CN109775666A - Coal gasification collaboration calcium sulfate calcining and carbon heat reducing prepare the device and method of sulphur - Google Patents
Coal gasification collaboration calcium sulfate calcining and carbon heat reducing prepare the device and method of sulphur Download PDFInfo
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Abstract
The present invention relates to a kind of collaboration calcium sulfate calcinings of coal gasification and carbon heat reducing to prepare sulphur technique and method.High concentration SO is generated with carbon material and sulfur reaction under calcium sulfate high temperature2Flue gas and metal calcium oxide, utilize U-shaped coal gasification calcining furnace, carbon heat reducing tower, sulfur recovery facility and various heat exchangers etc., by accurately controlling each reaction condition, sulphur is prepared with reluctant solid waste calcium sulfate, by-product calcium oxide simultaneously, by-product calcium oxide can replace lime stone as desulfurization denitrification agent.
Description
Technical field
The invention belongs to field of solid waste resource utilization, more particularly to a kind of collaboration calcium sulfate calcining of coal gasification and charcoal heat
Reduction prepares sulphur technique and method.
Background technique
Disclosing the information of the background technology part, it is only intended to increase understanding of the overall background of the invention, without certainty
It is considered as recognizing or implying in any form that information composition has become existing skill well known to persons skilled in the art
Art.
With the fast development of China's high concentration phosphate fertilizer and phosphoric acid industry, the yield of by-product ardealite is sharply increased, phosphorus
The main component of gypsum is CaSO4·2H2O, while also containing other a small amount of metal ion sulfate.China's ardealite at present
Nearly hundred million tons of annual emissions, accumulate nearly 500,000,000 tons of accumulating amount.At present although country's ardealite has certain utilization ways, but all exists
Certain problem, and treating capacity is smaller, can not alleviate the pollution situation of China's ardealite.Ardealite contains acid and nuisance
Matter, it is necessary to it is special to stack, not only took up an area waste of resource again, and ardealite is stacked understand polluted underground water for a long time.
With the continuous improvement that Environmental Protection in China requires, the sulfur-containing smoke gas of the discharges such as coal-burning power plant, steel plant needs that cigarette is arranged
Desulfurization device, wherein the wet desulphurization unit based on limestone-gypsum method accounts for 85% of total installation of generating capacity or so, this skill
It is stable although art has many advantages, such as desulfuration efficiency height, need to consume a large amount of lime stone, lime stone exhaustive exploitation,
Ecological environment is not only broken up, and desulfurizing byproduct is low-quality desulfurized gypsum, is worth low, it is difficult to utilize.China's desulfurization at present
Gypsum annual output is about 100,000,000 tons, and the ingredient of desulfurized gypsum is similar to ardealite, main component CaSO4·2H2O。
Sulphur is minimum in all sulfur-bearing product middle-molecular-weihydroxyethyls, and unit value is high；Storage and transport cost is lower；And sulphur can be made
It is widely used for the raw materials for production of most of sulfur-bearing products.China is the country of sulphur shortage of resources again, annual sulphur import volume
And consumption position is at the forefront in the world, external dependence degree is high, and sulphur is as important one of industrial chemicals, market value and application
Value is far longer than sulfuric acid.
Patent CN108640090A discloses a kind of carbon heat reducing SO2The device and method for preparing sulphur belongs to sulphur and returns
Receive technical field, including feed bin, gas-solid mixing storehouse, carbon heat reducing tower, high-temperature gas-solid separator, ash bucket, carbon based reductive buffering
Tank, carbon heat reducing tower are conversion zone and gas-solid mixing bunker from top to bottom, and feed bin is connect with the material inlet in gas-solid mixing storehouse, reaction
Section top setting also Primordial Qi outlet, also Primordial Qi outlet are sequentially connected high-temperature gas-solid separator, ash bucket, carbon based reductive surge tank,
Carbon based reductive surge tank is connect with the return port in gas-solid mixing storehouse, set gradually from top to bottom inside gas-solid mixing storehouse bracket,
Distribution grid mends inflation inlet, and reaction gas inlet pipe enters gas-solid mixing storehouse by the bottom in gas-solid mixing storehouse, and the bracket is located at material
The downside of import and return port, one end of reaction gas inlet pipe are located at the top of bracket, high concentration SO2Flue gas carry out it is tentatively de-
Sulphur, Recovered sulphur, it is therefore prevented that blocked caused by the accumulation of material, take full advantage of material.
Patent 201710017333.9 discloses a kind of method for producing calcium oxide and sulphur from gypsum, including walks as follows
Rapid: (1) gypsum pre-processes: by the dry dehydrated gypsum for forming total water content and being 2~10% of dihydrate gypsum, dehydrated gypsum wears into stone
Cream powder；(2) gypsum decomposes: the land plaster of step (1) being contacted with sulfur-bearing Process Gas, is reacted at 700~1200 DEG C, finally
Generate calcium oxide and sulfur dioxide gas；(3) sulphur dioxide reduction: also by sulfur dioxide gas obtained by step (2) and carbonaceous
Former agent contact, reacts at 600~1000 DEG C, generates sulfur-bearing Process Gas, and sulfur-bearing Process Gas is divided into two strands, one is used for step (2)
Gypsum decomposition reaction, another stock, which then takes out, to be condensed, is catalyzed the processes such as reaction, granulation, produces sulphur；The gypsum of this method turns
Rate is high, and consumption gypsum production has the calcium oxide and sulphur of high added value.But inventor has found: the raw material availability of this method
It is low, energy consumption is to be improved.
Summary of the invention
In order to overcome the above problem, present invention combination calcium sulfate reduction roasting technique and SO2Carbon heat reducing prepares sulphur
Technology proposes that a kind of coal gasification collaboration calcium sulfate is calcined and carbon heat reducing prepares sulphur technique and method, and designs corresponding
Device.Calcium sulfate is in carbon material and reducibility gas (CO, H2、S2Deng) additive synergistic effect under decomposite high concentration SO2Cigarette
Gas and solid oxidation calcium powder, high concentration SO2Flue gas can be reduced directly to elemental sulfur steaming by reacting at high temperature with carbon material
Gas, then in turn through being recycled to obtain sulphur by sulfur recovery facility after dedusting, cooling, refined dedusting technique；Solid oxidation calcium powder
End can replace lime stone as wet desulphurization denitration, the desulfurization denitrification agent of semi-dry desulfurization and denitrification, which can realize calcium sulfate
The multi-functional utilization of recycling.
