CN101306803A - Process for producing sulfate acid from gypsum - Google Patents
Process for producing sulfate acid from gypsum Download PDFInfo
- Publication number
- CN101306803A CN101306803A CNA2008100482390A CN200810048239A CN101306803A CN 101306803 A CN101306803 A CN 101306803A CN A2008100482390 A CNA2008100482390 A CN A2008100482390A CN 200810048239 A CN200810048239 A CN 200810048239A CN 101306803 A CN101306803 A CN 101306803A
- Authority
- CN
- China
- Prior art keywords
- gypsum
- raw material
- oxygen
- sulfuric acid
- gas
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910052602 gypsum Inorganic materials 0.000 title claims abstract description 47
- 239000010440 gypsum Substances 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 29
- 230000008569 process Effects 0.000 title claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 title claims description 10
- 239000002253 acid Substances 0.000 title description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 67
- 239000007789 gas Substances 0.000 claims abstract description 52
- 238000004519 manufacturing process Methods 0.000 claims abstract description 48
- 239000002994 raw material Substances 0.000 claims abstract description 41
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 29
- 239000001301 oxygen Substances 0.000 claims abstract description 29
- 239000004568 cement Substances 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 11
- 239000000571 coke Substances 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 239000004927 clay Substances 0.000 claims abstract description 5
- 239000003245 coal Substances 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 claims description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- 238000010521 absorption reaction Methods 0.000 claims description 10
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Inorganic materials [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 10
- 238000010304 firing Methods 0.000 claims description 10
- ZOMBKNNSYQHRCA-UHFFFAOYSA-J calcium sulfate hemihydrate Chemical compound O.[Ca+2].[Ca+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZOMBKNNSYQHRCA-UHFFFAOYSA-J 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- 239000011507 gypsum plaster Substances 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 6
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 5
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 239000004571 lime Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- XOCUXOWLYLLJLV-UHFFFAOYSA-N [O].[S] Chemical compound [O].[S] XOCUXOWLYLLJLV-UHFFFAOYSA-N 0.000 claims description 4
- 238000002485 combustion reaction Methods 0.000 claims description 4
- 239000003546 flue gas Substances 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000003795 desorption Methods 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 238000005201 scrubbing Methods 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 238000013467 fragmentation Methods 0.000 claims 1
- 238000006062 fragmentation reaction Methods 0.000 claims 1
- 238000011084 recovery Methods 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 7
- 230000007613 environmental effect Effects 0.000 abstract 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 9
- 239000005864 Sulphur Substances 0.000 description 8
- 239000002893 slag Substances 0.000 description 8
- 239000001117 sulphuric acid Substances 0.000 description 7
- 235000011149 sulphuric acid Nutrition 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000000428 dust Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000011800 void material Substances 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000012856 packing Methods 0.000 description 3
- 239000002686 phosphate fertilizer Substances 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000011398 Portland cement Substances 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- QLULGSLAHXLKSR-UHFFFAOYSA-N azane;phosphane Chemical compound N.P QLULGSLAHXLKSR-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000003588 decontaminative effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000002367 phosphate rock Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
Landscapes
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
A method for producing sulfuric acid from gypsum comprises the steps of crushing gypsum, clay, coke and auxiliary materials, homogenizing, preheating in a three-stage preheater, calcinating in a rotary kiln while introducing oxygen-enriched air to obtain SO2 gas and clinker, feeding the SO2 gas into a sulfuric acid system for sulfuric acid production, and cooling the clinker with a cooling machine and feeding into a cement system for cement production. The inventive method designs raw material ratio, etc. with the focus of sulfuric acid production through the steps of preheating with the three-stage preheater and introducing oxygen-enriched air to produce sulfuric acid; and has the advantages of reduced calcination difficulty, remarkably increased sulfuric acid yield, remarkably reduced production cost, remarkably reduced calcination heat consumption, and distinct environmental and economic benefits. Also, the tail gas emission comes up to standards.
