CN102020251B - Improved production process for preparing sulfuric acid and cement from gypsum - Google Patents
Improved production process for preparing sulfuric acid and cement from gypsum Download PDFInfo
- Publication number
- CN102020251B CN102020251B CN2010105366232A CN201010536623A CN102020251B CN 102020251 B CN102020251 B CN 102020251B CN 2010105366232 A CN2010105366232 A CN 2010105366232A CN 201010536623 A CN201010536623 A CN 201010536623A CN 102020251 B CN102020251 B CN 102020251B
- Authority
- CN
- China
- Prior art keywords
- sulfuric acid
- gypsum
- cement
- raw material
- production technique
- 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.)
- Active
Links
Images
Landscapes
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention relates to an improved production process for preparing sulfuric acid and cement from gypsum. Raw materials comprise dihydrate gypsum, clay and a reducing agent. The process comprises the following steps of: drying the raw materials; independently grinding; mechanically stirring and homogenizing; preheating green stock; decomposing and calcining through a rotary kiln; acid-washing and purifying kiln gas; drying through SO2; performing a double-conversion double-absorption process; and grinding the cement to prepare sulfuric acid and cement products, wherein a dihydrate gypsum process is adopted; the raw materials are dried by absolute dry tail gas at the temperature of between 70 and 85 DEG C which is discharged out of a sulfuric acid absorption device to obtain the dihydrate gypsum with free water content of less than 5 weight percent; and the dihydrate gypsum is then directly homogenized with the clay and the reducing agent in the presence of CaCl2 or Na2SO4 to produce the green stock. In the process, the heat consumption is reduced by 30 percent, the power consumption is reduced by 20 percent, the investment is reduced by 25 to 40 percent, and the cost is reduced by 25 to 30 percent. The process overcomes the disadvantages of high power consumption and heat consumption, large investment, low operation ratio and the like in the conventional method, 0.4 to 0.5 tonnage of steam serving as a byproduct is produced by every tonnage of sulfuric acid, and the process has obvious economic benefit.
Description
Technical field
The present invention relates to gypsum and produce the technology of sulfuric acid and cement, belong to production technology and the comprehensive utilization of industry by-product gypsum residue resource and the enviromental protection and improvement field of sulfuric acid, cement industry.
Background technology
The research of gypsum system sulfuric acid and cement technology started from for 20 beginnings of the century.1916, the Miu Le of Germany and wealthy receiving (Muller Kuhne) exploitation plaster of paris system sulfuric acid and cement technology were obtained success, and have set up pilot plant; Thereafter, it is raw material production sulfuric acid and cement plant that Britain, Germany, Poland, Austria, South Africa etc. have been built up with the plaster of paris, anhydrite and phosphogypsum in succession, and puts into production, and its average productive capacity is for producing each 160 tons of sulfuric acid and cement daily.Because investment is big, hear rate is high, operation factor is low, deficiency in economic performance, external production equipment successively stopped production in the seventies in last century.
The present industrial gypsum annual emissions of China surpasses 7,000 ten thousand tons, and increases year by year.Owing to contain objectionable impurities in the industry by-product gypsum, discharging can cause serious environmental to pollute arbitrarily; The stockyard is set, and not only occupation of land is many, investment is big, the slag expense is high, and the geologic condition in stockyard is required height, and long-term accumulation can cause surface water and phreatic pollution.
China is summing up on the technological both at home and abroad basis; Obtain the success that utilizes salt gypsum, phosphogypsum, the plaster of paris, desulfurated plaster system sulfuric acid and cement; And build 8 in last century Mo and overlap production equipments; The maximum scale that reaches 300,000 tons of cement of annual output 200000 tons of producing sulfuric acid and jointlies of phosphogypsum system becomes advanced, the largest device of world's gypsum relieving haperacidity technology.Investment is high, hear rate is big, power consumption is big, the shortcoming of deficiency in economic performance, so the stopping production that has but each device all exists.For example application number is 200810139276.2, and name is called a kind of gypsum produces in the patented claim of improvement production technique of sulfuric acid and cement and use the semi-hydrated gypsum production technique, owing to raw material is that the hyperthermia drying that dihydrate gypsum need be heated to more than 160 ℃ just can obtain semi-hydrated gypsum; The complicacy that hear rate is very big, device also compares, and rotary kiln ring formation very easily when adopting this technology, operation factor is low; Investment is high; Hear rate is big, and power consumption is big, deficiency in economic performance.