To realize the above-mentioned technical purpose, The technical solution adopted by the invention is as follows:
A kind of collaboration calcium sulfate calcining of coal gasification and carbon heat reducing prepare the device of sulphur, comprising: U-shaped furnace, separating at high temperature
Device I, calcium sulfate warehouse, carbon material warehouse I, carbon heat reducing tower, high-temperature separator II, reheater, dust-extraction unit, Sulfur recycling installment
It sets, sulphur storage tank；The U-shaped furnace is divided into left side and calcines section, right side coal gasification section, left side calcining section and calcium sulfate warehouse,
Carbon material warehouse I is connected, and the outlet on coal gasification section top is connected with I import of high-temperature separator on the right side of the U-shaped furnace, the high temperature
The bottoms material outlet of separator I is connected with coal gasification section, calcium oxide cooler on the right side of U-shaped furnace respectively by part flow arrangement, institute
The gas vent for stating I top of high-temperature separator is connected with the material inlet of carbon heat reducing top of tower, the carbon heat reducing tower side wall
Outlet be connected with high-temperature separator II, coal gasification on the right side of the material outlet of II bottom of high-temperature separator and the U-shaped furnace
The air inlet of section side wall is connected, the gas outlet at II top of high-temperature separator and reheater, dust-extraction unit, Sulfur recycling installment
It sets, sulphur storage tank is sequentially connected；
The carbon heat reducing top of tower material inlet is also connected with carbon material warehouse II.
Produce that calcium oxide, the generally existing raw material availability of device of sulphur is not high, energy consumption is excessive asks by calcium sulfate at present
Topic.For this purpose, the present invention realizes the synchronous progress that coal gasification is decomposed with calcium sulfate using U-shaped furnace, and coal gasification generates reproducibility
Gas provides heat and reducing substances again for calcium sulfate decomposition；On the other hand, the present invention is additionally provided with carbon heat reducing tower,
700 DEG C -1000 DEG C of optimum temperature of sulphur technique are prepared, with calcium sulfate " coal gasification generate reducibility gas " in the presence of
Decomposition temperature (800 DEG C -1100 DEG C) matches, and therefore, the two is combined, and substantially increases the conversion ratio of sulfur product, and charcoal
Weary burnt, also Primordial Qi after thermal reduction reaction can make raw material for coal gasification reaction or calcium sulfate decomposition again, lack of gas then mainly as
Transport of the inert gas for materials and heat such as calcium sulfate reduces influence of the moisture to each reaction.Therefore, the present invention pass through by
Coal gasification and calcium sulfate decompose, carbon heat reducing three organically combines, and effectively improve the utilization rate of raw material and the energy of operation
Consumption.
In order to make full use of the also Primordial Qi thermal energy containing sulfur vapor, meanwhile, deposit thionic step, in some embodiments
In, the cooling medium of reheater is carbon heat reducing lack of gas in the present invention, since carbon heat reducing lack of gas are also as the sulfuric acid after preheating
The carrier gas of calcium, therefore, the carbon heat reducing lack of gas after heat absorption are more conducive to the decomposition and heating of calcium sulfate.
In some embodiments, the air inlet of the carbon heat reducing tower bottom and the U-shaped furnace right side coal gasification section side wall
It is connected, together, passes through partial reduction from the weary coke of carbon heat reducing tower bottom exclusion, with from the weary coke of II lower part of high-temperature separator discharge
Conductance enters the raw material in U-shaped furnace as coal gasification reaction, during both having realized the recycling, eliminate carbon heat reducing of weary coke
The solid waste (solid waste, that is, weary coke) of generation, meanwhile, the thermal energy and activity of weary coke promote the raising of coal gasification reaction efficiency again.
In some embodiments, the material outlet of the deduster bottom is connected with coal gasification section on the right side of U-shaped furnace, also Primordial Qi
Solid powder in body is after deduster separates, since main component is C, can be used as the raw material of coal gasification reaction, improve
The efficiency of coal gasification reaction.
In some embodiments, the gas vent of the sulfur recovery facility is also left with flue gas purification system, U-shaped furnace respectively
Side calcining section is connected with reheater, and lack of gas a part after Recovered sulphur urges calcium sulfate and solid carbonaceous material as conveying gas
Agent, which is delivered on the left of U-shaped furnace, calcines section, after a part of reheated device heating, is warming up to 500 DEG C -800 by 120 DEG C -250 DEG C
DEG C, carbon heat reducing tower is returned as temperature adjustment gas, and last part lack of gas are discharged after entering flue gas purification system.
In some embodiments, preheater is provided between the calcium sulfate warehouse and U-shaped furnace.By preheating calcium sulfate
Dead plaster is converted to, and steam is excluded, avoids influencing subsequent decomposition reaction, while realizing the step of system waste heat
It utilizes.
In some embodiments, the calcium oxide cooler is connected with calcium oxide warehouse, and calcium oxide can replace lime masonry
Therefore calcium oxide after cooling is collected using calcium oxide warehouse for desulfurization denitrification agent, it is spare.
In some embodiments, the calcium sulfate warehouse outlet, the outlet of carbon material warehouse, the weary burnt discharge of carbon heat reducing, height
Lock gas batcher is set at warm II lower part outlet pipeline of separator, accurately to control conveying amount, and guarantees the leakproofness of system.
The present invention also provides the methods that a kind of collaboration calcium sulfate calcining of coal gasification and carbon heat reducing prepare sulphur, comprising:
By after preheating calcium sulphate powders, with solid carbonaceous material, the reducibility gas haptoreaction at 800 DEG C -1100 DEG C,
Collect fired slags, high concentration SO2The excessive reducibility gas of gas and part；
By fired slags, high concentration SO2The excessive reducibility gas gas solid separation of gas and part, makes SO2Gas and portion
Divide excessive reducibility gas to react at 500 DEG C -1000 DEG C with carbon material, generates simple substance sulfur vapor；
Wherein, weary burnt, the also Primordial Qi after reducibility gas is reacted by carbon heat reducing carries out coal gasification reaction generation.
