and plasma feeder, the second plasma generator variable valve is installed all; The connection site of described the 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 the 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. the device of described realization decomposing gypsum with plasma method according to claim 4 is characterized in that the top of described 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.
6. the device of described realization decomposing gypsum with plasma method according to claim 4, it is characterized in that, described plasma feeder comprises feeder and the first plasma generator, the plasma spout of described the first plasma generator is near the discharge port setting of feeder, and the axis of the plasma spout of the first plasma generator is vertical with the discharge port axis of feeder.
7. the device of described realization decomposing gypsum with plasma method according to claim 4 is characterized in that, each decomposing furnace is equipped with 2-4 plasma feeder, and each plasma feeder evenly distributes at 1/4 At The Height of decomposing furnace; Each decomposing furnace is equipped with 2-4 plasma generator simultaneously, and each plasma generator evenly distributes at 3/4 At The Height of decomposing furnace.
8. the device of described realization decomposing gypsum with plasma method according to claim 4 is characterized in that, described decomposing furnace is installed air distribution plate near decomposing furnace blast inlet place.
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| 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 |
| CN109663555B (en) * | 2019-01-27 | 2019-12-31 | 浙江大学 | System and method for synergistically converting greenhouse gas and biochar by pulsating jet plasma |
| 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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| CN1331738C (en) * | 2000-09-01 | 2007-08-15 | 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 |
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