Description
Technical field
The present invention relates to a kind of residue phosphogypsum of phosphate fertilizer industry or the mixture of the plaster of paris or desulfurized gesso of flue gas or several gypsum and produce the vitriolic technology, belong to the gas washing in SA production technical field, a kind of specifically mixture of phosphogypsum or the plaster of paris or desulfurized gesso of flue gas or several gypsum that utilizes is produced sulfuric acid and attached product Cement Production method.
Background technology
China is the large agricultural country of a sulphur resource shortage, account for more than 70% of sulfuric acid consumption in the production of phosphate fertilizer, the thiosulfonic acid that with sulphur is raw material accounts for 50% of sulfuric acid ultimate production, and the raw material of acid production with sulphur from import, adds the external interdependency of upper inlet sulfuric acid China sulphur resource and surpassed 55% more than 95%.The sulphur price has risen suddenly and sharply and is high in the recent period.Be that to produce sulfuric acid be that the problem that solves China's sulphur resource shortage will be walked out a new road to raw material with the gypsum.In production of phosphate fertilizer, one ton of phosphorus ammonium of every production just produces about 4 tons of phosphogypsum slags, stores up contaminate environment.Simultaneously, China's gypsum reserves are abundant, and proven reserve are about 1,000 hundred million tons.Various desulfurized gesso of flue gas are also in continuous increase.Utilize gypsum relieving haperacidity can solve the predicament of China's sulphur resource shortage, the restricted external raw material of acid production with sulphur fully.
China's phosphate rock resource is rich, and along with a large amount of uses of rich ore, the phosphorus ore dilution is on the rise and not rich, P
2O
5Content generally is lower than 30%, SiO
2Content is higher than 12%, causes the phosphogypsum slag that produces in the phosphoric acid production of poor quality, and phosphogypsum slag can't be utilized.Early there is report of poor quality to device can't be moved because of phosphogypsum slag.Mineral reserve plaster of paris grade difference is bigger, most of SiO
2Content height (essence is to be mixed with certain earth) influences the utilization of the plaster of paris.
Original gypsum system vitriolic method, strict to the raw material phosphogypsum or the plaster of paris, as require gypsum P
2O
5Content less than 1.0%, SiO
2Content is less than 5.5%, and the raw material rate value index too biases toward manufacture of cement, causes the calcining temperature height, and firing rate is big, enters sulfate system SO
2Gas concentration is low, SO
2Conversion is difficult to realize that autothermal equilibrium causes hanging electric furnace and keeps production, and oxygen sulphur is than the low SO that makes simultaneously
2Transformation efficiency can't improve, SO in the discharging tail gas
2Concentration over-standard.Simultaneously, sulfuric acid, cement output are low, and the plant construction investment is high, and production cost increases, and deficiency in economic performance has seriously restricted the development of gypsum system vitriolic.
Summary of the invention
The objective of the invention is to overcome the existing methods defective, is purpose with raising sulphuric acid output, optimization sulfuric acid production process, protection environment, provides a kind of and utilizes various gypsum resources to produce the vitriolic method.By the present invention, utilize relatively poor raw material, produce sulfuric acid and ordinary Portland cement, technical process is smooth and easy, reduces cement firing operation difficulty, and sulphuric acid output increases, and advances sulfate system SO
2The gas concentration height, the tail gas qualified discharge.
The present invention is achieved by the following technical solutions: (with the claim part)
It is provided by the present invention with gypsum production vitriolic method,
(1) improving sulphuric acid output, to optimize sulfuric acid production process and attach most importance to, particularly lime saturation factor is reasonable in design to the rate value of gypsum raw material, the good raw material of preparation burn-ability, and sulphuric acid output improves obviously, significantly reduces production costs.
(2) adopt three grades of cyclone preheaters of structural similitude and use oxygen-rich air, reduce investment, reduce heat-energy losses, burn till hear rate and be reduced to the 6000kj/kg grog, reduce exhaust emissions 0.5Nm by the 7500kj/kg grog
3/ kg grog, energy consumption reduces 20-25%.
(3) reduce the firing operation difficulty by preparing good raw material of burn-ability and use oxygen-rich air etc., solved the low problem of moving difficulty of device driving rate substantially.