Studies have shown that itself decomposition temperature of calcium sulfate be 1350 DEG C -1400 DEG C between, but be added carbon material, reproducibility
Gas (CO, H2、S2Deng) etc. after reducing substances, calcium sulfate decomposition temperature substantially reduces, and decomposition temperature is about 800 DEG C -1100
DEG C, the reduction of temperature not only reduces energy consumption, while temperature and carbon heat reducing SO after reduction2Prepare the best temperature of sulphur technique
700 DEG C -1000 DEG C of degree matches, and can greatly improve the conversion ratio of sulfur product；Calcium sulfate reduction roasting product main component
For solid metal calcium oxide and high concentration SO2Gas (SO in gas2Concentration 5%-30%), the SO of high concentration2Gas can be direct
Redox reaction is carried out into carbon heat reducing tower and prepares sulphur, and calcium oxide can be used as desulfurizing agent and recycle；Reproducibility gas
Body cooperates with carbon material to restore SO2, carbon heat reducing temperature is by 700 DEG C -- and 1000 DEG C are reduced to 500 DEG C -800 DEG C, reduce energy consumption, mention
High economy.
In some embodiments, the calcium sulfate, 60 μm of -3mm of partial size, be wet desulphurization gypsum, semi-dry processed desulfurization gypsum,
At least one of the natural gypsum and ardealite；
The carbon material, 60 μm of -3mm of partial size are coal dust, activated coke, active carbocoal, active carbon, carbonized material, graphite kind
It is at least one.
A kind of coal gasification collaboration calcium sulfate calcining proposed by the present invention and carbon heat reducing prepare sulphur technique and method.For
High concentration SO is generated with carbon material and sulfur reaction under calcium sulfate high temperature2Flue gas and metal calcium oxide are calcined using U-shaped coal gasification
Furnace, carbon heat reducing tower, sulfur recovery facility and various heat exchangers etc., by accurately controlling each reaction condition, with being difficult to handle
Solid waste calcium sulfate prepare sulphur, while by-product calcium oxide, by-product calcium oxide can replace lime stone as desulfurization denitrification agent.
The technique has the beneficial effect that
1, calcium sulfate and SO are decomposed in carbon material, reducibility gas collaboration2Carbon heat reducing, greatly reduce calcium sulfate
Decomposition and carbon heat reducing temperature；
2, system capacity cascade utilization reduces process energy consumption, improves economy；
3, lime stone conduct can be replaced by solid waste calcium sulfate resource utilization being produced high value sulphur and calcium oxide, calcium oxide
Desulfurization denitrification agent, sulphur have high utility value as the important raw material of industry；
4, it is coal gasification raw material using weary Jiaozhuo of carbon heat reducing technique discharge, not only solves the generation of carbon heat reducing technology
The reluctant problem of solid waste, while saving the consumption of high-quality carbon material, economize on resources, improve economy.
The technique is not only that current reluctant calcium sulfate solid waste provides completely new sustainable free of contamination processing
Mode realizes the resource utilization of calcium sulfate, while can alleviate the status of China's sulphur resource scarcity, reduces Sulphur ressource pair
Outer interdependency, by-product calcium oxide can replace lime stone as desulfurization denitrification agent, reduce the exploitation to lime stone, protect
Ecological environment, therefore, the technique have a vast market foreground.
Detailed description of the invention
The Figure of description for constituting a part of the invention is used to provide further understanding of the present invention, and of the invention shows
Examples and descriptions thereof are used to explain the present invention for meaning property, does not constitute improper limitations of the present invention.
Fig. 1 is that the coal gasification of embodiment 1 cooperates with calcium sulfate calcining and carbon heat reducing to prepare sulphur technique and method system figure.
Wherein, 1. calcium sulfate warehouses, 2. calcium sulfate preheaters, 3. carbon material warehouses I, 4.U type furnace, 5. high-temperature separators I,
6. calcium oxide cooler, 7. calcium oxide warehouses, 8. carbon material warehouses II, 9. carbon heat reducing towers, 10. high-temperature separators II, 11. are again
Hot device, 12. refined dedusting devices, 13 sulfur recovery facilities, 14. sulphur storage tanks, 15. flue gas purification systems.
Specific embodiment
It is noted that following detailed description is all illustrative, it is intended to provide further instruction to the present invention.Unless another
It indicates, all technical and scientific terms that the present invention uses have logical with general technical staff of the technical field of the invention
The identical meanings understood.
It should be noted that term used herein above is merely to describe specific embodiment, and be not intended to restricted root
According to exemplary embodiments of the present invention.As used herein, unless the context clearly indicates otherwise, otherwise singular
Also it is intended to include plural form, additionally, it should be understood that, when in the present specification using term "comprising" and/or " packet
Include " when, indicate existing characteristics, step, operation, device, component and/or their combination.
As background technique is introduced, it is difficult to handle for current China low-grade gypsum (mainly calcium sulfate), sulphur
The problem of sulphur shortage of resources.Therefore, the present invention proposes that a kind of coal gasification collaboration calcium sulfate is calcined and carbon heat reducing prepares sulphur work
Skill and method, specifically include that
Calcium sulphate powders, which pass through batcher first and accurately control feeding coal and be delivered to calcium sulfate preheater, to be preheated, by normal
Temperature is heated to 400 DEG C -600 DEG C, and heat medium is inert gas or air, and heat is cooling from reaction solid product calcium oxide
Thermal discharge；Calcium sulfate after preheating is delivered on the left of U-shaped furnace by carbon heat reducing lack of gas calcines section；Solid for calcium sulfate calcining
Carbon material accurately controls feeding coal by batcher, is delivered on the left of U-shaped furnace by carbon heat reducing lack of gas and calcines section as calcium sulfate
The solid catalyst of calcining；Weary coke after participating in carbon heat reducing reaction in carbon heat reducing tower is delivered to the U-shaped furnace right side by also Primordial Qi
Side gasification section carries out coal gasification reaction, 1100 DEG C -1500 DEG C of reaction temperature, generates reducibility gas and provides calcium sulfate calcining simultaneously
Institute's calorific requirement, coal gasification institute calorific requirement are provided by burner；Reducibility gas is by U-shaped furnace bottom channel, by right side gasification section
Into left side calcine section, calcining Duan Zhongyu solid carbonaceous material and calcium sulfate contact react, reaction temperature be 800 DEG C-
1100 DEG C, by accurately controlling reaction condition and reaction process, calcined product is fired slags, high concentration SO2Gas and
The excessive reducibility gas in part；Calcined gas-solid product initially enters high-temperature separator I, the fired slags root after gas solid separation
It is shunted according to whether the mass fraction of calcium oxide in slag is up to standard: if calcium oxide mass fraction is below standard, illustrating most sulfuric acid
Calcium is not calcined completely, and fired slags are returned to U-shaped furnace by L-type returning charge valve on the left of part flow arrangement at this time and carry out Cyclic Calcination, to protect
Demonstrate,prove the calcining rate of calcium sulfate；If calcium oxide mass fraction is up to standard, illustrate that calcium sulfate calcining is more complete, at this time by shunting dress
It sets right side L-type returning charge valve and enters the cooling of calcium oxide cooler, temperature is cooled to 20 DEG C -80 DEG C by 900 DEG C -1100 DEG C, calcium oxide
Cooling thermal discharge is used for the preheating of calcium sulfate, and fired slags after cooling are stored in calcium oxide warehouse；Gas after gas solid separation
In containing concentration be 3%-30% SO2And the reducibility gas of 3%-30%, enter carbon heat reducing tower from top, with charcoal heat
Redox reaction, the SO of high concentration occur in 500 DEG C of -1000 DEG C of temperature ranges for the carbon material in reduction tower2It is reduced to
Simple substance sulfur vapor, the carbon material for participating in carbon heat reducing accurately control feeding coal by batcher and input above carbon heat reducing tower；
Weary burnt a part after carbon heat reducing is directly discharged from carbon heat reducing tower bottom, and a part is carried along into separating at high temperature by also Primordial Qi
Device II is discharged from II lower part of high-temperature separator, and the weary coke of carbon heat reducing tower discharge is delivered on the right side of U-shaped furnace by partial reduction gas
Gasification section is as coal gasification raw material；High-temperature separator II isolate also Primordial Qi enter reheater cooling, also Primordial Qi from 500 DEG C-
1000 DEG C are cooled to 450 DEG C -500 DEG C, and cooling medium is carbon heat reducing lack of gas；Also Primordial Qi a part after cooling is as conveying gas
Body carries weary coke and send on the right side of U-shaped furnace, and a part enters refined dedusting device, removes the lesser solid powder of partial size in also Primordial Qi,
The solid powder separated returns to U-shaped furnace right side gasification section as raw material；Also Primordial Qi after dedusting enters sulfur recovery facility
Recycling obtains sulphur, collects the sulphur storage to get off in sulphur storage tank, and lack of gas a part after Recovered sulphur is as conveying gas
Body will calcine section on the left of calcium sulfate and solid carbonaceous material catalyst transport to U-shaped furnace, after a part of reheated device heating, by 120
DEG C -250 DEG C are warming up to 500 DEG C -800 DEG C, return to carbon heat reducing tower as temperature adjustment gas, it is net that last part lack of gas enter flue gas
It is discharged after change system.
The calcium sulfate, 60 μm of -3mm of partial size, can be wet desulphurization gypsum, semi-dry processed desulfurization gypsum, the natural gypsum with
A variety of calcium sulfate products such as ardealite；
The carbon material, 60 μm of -3mm of partial size can be coal dust, activated coke, active carbocoal, active carbon, carbonized material, graphite
Etc. a plurality of types of carbon materials；
The inert gas, including a variety of inert gases such as nitrogen, argon gas, helium and their mixture；
The fired slags, 60 μm of -3mm of partial size, main component are solid oxidation calcium powder, do not calcine complete sulfuric acid calcium powder
Last and a small amount of impurity；
The U-shaped furnace can be a variety of type of furnaces such as air flow bed, fluidized bed, ebullated bed, bubbling bed, spouted bed, sedimentation bed；
More specifically, the U-shaped furnace is USC-80U type furnace.
The reducibility gas, 1200 DEG C -1500 DEG C of temperature, main component N2、CO、H2、CH4、CO2Deng；
The also Primordial Qi, 800 DEG C -1100 DEG C of temperature, main component N2, S steam (concentration 5%-35%), CO, CO2Deng；
The lack of gas, main component N2、CO、CO2Deng；
The weary coke, main component C, the substance after carbon heat reducing reaction；
The batcher can be a variety of feed forms such as screw(-type) feeder, lock gas batcher；
The burner, fuel can be the burner of the pluralities of fuels forms such as coal dust, natural gas, diesel oil；
The high-temperature separator can be the separator of the diversified forms such as high temperature cyclone separator, high temperature axis stream separator；
The refined dedusting device can be the refined dedusting filter of the diversified forms such as metal cloth filter, ceramic filter；
The carbon heat reducing tower can be the diversified forms such as air flow bed, bubbling bed, Micro Fluid bed, spouted bed and fluidized bed；
Above-mentioned gas transmission process provides conveying power by air-introduced machine or pressure fan；
The outlet of calcium sulfate warehouse, the outlet of carbon material warehouse, the weary burnt discharge of carbon heat reducing, II lower part outlet pipe of high-temperature separator
Lock gas batcher is set at road, guarantees the leakproofness of system while accurately controlling conveying amount；
Also Primordial Qi enters refined dedusting device after high-temperature separator isolates powdery fired slags, then after the cooling of reheated device
Final dusting is carried out, by sulfur condenser condensing recovery sulphur.Recovered sulphur purity reaches 99.7% or more, meets industrial sulphur
Grade A standard.
Compared with existing gypsum produces the method for calcium oxide and sulphur, the application is had the advantage that
1, the technique realizes the cascade utilization of system capacity, more energy saving；
2, by carbon heat reducing generate solid wastes recycling using carry out coal gasification reaction, for calcine provide reducing atmosphere and
Energy, resource utilization degree are higher；
3, the technique combination high-temperature separator and material-returning device, may be implemented the Cyclic Calcination of calcium sulfate；
4, more reducing substances cooperate with calcined calcium sulfate hemihydrate, reduce calcination temperature, improve SO in calcining flue gas2Concentration,
Improve calcining rate；
5, the process flow combines relatively complete device and equipment, has more feasibility；
6, the technique sulphur recovery have passed through two-stage dust removal and filtration, and sulphur quality is higher；
7, calcium sulfate calcining and carbon heat reducing are the reaction for fluidizing state in the technique, and gas-solid contact is more preferable, reaction efficiency
It is higher.
Present invention will be further explained below with reference to the attached drawings and examples, and implementation is raw materials used to be all made of commercial product.