(4) by advancing convertor SO
2The raising of gas concentration has realized the double conversion and double absorption flow process fully, and transformation efficiency brings up to 99.8%, and the tail gas qualified discharge has solved the secondary pollution problem at all.
(5) utilize multiple gypsum raw material, draw materials extensively, energy-conserving and environment-protective in addition, production cost are low, and economic benefit is obvious, has possessed the condition that substitutes other raw material development sulfuric acid industry.
Description of drawings
The invention will be further described below in conjunction with drawings and Examples.
Fig. 1 is a process flow sheet of the present invention.
Embodiment
1, the residue phosphogypsum or the oven dry of the two water plasters of paris of phosphoric acid production is extremely moisture below 10.0%, natural anhydrite can not dried (but wanting broken, grinding), stores.Subsidiary material such as coke, clay oven dry back stores, grinding.Various raw materials enter the raw material homogenizing storehouse after preparing burden according to certain ratio.The rate value control of gypsum raw material is as follows: lime saturation factor KH is 0.80-0.97, and silica modulus SM is 2.40-4.50, and iron rate IM is 2.10-3.30.
2, the raw material in the homogenizing storehouse are sent into three grades of whirlwind pre-heating systems after multiple spot blanking homogenizing, and raw material are elevated to 550--660 ℃ by about 50 ℃ in the homogenizing storehouse, enter in the kiln.The gas temperature that kiln discharge enters preheater is 650--850 ℃, becomes about 300 ℃ after to the material preheating.Go out preheater SO
2Gas concentration is that 12.0-16.6% (butt, volume ratio) enters sulfate system production sulfuric acid.
3, going into the kiln raw material calcines to generate in rotary kiln and contains SO
2The kiln gas of gas and cement clinker.The calcining temperature of burning till in the kiln is 1100--1350 ℃, and coal burner adopts three air channels or four air channel coal rifles, and feeds oxygen-rich air.Oxygen-rich air can feed an air channel or partly or entirely feed.Also can add oxygen-rich air according to combustion case at kiln hood or cooler.
Along with the development of oxygen enrichment technologies such as membrane separation process, pressure swing adsorption process, characteristics such as particularly embrane method production has that flow process is simple, volume is little, self energy consumption is low in the production of oxygen-rich air, long service life, investment are less, energy-saving effect is remarkable.The content of oxygen can be 20.93-100% in the oxygen-rich air of adding coal rifle, and recommending the content of oxygen in the economic oxygen-rich air according to existing oxygen enrichment technology is about 30%.This has also reached the purpose of optimizing sulfuric acid production process fully.
4, go out preheater SO
2Gas at first enters the purification section of sulfuric acid apparatus through induced draft fan.Its acid-scrubbing cleaning flow process is electric, empty, cold, electric, electric current journey, i.e. SO
2Gas enters electric precipitation, void tower, cooling tower (also can be void tower or packing tower), electric demist, electric demist successively.Also can before electric precipitation, increase the one-level tornado dust collector, to alleviate the electric precipitation load.Adverse current sealing pickling, void tower recycle acid concentration is 3-30%, its concentration is by the dust content of gas, the decisions such as content of fluorine.Gas institute heat content is mainly cooled off by the recycle acid heat exchange and is removed.The recycle acid that goes out system removes SO by desorption tower
2, take off suck and can partly or entirely adopt oxygen-rich air.This process Selection is that the characteristics according to gypsum relieving haperacidity kiln gas design fully.
5, purified gas enters conversion system after gas blower is sent into drying tower, and multiple flow process is arranged, and can adopt twice conversion of 3+1, III I--IV II heat exchange process.Advance to transform SO
2Gas concentration 〉=7.2%, oxygen sulphur is than (O
2/ SO
2) 〉=1.15, total conversion rate 〉=99.8%.
6, a reforming gas that is come by conversion system enters intermediate absorber, absorbs SO with 98% recycle acid circulated sprinkling in the tower
3Gas, the gas that goes out inter-chamber tower enters final absorption tower behind twice transformation, also absorb SO with 98% recycle acid circulated sprinkling in the tower
3Gas.Through twice absorption, total absorptivity can reach more than 99.95%, the gas qualified discharge after the absorption.