Embodiment 1:
A kind of collaboration calcium sulfate calcining of coal gasification and carbon heat reducing prepare the device of sulphur, comprising: U-shaped furnace 4, separating at high temperature
Device I (5), calcium sulfate warehouse 1, carbon material warehouse I (3), carbon heat reducing tower 9, high-temperature separator II (10), reheater 11, dedusting
Device 12, sulfur recovery facility 13, sulphur storage tank 14；The U-shaped furnace 4, which divides, calcines section, right side coal gasification section, the left side for left side
Side calcining section is connected with calcium sulfate warehouse 1, carbon material warehouse I (3), the outlet on the U-shaped 4 right side coal gasification section top of furnace and height
Warm separator I (5) import is connected, the outlet of the bottoms material of the high-temperature separator I (5) by part flow arrangement respectively with U-shaped furnace 4
Right side coal gasification section, calcium oxide cooler 6 are connected, gas vent and carbon heat reducing tower 9 at the top of the high-temperature separator I (5)
The material inlet at top is connected, and the outlet of 9 side wall of carbon heat reducing tower is connected with high-temperature separator II (10), the high temperature point
Material outlet from device II (10) bottom is connected with the air inlet of the U-shaped 4 right side coal gasification section side wall of furnace, the separating at high temperature
Gas outlet at the top of device II (10) and reheater 11, refined dedusting device 12, sulfur recovery facility 13, sulphur storage tank 14 successively phase
Even；
The 9 top material entrance of carbon heat reducing tower is also connected with carbon material warehouse II.
The operation method of above-mentioned apparatus is as follows:
Calcium sulphate powders, which pass through batcher first and accurately control feeding coal and be delivered to calcium sulfate preheater 2, to be preheated, by
Room temperature is heated to 400 DEG C -600 DEG C, and heat medium is inert gas or air, and heat is cold from reaction solid product calcium oxide
But thermal discharge；Calcium sulfate after preheating is delivered on the left of U-shaped furnace 4 by carbon heat reducing lack of gas calcines section；For calcium sulfate calcining
Solid carbonaceous material accurately controls feeding coal by batcher, is delivered on the left of U-shaped furnace 4 by carbon heat reducing lack of gas and calcines section as sulphur
The solid catalyst of sour calcium calcining；Weary coke after participating in carbon heat reducing reaction in carbon heat reducing tower 9 is delivered to U-shaped by also Primordial Qi
4 right side gasification section of furnace carries out coal gasification reaction, 1100 DEG C -1500 DEG C of reaction temperature, generates reducibility gas and provides sulfuric acid simultaneously
Calcium calcines institute's calorific requirement, and coal gasification institute calorific requirement is provided by burner；Reducibility gas is by U-shaped 4 foot passage of furnace, by right side
Gasification section enters left side and calcines section, reacts in calcining Duan Zhongyu solid carbonaceous material and calcium sulfate contact, reaction temperature is
800 DEG C -1100 DEG C, by accurately controlling reaction condition and reaction process, calcined product is fired slags, high concentration SO 2 gas
The excessive reducibility gas of body and part；Calcined gas-solid product initially enters high-temperature separator I (5), after gas solid separation
Fired slags shunted according to whether the mass fraction of calcium oxide in slag up to standard: if calcium oxide mass fraction is below standard, say
Bright majority calcium sulfate is not calcined completely, and fired slags are returned to U-shaped furnace 4 by L returning charge valve on the left of part flow arrangement at this time and are recycled
Calcining, to guarantee the calcining rate of calcium sulfate；If calcium oxide mass fraction is up to standard, illustrate that calcium sulfate calcining is more complete, at this time
Enter the cooling of calcium oxide cooler 6 by L returning charge valve on the right side of part flow arrangement, temperature is cooled to 20 DEG C -80 by 900 DEG C -1100 DEG C
DEG C, the cooling thermal discharge of calcium oxide is used for the preheating of calcium sulfate, and fired slags after cooling are stored in calcium oxide warehouse 7；Gas-solid point
The SO for being 3%-30% containing concentration in gas from after2And the reducibility gas of 3%-30%, enter charcoal heat also from top
In 500 DEG C of -1000 DEG C of temperature ranges redox reaction, high concentration occur for former tower 9 with the carbon material in carbon heat reducing tower 9
SO2It is reduced to simple substance sulfur vapor, the carbon material of carbon heat reducing is participated in by batcher and accurately controls feeding coal from charcoal heat also
It is inputted above former tower 9；Weary burnt a part after carbon heat reducing is directly discharged from 9 bottom of carbon heat reducing tower, and a part is by also Primordial Qi
It is carried along into high-temperature separator II (10), is discharged from high-temperature separator II (10) lower part, the weary coke that carbon heat reducing tower 9 is discharged passes through
Partial reduction gas is delivered to U-shaped 4 right side gasification section of furnace as coal gasification raw material；The also Primordial Qi that high-temperature separator II (10) is isolated
Cool down into reheater 11, also Primordial Qi is cooled to 450 DEG C -500 DEG C from 500 DEG C -1000 DEG C, and cooling medium is that carbon heat reducing is weary
Gas；Also Primordial Qi a part after cooling carries weary coke as conveying gas and send to U-shaped 4 right side of furnace, and a part enters refined dedusting and fills
12 are set, the lesser solid powder of partial size in also Primordial Qi is removed, the solid powder separated returns to U-shaped 4 right side gasification section of furnace and makees
For raw material；Also Primordial Qi after dedusting enters the recycling of sulfur recovery facility 13 and obtains sulphur, collects the sulphur storage to get off in sulphur
In storage tank 14, lack of gas a part after Recovered sulphur is as conveying gas by calcium sulfate and solid carbonaceous material catalyst transport to U
Section is calcined on the left of type furnace 4 to be warming up to 500 DEG C -800 DEG C after a part of reheated device heating by 120 DEG C -250 DEG C, return to charcoal heat
It restores tower 9 and is used as temperature adjustment gas, last part lack of gas are discharged after entering flue gas purification system 15.
Embodiment 2:
A kind of collaboration calcium sulfate calcining of coal gasification and carbon heat reducing prepare the device of sulphur, comprising: U-shaped furnace 4, separating at high temperature
Device I (5), calcium sulfate warehouse 1, carbon material warehouse I (3), carbon heat reducing tower 9, high-temperature separator II (10), reheater 11, dedusting
Device 12, sulfur recovery facility 13, sulphur storage tank 14；The U-shaped furnace 4, which divides, calcines section, right side coal gasification section, the left side for left side
Side calcining section is connected with calcium sulfate warehouse 1, carbon material warehouse I (3), the outlet on the U-shaped 4 right side coal gasification section top of furnace and height
Warm separator I (5) import is connected, the outlet of the bottoms material of the high-temperature separator I (5) by part flow arrangement respectively with U-shaped furnace 4
Right side coal gasification section, calcium oxide cooler 6 are connected, gas vent and carbon heat reducing tower 9 at the top of the high-temperature separator I (5)
The material inlet at top is connected, and the outlet of 9 side wall of carbon heat reducing tower is connected with high-temperature separator II (10), the high temperature point
Material outlet from device II (10) bottom is connected with the air inlet of the U-shaped 4 right side coal gasification section side wall of furnace, the separating at high temperature
Gas outlet at the top of device II (10) is sequentially connected with reheater 11, dust-extraction unit 12, sulfur recovery facility 13, sulphur storage tank 14；
The 9 top material entrance of carbon heat reducing tower is also connected with carbon material warehouse II.
In order to make full use of the thermal energy of sulfur vapor, meanwhile, deposit thionic step, in the present embodiment, in the present invention
The cooling medium of reheater 11 is carbon heat reducing lack of gas, the carrier gas due to carbon heat reducing lack of gas also as the calcium sulfate after preheating,
Therefore, the carbon heat reducing lack of gas after heat absorption are more conducive to the decomposition and heating of calcium sulfate.
Embodiment 3:
A kind of collaboration calcium sulfate calcining of coal gasification and carbon heat reducing prepare the device of sulphur, comprising: U-shaped furnace 4, separating at high temperature
Device I (5), calcium sulfate warehouse 1, carbon material warehouse I (3), carbon heat reducing tower 9, high-temperature separator II (10), reheater 11, dedusting
Device 12, sulfur recovery facility 13, sulphur storage tank 14；The U-shaped furnace 4, which divides, calcines section, right side coal gasification section, the left side for left side
Side calcining section is connected with calcium sulfate warehouse 1, carbon material warehouse I (3), the outlet on the U-shaped 4 right side coal gasification section top of furnace and height
Warm separator I (5) import is connected, the outlet of the bottoms material of the high-temperature separator I (5) by part flow arrangement respectively with U-shaped furnace 4
Right side coal gasification section, calcium oxide cooler 6 are connected, gas vent and carbon heat reducing tower 9 at the top of the high-temperature separator I (5)
The material inlet at top is connected, and the outlet of 9 side wall of carbon heat reducing tower is connected with high-temperature separator II (10), the high temperature point
Material outlet from device II (10) bottom is connected with the air inlet of the U-shaped 4 right side coal gasification section side wall of furnace, the separating at high temperature
Gas outlet at the top of device II (10) is sequentially connected with reheater 11, dust-extraction unit 12, sulfur recovery facility 13, sulphur storage tank 14；
The 9 top material entrance of carbon heat reducing tower is also connected with carbon material warehouse II.
In the present embodiment, the air inlet of 9 bottom of carbon heat reducing tower and the U-shaped 4 right side coal gasification section side wall of furnace
It is connected, together from the weary burnt of 9 bottom of carbon heat reducing tower exclusion and from the weary coke of high-temperature separator II (10) lower part discharge, pass through portion
Divide reduction conductance to enter the raw material in U-shaped furnace 4 as coal gasification reaction, both realizes recycling for weary coke, meanwhile, the heat of weary coke
The raising of coal gasification reaction efficiency can be promoted again with activity.
Embodiment 4:
A kind of collaboration calcium sulfate calcining of coal gasification and carbon heat reducing prepare the device of sulphur, comprising: U-shaped furnace 4, separating at high temperature
Device I (5), calcium sulfate warehouse 1, carbon material warehouse I (3), carbon heat reducing tower 9, high-temperature separator II (10), reheater 11, dedusting
Device 12, sulfur recovery facility 13, sulphur storage tank 14；The U-shaped furnace 4, which divides, calcines section, right side coal gasification section, the left side for left side
Side calcining section is connected with calcium sulfate warehouse 1, carbon material warehouse I (3), the outlet on the U-shaped 4 right side coal gasification section top of furnace and height
Warm separator I (5) import is connected, the outlet of the bottoms material of the high-temperature separator I (5) by part flow arrangement respectively with U-shaped furnace 4
Right side coal gasification section, calcium oxide cooler 6 are connected, gas vent and carbon heat reducing tower 9 at the top of the high-temperature separator I (5)
The material inlet at top is connected, and the outlet of 9 side wall of carbon heat reducing tower is connected with high-temperature separator II (10), the high temperature point
Material outlet from device II (10) bottom is connected with the air inlet of the U-shaped 4 right side coal gasification section side wall of furnace, the separating at high temperature
Gas outlet at the top of device II (10) is sequentially connected with reheater 11, dust-extraction unit 12, sulfur recovery facility 13, sulphur storage tank 14；
The 9 top material entrance of carbon heat reducing tower is also connected with carbon material warehouse II.
In the present embodiment, the material outlet of 12 bottom of deduster is connected with U-shaped 4 right side coal gasification section of furnace, reduction
Solid powder in gas is after the separation of deduster 12, since main component is C, it can be used as the raw material of coal gasification reaction,
Improve the efficiency of coal gasification reaction.
Embodiment 4:
A kind of collaboration calcium sulfate calcining of coal gasification and carbon heat reducing prepare the device of sulphur, comprising: U-shaped furnace 4, separating at high temperature
Device I (5), calcium sulfate warehouse 1, carbon material warehouse I (3), carbon heat reducing tower 9, high-temperature separator II (10), reheater 11, dedusting
Device 12, sulfur recovery facility 13, sulphur storage tank 14；The U-shaped furnace 4, which divides, calcines section, right side coal gasification section, the left side for left side
Side calcining section is connected with calcium sulfate warehouse 1, carbon material warehouse I (3), the outlet on the U-shaped 4 right side coal gasification section top of furnace and height
Warm separator I (5) import is connected, the outlet of the bottoms material of the high-temperature separator I (5) by part flow arrangement respectively with U-shaped furnace 4
Right side coal gasification section, calcium oxide cooler 6 are connected, gas vent and carbon heat reducing tower 9 at the top of the high-temperature separator I (5)
The material inlet at top is connected, and the outlet of 9 side wall of carbon heat reducing tower is connected with high-temperature separator II (10), the high temperature point
Material outlet from device II (10) bottom is connected with the air inlet of the U-shaped 4 right side coal gasification section side wall of furnace, the separating at high temperature
Gas outlet at the top of device II (10) is sequentially connected with reheater 11, dust-extraction unit 12, sulfur recovery facility 13, sulphur storage tank 14；
The 9 top material entrance of carbon heat reducing tower is also connected with carbon material warehouse II.