Finished acid drying acid circulation groove or absorb sour circulation groove and draw is to produce 93% or 98% sulfuric acid.
7, go out rotary kiln clinker storage after the cooler cooling, batching, grinding, homogenizing, packing etc. and become cement products.
The embodiment explanation
1, the present invention adopts second-rate raw material, to adapt to the decline of phosphorus ore grade in the phosphoric acid production.At phosphorus ore P
2O
5Content generally is lower than 30%, SiO
2Content is higher than 12%, causes the phosphogypsum slag that produces in the phosphoric acid production of poor quality, makes the unserviceable situation of phosphogypsum slag, by the present invention, and the phosphogypsum slag of functional quality difference or the plaster of paris etc., oven dry is to moisture less than 10.0%, SiO
2Content can be loosened to 10%, P
2O
5Content can be loosened to 1.6%, improves sulphuric acid output simultaneously, reduces production costs.The oven dry of phosphogypsum can be adopted energy-saving fluidizing furnace, and the raw coal of functional quality difference or coal gangue are sent the gypsum oven dry into the gypsum bank.
Need to prove that the gypsum raw material oven dry back of batching is moisture low more, and production cost of products is also low more.Because if the moisture in the gypsum is not to deviate from by oven dry, but removes in the firing system of kiln, this part dehydration energy consumption just is converted into burns till hear rate.Its waste gas that coal burning produced that increases the energy consumption part just enters and contains SO
2Kiln gas in, this must water down kiln gas, reduces SO in the gas
2Concentration.Cause the sulfuric acid conversion system can only adopt a commentaries on classics one suction or double conversion and double absorption to be difficult to operation, double conversion and double absorption is operated in the preferred range.The increase of burning till hear rate has simultaneously also reduced production intensity, and sulphuric acid output is difficult to improve.
2, carry out grinding after coke and other subsidiary material are prepared burden in proportion, needn't grinding and account for the phosphogypsum of proportion scale about 90%, the effect of save energy is obvious.
3, in the rate value control of gypsum raw material, lime saturation factor KH is 0.80-0.97, is under the prerequisite that guarantees the cement quality basic demand, reduces calcining temperature and burns till hear rate, to improve SO
2Gas concentration.By the grog that forms under this proportioning, can reach the requirement of normal silicate grog fully.C during its clinker mineral is formed
3The content of S compares C
2The content of S is low, and the enhancement speed of early strength is slow slightly, but its significant advantage is the later strength height, compares with the similar cement of Wingdale raw material production, and later strength increases obviously.So in the approval that more obtains the human consumer qualitatively.
The proportioning of main raw material is: gypsum 87-93%
Clay 0-7%
Coke 4.5-7.5%
Subsidiary material 0-4%
Wherein subsidiary material are iron powder or aluminium vanadine or both mixtures.
4, the raw material that prepare enter three grades of preheaters, and after three grades of preheaters were to the raw material preheating, the raw material temperature was elevated to 550--660 ℃ and goes into kiln.The gas temperature that kiln discharge enters preheater is 650--850 ℃, and the gas temperature that goes out preheater after to the raw material preheating becomes about 300 ℃, enters sulfate system and produces sulfuric acid.
Three grades of preheaters all adopt the low-drag type cyclone preheater, or band one-level shaft preheater multistage with employing compared, and pre-heat effect is good, and the structural similitude of three grades of preheaters, and fabrication and installation are simple, also reduced plant investment.By optimizing the structure of three grades of cyclone preheaters, three grades of preheaters have reached level Four preheater effect fully.Simultaneously, needn't require the too high kiln temperature of charge of going into.Will cause a large amount of cokes to burn in advance because temperature of charge surpasses 650 ℃, bring difficulty for the decomposition of raw material, calcining, or artificially increased the loss of coke, also improve production cost.Simultaneously, the burning of these carbon has caused the temperature reversal of the natural order of things of preheater, and operation is worsened.
Adopting three grades of preheaters is suitable to the preheating of the gypsum raw material of being furnished with a certain proportion of coke.
The use of three grades of preheaters has effectively reduced the length of rotary kiln, and length-to-diameter ratio drops to 18.2-23.2 by 30, has reduced facility investment, has reduced surface radiating, has reduced and has burnt till hear rate.
By adopting three grades of preheaters to make the into reduction of sulfate system kiln gas temperature and the minimizing of surface radiating, reduce and burn till hear rate above the 800kj/kg grog, promptly reduce and burn till coal consumption 0.03kj/kg grog, reduce exhaust emissions 0.2Nm
3/ kg grog.
In order to improve decontamination effect improving, for vitriolic production creates favorable conditions, can before electric precipitator, increase tornado dust collector, efficiency of dust collection is more than 90%, to alleviate the load of electric precipitation.
5, enter the interior material of kiln, calcining and decomposing in kiln generates SO
2The grog of gas and production cement.General manufacture of cement or gypsum raw material are produced the device of producing sulfuric acid and jointly cement, its clinker burning temperature is usually at 1300--1450 ℃, and the present invention serves as the main Cement Production of taking into account to produce sulfuric acid, so in the raw material rate value design of batching, adopted lower lime saturation factor, the incinerating firing temperature can be reduced to 1100--1350 ℃ in the kiln, and to the decomposition temperature of calcium sulfate about 900 ℃ enough, also can finish burning till of grog.By the reduction of firing temperature, can reduce greatly and burn till hear rate, promptly, reduced the firing operation difficulty by the good gypsum raw material of preparation burn-ability, improved plant capacity 10--30%.By the raising of output, the benefit that has significantly reduced production cost, particularly sulfuric acid product is the main body that gypsum relieving haperacidity jointly producing cement device brings benefits, and by improving vitriolic output (grog also increases on year-on-year basis), economic benefit also significantly improves.
When bunker coal burns in air, utilization be 21% oxygen in the air, and it has brought 79% nitrogen simultaneously into, this has increased the quantity discharged of tail gas, has also increased the loss of heat energy with tail gas.The more important thing is that it has reduced the SO in the gas
2Concentration, the preferable states that makes gas washing in SA production operate in double conversion and double absorption are difficult to realize.By adding oxygen-rich air, can improve the burning of coal rate, overcome kiln atmosphere based on weak oxide atmosphere, cause that the coal combustion rate is low, the insufficient smoulder in kiln of the gun burner that produces coal, even generate portion C O earlier, increase the situation that sublimed sulphur occurs.Simultaneously, can improve efficiency of combustion 30%, control kiln atmosphere easily, reduce the firing operation difficulty of kiln.Adopt oxygen-rich air, overcome above shortcoming, reduced and burnt till hear rate, improved kiln gas SO
2Concentration.
As add 20% oxygen-rich air, can reduce N
2Discharging 0.1Nm
3/ kg grog or operating mode air quantity 0.5m
3/ kg grog reduces it and takes away heat 100kj/kg grog, reduces and burns till coal consumption 0.004kg/kg grog, kiln discharge gas SO
2Concentration improves 0.5%.
By above multiple measure, make and burn till hear rate and be reduced to about 6000kj/kg grog by the 7500kj/kg grog, energy consumption reduces 20-25%.
6, go out the SO that contains of preheater
2Kiln gas enters the purification section of sulfuric acid apparatus.SO
2Gas enters electric precipitation, void tower, cooling tower, the demist of two-stage electricity successively, and gas temperature drops to below 38 ℃, is pressed into drying tower by gas blower then, and the dry kiln air water divides the qualified sulfuric acid conversion workshop section that enters.In order to reach O
2/ SO
2〉=1.15 index, the desorption tower adding oxygen-rich air at purification section also can add before gas blower, and the size of add-on is with O
2/ SO
2〉=1.15 determine.The oxygen sulphur of twice transformation gas is than (O
2/ SO
2) can reach 15-20.Add oxygen-rich air,, improve and advance convertor SO exactly in order to reduce bringing into of nitrogen
2Gas concentration, the autothermal equilibrium of realization double conversion and double absorption.Can also reduce the specification of sulphuric acid device, reduce investment.Total conversion rate 〉=99.8%, exhaust emissions SO
2Concentration≤300PPm.