In the present embodiment, the exhanst gas outlet of the sulfur recovery facility 13 also respectively with flue gas purification system 15, U-shaped furnace
4 left side calcining sections are connected with reheater 11, and lack of gas a part after Recovered sulphur is used as conveying gas by calcium sulfate and solid carbon
Material catalyst, which is delivered on the left of U-shaped furnace 4, calcines section, after a part of reheated device 11 heats up, is warming up to by 120 DEG C -250 DEG C
It 500 DEG C -800 DEG C, returns to carbon heat reducing tower 9 and is used as temperature adjustment gas, last part lack of gas enter 15 heel row of flue gas purification system
Out.
Embodiment 5:
A kind of collaboration calcium sulfate calcining of coal gasification and carbon heat reducing prepare the device of sulphur, comprising: U-shaped furnace 4, separating at high temperature
Device I (5), calcium sulfate warehouse 1, carbon material warehouse I (3), carbon heat reducing tower 9, high-temperature separator II (10), reheater 11, dedusting
Device 12, sulfur recovery facility 13, sulphur storage tank 14；The U-shaped furnace 4, which divides, calcines section, right side coal gasification section, the left side for left side
Side calcining section is connected with calcium sulfate warehouse 1, carbon material warehouse I (3), the outlet on the U-shaped 4 right side coal gasification section top of furnace and height
Warm separator I (5) import is connected, the outlet of the bottoms material of the high-temperature separator I (5) by part flow arrangement respectively with U-shaped furnace 4
Right side coal gasification section, calcium oxide cooler 6 are connected, gas vent and carbon heat reducing tower 9 at the top of the high-temperature separator I (5)
The material inlet at top is connected, and the outlet of 9 side wall of carbon heat reducing tower is connected with high-temperature separator II (10), the high temperature point
Material outlet from device II (10) bottom is connected with the air inlet of the U-shaped 4 right side coal gasification section side wall of furnace, the separating at high temperature
Gas outlet at the top of device II (10) is sequentially connected with reheater 11, dust-extraction unit 12, sulfur recovery facility 13, sulphur storage tank 14；
The 9 top material entrance of carbon heat reducing tower is also connected with carbon material warehouse II.
In the present embodiment, calcium sulfate preheater 2 is provided between the calcium sulfate warehouse 1 and U-shaped furnace 4.Pass through preheating
Calcium sulfate is converted into dead plaster, and steam is excluded, avoids influencing subsequent decomposition reaction.
Embodiment 6:
A kind of collaboration calcium sulfate calcining of coal gasification and carbon heat reducing prepare the device of sulphur, comprising: U-shaped furnace 4, separating at high temperature
Device I (5), calcium sulfate warehouse 1, carbon material warehouse I (3), carbon heat reducing tower 9, high-temperature separator II (10), reheater 11, dedusting
Device 12, sulfur recovery facility 13, sulphur storage tank 14；The U-shaped furnace 4, which divides, calcines section, right side coal gasification section, the left side for left side
Side calcining section is connected with calcium sulfate warehouse 1, carbon material warehouse I (3), the outlet on the U-shaped 4 right side coal gasification section top of furnace and height
Warm separator I (5) import is connected, the outlet of the bottoms material of the high-temperature separator I (5) by part flow arrangement respectively with U-shaped furnace 4
Right side coal gasification section, calcium oxide cooler 6 are connected, gas vent and carbon heat reducing tower 9 at the top of the high-temperature separator I (5)
The material inlet at top is connected, and the outlet of 9 side wall of carbon heat reducing tower is connected with high-temperature separator II (10), the high temperature point
Material outlet from device II (10) bottom is connected with the air inlet of the U-shaped 4 right side coal gasification section side wall of furnace, the separating at high temperature
Gas outlet at the top of device II (10) is sequentially connected with reheater 11, dust-extraction unit 12, sulfur recovery facility 13, sulphur storage tank 14；
The 9 top material entrance of carbon heat reducing tower is also connected with carbon material warehouse II.
In the present embodiment, the calcium oxide cooler 6 is connected with calcium oxide warehouse 7, and calcium oxide can replace lime masonry
Therefore calcium oxide after cooling is collected using calcium oxide warehouse 7 for desulfurization denitrification agent, it is spare.
1. calcium sulfate warehouse, 2. calcium sulfate preheaters, 3. carbon material warehouses I, 4.U type furnace, 5. high-temperature separators I, 6. oxygen
Change calcium cooler, 7. calcium oxide warehouses, 8. carbon material warehouses II, 9. carbon heat reducing towers, 10. high-temperature separators II, 11. reheating
Device, 12. refined dedusting devices, 13 sulfur recovery facilities, 14. sulphur storage tanks, 15. flue gas purification systems
Embodiment 7:
A kind of collaboration calcium sulfate calcining of coal gasification and carbon heat reducing prepare the device of sulphur, comprising: U-shaped furnace 4, separating at high temperature
Device I (5), calcium sulfate warehouse 1, carbon material warehouse I (3), carbon heat reducing tower 9, high-temperature separator II (10), reheater 11, dedusting
Device 12, sulfur recovery facility 13, sulphur storage tank 14；The U-shaped furnace 4, which divides, calcines section, right side coal gasification section, the left side for left side
Side calcining section is connected with calcium sulfate warehouse 1, carbon material warehouse I (3), the outlet on the U-shaped 4 right side coal gasification section top of furnace and height
Warm separator I (5) import is connected, the outlet of the bottoms material of the high-temperature separator I (5) by part flow arrangement respectively with U-shaped furnace 4
Right side coal gasification section, calcium oxide cooler 6 are connected, gas vent and carbon heat reducing tower 9 at the top of the high-temperature separator I (5)
The material inlet at top is connected, and the outlet of 9 side wall of carbon heat reducing tower is connected with high-temperature separator II (10), the high temperature point
Material outlet from device II (10) bottom is connected with the air inlet of the U-shaped 4 right side coal gasification section side wall of furnace, the separating at high temperature
Gas outlet at the top of device II (10) is sequentially connected with reheater 11, dust-extraction unit 12, sulfur recovery facility 13, sulphur storage tank 14；
The 9 top material entrance of carbon heat reducing tower is also connected with carbon material warehouse II.