Through double conversion and double absorption, produce qualified finished product sulfuric acid.
7, cement clinker through cooler cooling, store and laggardly go into the cement system and subsidiary material batching back grinding, homogenizing, packings such as volcanic ash or slag, gypsum are produced cement products.To burn till hear rate in order reducing, to improve SO
2Gas concentration adopts high cooler such as the grate cooler of heat exchange efficiency.
Claims (10)
1, a kind of with gypsum production vitriolic method, it is characterized in that: this method comprises:
(1) gypsum raw material preparation:
Raw material are mixed by following weight ratio raw material: gypsum 87-93%
Clay 0-7%
Coke 4.5-7.5%
Subsidiary material 0-4%
Wherein subsidiary material are iron powder or aluminium vanadine or both mixtures.
Enter the raw material homogenizing storehouse behind gypsum, clay, coke and subsidiary material fragmentation, oven dry, the grinding and carry out homogenizing, rate value control to the gypsum raw material is as follows: lime saturation factor KH is 0.80-0.97, silica modulus SM is 2.40-4.50, and iron rate IM is 2.10-3.30;
(2) raw material in the homogenizing storehouse are sent into firing system, in three grades of cyclone preheaters, carry out preheating, raw material are elevated to 550--660 ℃ by 50 ℃ in the homogenizing storehouse, entering rotary kiln calcines, calcining temperature is 1100--1350 ℃ in the kiln, coal burner adopts three air channels or four air channel coal rifles, and feeds oxygen-rich air, the SO that obtains after the calcining
2Gas enters sulfate system and is used for producing sulfuric acid, and another product grog after the calcining is gone into the cement system and is used for producing cement by cooler cooling is laggard;
(3) come out to enter the SO of sulfate system from kiln tail preheater
2Gas adopts acid-scrubbing cleaning, double conversion and double absorption flow process, obtains sulfuric acid;
2, according to claim 1 it is characterized in that: used gypsum can be the phosphogypsum of the attached product of phosphoric acid or the mixture of the plaster of paris or desulfurized gesso of flue gas or these several gypsum with gypsum production vitriolic method, and gypsum is moisture less than 10.0% before the batching, SiO
2Content is less than 10.0%, P
2O
5Content is less than 1.6%.
3, according to claim 1 with gypsum production vitriolic method, it is characterized in that: three grades of cyclone preheaters of the low-drag type of the pre-thermal recovery of gypsum raw material, preheaters at different levels all adopt cyclone preheater.
4, according to claim 1 with gypsum production vitriolic method, it is characterized in that: the SO that enters sulfate system
2Gas is in butt, volume by volume concentration 〉=7.2%, and oxygen sulphur is than (O
2/ SO
2) 〉=1.15.
5, according to claim 1 with gypsum production vitriolic method, it is characterized in that: the content of oxygen is counted 20.93-100% with volume ratio in the oxygen-rich air of adding.
6, gypsum is produced the vitriolic method according to claim 1 or 5, and it is characterized in that: the content of oxygen is counted 28-32% with volume ratio in the oxygen-rich air of adding.
7, gypsum according to claim 1 is produced the vitriolic method, and it is characterized in that: the amount of the oxygen-rich air of adding is counted the 10-150% that burns till the coal combustion required air quantity with volume ratio.
8, produce the vitriolic method according to the described gypsum of claim 1, it is characterized in that: with the length (length) of the supporting rotary kiln of three grades of cyclone preheaters directly (external diameter) than being 18.2-23.2.
9, describedly produce the vitriolic method according to claim 1 or 7, it is characterized in that: in firing system, add oxygen-rich air at coal rifle or kiln hood or cooler with gypsum.
10, according to claim 1 with gypsum production vitriolic method, it is characterized in that: in sulfate system, at acid-scrubbing cleaning desorption tower or SO
2Add oxygen-rich air before the fans entrance.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100482390A CN101306803A (en) | 2008-06-27 | 2008-06-27 | Process for producing sulfate acid from gypsum |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100482390A CN101306803A (en) | 2008-06-27 | 2008-06-27 | Process for producing sulfate acid from gypsum |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101306803A true CN101306803A (en) | 2008-11-19 |
Family
ID=40123514
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2008100482390A Pending CN101306803A (en) | 2008-06-27 | 2008-06-27 | Process for producing sulfate acid from gypsum |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101306803A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101830442A (en) * | 2010-04-27 | 2010-09-15 | 重庆三圣特种建材股份有限公司 | Process for co-producing sulphuric acid and cement by using gypsum |
| CN101863500A (en) * | 2010-06-04 | 2010-10-20 | 中南大学 | A method for producing alumina from aluminum-containing metallurgical materials |
| WO2012003619A1 (en) * | 2010-07-05 | 2012-01-12 | Yin Xiaolin | Process for directly producing sulfur trioxide and sulfuric acid using gypsum as raw material |
| CN103304170A (en) * | 2013-06-28 | 2013-09-18 | 重庆大学 | Method for producing sulphate aluminum cement |
| CN109279582A (en) * | 2018-10-23 | 2019-01-29 | 山东汇泰再生资源有限公司 | A kind of ardealite acid preparation method using electrolytic aluminium waste cathode carbon block |
| CN112209692A (en) * | 2020-09-16 | 2021-01-12 | 贵州正和天筑科技有限公司 | Phosphogypsum anti-cracking plastering mortar and preparation method thereof |
| CN115432670A (en) * | 2021-06-01 | 2022-12-06 | 昆明理工大学 | Method and device for preparing sulfuric acid and co-producing cement clinker by oxygen-enriched calcination of phosphogypsum |
| CN115650611A (en) * | 2022-10-05 | 2023-01-31 | 湖北三宁化工股份有限公司 | Method for preparing cement clinker heat source by using carbon-sulfur mixed calcination as phosphogypsum |
| CN116282983A (en) * | 2023-02-21 | 2023-06-23 | 江苏安达环保科技有限公司 | Production method for co-production of sulfuric acid and cement by gypsum |
| CN117902584A (en) * | 2023-12-11 | 2024-04-19 | 宜都兴发化工有限公司 | Preparation of silicon-calcium aggregate, sulfuric acid and CO by phosphogypsum oxygen-enriched pyrolysis2Method and apparatus of (a) |
-
2008
- 2008-06-27 CN CNA2008100482390A patent/CN101306803A/en active Pending
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101830442A (en) * | 2010-04-27 | 2010-09-15 | 重庆三圣特种建材股份有限公司 | Process for co-producing sulphuric acid and cement by using gypsum |
| CN101830442B (en) * | 2010-04-27 | 2011-07-27 | 重庆三圣特种建材股份有限公司 | Process for co-producing sulphuric acid and cement by using gypsum |
| CN101863500A (en) * | 2010-06-04 | 2010-10-20 | 中南大学 | A method for producing alumina from aluminum-containing metallurgical materials |
| WO2011150584A1 (en) * | 2010-06-04 | 2011-12-08 | 中南大学 | Method for producing alumina from metallurgical material containing aluminium |
| CN101863500B (en) * | 2010-06-04 | 2012-11-14 | 中南大学 | Method for producing alumina with aluminum-containing metallurgical material |
| WO2012003619A1 (en) * | 2010-07-05 | 2012-01-12 | Yin Xiaolin | Process for directly producing sulfur trioxide and sulfuric acid using gypsum as raw material |
| CN103304170A (en) * | 2013-06-28 | 2013-09-18 | 重庆大学 | Method for producing sulphate aluminum cement |
| CN109279582A (en) * | 2018-10-23 | 2019-01-29 | 山东汇泰再生资源有限公司 | A kind of ardealite acid preparation method using electrolytic aluminium waste cathode carbon block |
| CN109279582B (en) * | 2018-10-23 | 2019-05-24 | 山东汇泰再生资源有限公司 | A kind of ardealite acid preparation method using electrolytic aluminium waste cathode carbon block |