In the present embodiment, the outlet of calcium sulfate warehouse 1, carbon material warehouse I, II (3,8) outlet, the weary coke of carbon heat reducing
Lock gas batcher is set at discharge, high-temperature separator II (10) lower part outlet pipeline, accurately to control conveying amount, and guarantees system
Leakproofness.
Embodiment 8:
A kind of method that coal gasification cooperates with calcium sulfate calcining and carbon heat reducing to prepare sulphur, comprising:
By after preheating calcium sulphate powders, with solid carbonaceous material, the reducibility gas haptoreaction at 800 DEG C -1100 DEG C,
Collect fired slags, high concentration SO2The excessive reducibility gas of gas and part；
By fired slags, high concentration SO2The excessive reducibility gas gas solid separation of gas and part, makes SO2Gas and portion
Divide excessive reducibility gas to react at 500 DEG C -1000 DEG C with carbon material, generates simple substance sulfur vapor；
Wherein, weary burnt, the also Primordial Qi after reducibility gas is reacted by carbon heat reducing carries out coal gasification reaction generation.
Finally it should be noted that the foregoing is only a preferred embodiment of the present invention, it is not limited to this hair
It is bright, although the present invention is described in detail referring to the foregoing embodiments, for those skilled in the art, still
It can modify to technical solution documented by previous embodiment, or part is equivalently replaced.It is all in this hair
Within bright spirit and principle, any modification, equivalent replacement, improvement and so on should be included in protection scope of the present invention
Within.Above-mentioned, although the foregoing specific embodiments of the present invention is described with reference to the accompanying drawings, not to the scope of the present invention
Limitation, those skilled in the art should understand that, based on the technical solutions of the present invention, those skilled in the art are not required to
Make the creative labor the various modifications or changes that can be made still within protection scope of the present invention.
Claims (10)
1. the device that a kind of coal gasification collaboration calcium sulfate calcining and carbon heat reducing prepare sulphur characterized by comprising U-shaped furnace,
High-temperature separator I, calcium sulfate warehouse, carbon material warehouse I, carbon heat reducing tower, high-temperature separator II, reheater, dust-extraction unit, sulphur
Sulphur recyclable device, sulphur storage tank；The U-shaped furnace is divided into left side and calcines section, right side coal gasification section, the left side calcining section and sulfuric acid
Calcium warehouse, carbon material warehouse I are connected, and the outlet on coal gasification section top is connected with I import of high-temperature separator on the right side of the U-shaped furnace,
The bottoms material outlet of the high-temperature separator I by part flow arrangement respectively with coal gasification section, calcium oxide cooler on the right side of U-shaped furnace
It is connected, the gas vent at I top of high-temperature separator is connected with the material inlet of carbon heat reducing top of tower, the carbon heat reducing
The outlet of tower side wall is connected with high-temperature separator II, on the right side of the material outlet of II bottom of high-temperature separator and the U-shaped furnace
The air inlet of coal gasification section side wall is connected, and the gas outlet at II top of high-temperature separator and reheater, dust-extraction unit, sulphur return
Receiving apparatus, sulphur storage tank are sequentially connected；
The carbon heat reducing top of tower material inlet is also connected with carbon material warehouse II.
2. device as described in claim 1, which is characterized in that the cooling medium of the reheater is carbon heat reducing lack of gas.
3. device as described in claim 1, which is characterized in that coal gas on the right side of the carbon heat reducing tower bottom and the U-shaped furnace
The air inlet for changing section side wall is connected.
4. device as described in claim 1, which is characterized in that coal on the right side of the material outlet of the deduster bottom and U-shaped furnace
Gasification section is connected.
5. device as described in claim 1, which is characterized in that the gas vent of the sulfur recovery facility also respectively with flue gas
Calcining section is connected with reheater on the left of purification system, U-shaped furnace.
6. device as described in claim 1, which is characterized in that the calcium sulfate warehouse and U-shaped furnace are provided directly with preheater.
7. device as described in claim 1, which is characterized in that the calcium oxide cooler is connected with calcium oxide warehouse.
8. device as described in claim 1, which is characterized in that the calcium sulfate warehouse outlet, the outlet of carbon material warehouse, charcoal heat
Weary coke is restored to be discharged, set lock gas batcher at II lower part outlet pipeline of high-temperature separator.
9. a kind of method that coal gasification collaboration calcium sulfate calcining and carbon heat reducing prepare sulphur characterized by comprising
By the calcium sulphate powders and solid carbonaceous material, the reducibility gas haptoreaction at 800 DEG C -1100 DEG C after preheating, collect
Fired slags, high concentration SO2The excessive reducibility gas of gas and part；
By fired slags, high concentration SO2The excessive reducibility gas gas solid separation of gas and part, makes SO2Gas and part mistake
The reducibility gas of amount is reacted at 500 DEG C -1000 DEG C with carbon material, generates simple substance sulfur vapor；
Wherein, weary burnt, the also Primordial Qi after reducibility gas is reacted by carbon heat reducing carries out coal gasification reaction generation.
10. the method as described in claim 1, which is characterized in that the calcium sulfate, 60 μm of -3mm of partial size are wet desulphurization stone
At least one of cream, semi-dry processed desulfurization gypsum, the natural gypsum and ardealite；
The carbon material, 60 μm of -3mm of partial size, at least for coal dust, activated coke, active carbocoal, active carbon, carbonized material, graphite kind
It is a kind of.
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Application publication date: 20190521 Assignee: QINGDAO DANENG ENVIRONMENTAL PROTECTION EQUIPMENT INCORPORATED Co. Assignor: SHANDONG University Contract record no.: X2021980000808 Denomination of invention: Device and method for preparation of sulfur by coal gasification combined with calcination of calcium sulfate and carbothermal reduction Granted publication date: 20200707 License type: Common License Record date: 20210129 |