| CN112209692A (en) * | 2020-09-16 | 2021-01-12 | 贵州正和天筑科技有限公司 | Phosphogypsum anti-cracking plastering mortar and preparation method thereof |
| CN115432670A (en) * | 2021-06-01 | 2022-12-06 | 昆明理工大学 | Method and device for preparing sulfuric acid and co-producing cement clinker by oxygen-enriched calcination of phosphogypsum |
| CN115650611A (en) * | 2022-10-05 | 2023-01-31 | 湖北三宁化工股份有限公司 | Method for preparing cement clinker heat source by using carbon-sulfur mixed calcination as phosphogypsum |
| CN115650611B (en) * | 2022-10-05 | 2024-02-13 | 湖北三宁化工股份有限公司 | Method for preparing cement clinker heat source by taking carbon-sulfur mixed calcination as phosphogypsum |
| CN116282983A (en) * | 2023-02-21 | 2023-06-23 | 江苏安达环保科技有限公司 | Production method for co-production of sulfuric acid and cement by gypsum |
| CN117902584A (en) * | 2023-12-11 | 2024-04-19 | 宜都兴发化工有限公司 | Preparation of silicon-calcium aggregate, sulfuric acid and CO by phosphogypsum oxygen-enriched pyrolysis2Method and apparatus of (a) |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101306803A (en) | Process for producing sulfate acid from gypsum | |
| CN101343047B (en) | Improved preparation technique for preparing sulphuric acid and cement with gypsum | |
| CN107056102B (en) | System and method for producing sulphoaluminate cement and co-producing sulfur by utilizing desulfurized gypsum and aluminum ash | |
| CN110498622A (en) | A kind of method of the outer decomposing and calcining calcium oxide of powder multistage suspension preheating kiln | |
| CN103011090B (en) | Method for producing sulfur by using pyrolysis-reducing united technique | |
| CN102502524B (en) | Method for producing sulfur dioxide from calcium sulfate and sulfur | |
| CN101955166B (en) | Method for decomposing semi-hydrated phosphogypsum | |
| CN101244811B (en) | Method for improving SO2 concentration in acid making technique with decomposition of calcium sulphate | |
| CN105152141B (en) | A kind of gypsum relieving haperacidity thermal technology and device | |
| CN102020251B (en) | Improved production process for preparing sulfuric acid and cement from gypsum | |
| CN102127634B (en) | Molybdenite concentrate suspended-state roasting process and equipment | |
| JP2023530366A (en) | Quicklime production process and system with reduced carbon emissions | |
| CN111574080B (en) | Method for preparing belite sulphoaluminate cement and co-producing sulfuric acid by reducing gypsum with sulfur gas | |
| CN111517680B (en) | A kind of method for preparing Belite sulfoaluminate cement co-producing sulfuric acid | |
| CN109775666B (en) | Device and method for preparing sulfur by coal gasification in cooperation with calcium sulfate calcination and carbon thermal reduction | |
| CN1040009A (en) | A kind of by gypsum production vitriolic method | |
| CN114409290B (en) | Device and method for heating and modifying desulfurized ash based on blast furnace gas | |
| CN100522860C (en) | Method for producing cement and vitriol from desulfurized gesso of flue gas | |
| CN111574079B (en) | Method for co-producing sulfuric acid by co-reducing gypsum with gas sulfur and high-sulfur bauxite to produce sulfoaluminate cement | |
| CN115259102B (en) | Process and equipment for preparing sulfur dioxide concentrated flue gas and silicate clinker by flue gas diversion | |
| CN101941806A (en) | Method for utilizing composite reducing agent to decompose phosphogypsum | |
| CN205023854U (en) | Gypsum relieving haperacidity thermal technology device | |
| CN206692569U (en) | A kind of system using desulfurated plaster and aluminium ash production sulphate aluminium cement coproduction sulphur | |
| CN1330599C (en) | Method for producing sulfuric acid associated with high Belite cement through anhydrite | |
| CN102808080A (en) | Method for increasing waste gas circulation sintering utilization coefficient and sintered ore barrate strength |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20081119 |