Summary of the invention
Technical problem to be solved by this invention is to overcome that the hear rate that above-mentioned technology exists is big, the defective of deficiency in economic performance; A kind of gypsum system sulfuric acid and cement industry are provided, have raw material and draw materials extensively, energy consumption is low; Less investment, high efficiency, the advantage of no waste water, waste sludge discharge.
Technical scheme of the present invention is: the improvement production technique of a kind of gypsum system sulfuric acid and cement; Raw material comprises dihydrate gypsum, clay and reductive agent, through raw material stoving, independent grinding, mechanical stirring homogenizing, raw material preheating, rotary kiln decomposing and calcining, kiln gas acid-scrubbing cleaning, SO
2Drying, double conversion and double absorption technology, the cement process of grinding make sulfuric acid and cement products; Adopt dihydrate gypsum technology; Raw material stoving is to adopt the dihydrate gypsum that is obtained free water content＜5%wt by 70～85 ℃ that come out in the sulfuric acid absorption device over dry tail gas drying material, and then with clay and reductive agent at CaCl
2Or Na
2SO
4Existence under direct homogenizing be raw material.
Described CaCl
2Or Na
2SO
4Add-on account for 0.5～3% of raw material gross weight.
Described reductive agent is any one in the coke, refinery coke, hard coal of sulphur or C >=60%wt, odor component Vad＜6%wt.
Described mechanical stirring homogenizing adopts bottom mechanical to stir the homogenizing storehouse
Preheating adopts 2～5 grades of compound preheating rotary kilns to carry out preheating.
Said gypsum is the industry by-product gypsum waste residue or the plaster of paris, SO
3>=32%wt, CaO>=29%wt, SiO
2≤8.0%wt, P
2O
5＜2%wt, F＜0.35%wt.
Adopt the low-temperature heat recovery technology during described double conversion and double absorption; The sulfuric acid absorption device divides two sections absorptions; The bottom is 200～240 ℃ a high temperature absorber portion, and top is 85～110 ℃ low temperature absorption section, establishes vapour generator in the high temperature sulfuric acid exit of high temperature absorber portion; Produce steam and be used for power generation and heat supply, but sulfuric acid producing steam 0.4-0.5 ton per ton.
Beneficial effect:
1, two water conservancy project process flows are adopted in the gypsum oven dry, and drying plant adopts the pneumatic floating dryer, and 70～85 ℃ the over dry tail gas that thermal source adopts the sulfuric acid absorption device to come out can remove the free-water in the dihydrate gypsum.More traditional half water conservancy project process flow equipment volume is little, reduce investment outlay, throughput is big, practices thrift the power consumption of 30% overall heat consumption and 20%.The employing dihydrate gypsum is a raw material, and the good stability of dihydrate gypsum does not lump, as long as free-water contained in the raw material is dried＜5%, need not be heated to high temperature more than 160 ℃ as half water conservancy project skill.Because sulfuric acid per ton is discharged 3.2～3.6 tons 70～85 ℃ over dry tail gas, consume 1.5 tons of dihydrate gypsums, amount to and contain 1.8 tons in free-water 20% gypsum, should remove 0.22 ton of moisture content like oven dry when containing free-water 5%.It is feasible removing 0.22 ton of free-water with 3.2～3.6 tons 70～85 ℃ over dry tail gas in the airflow dryer baking.
2. the raw material preparation adopts bottom mechanical to stir discharging steel cylinder homogenizing storehouse, and gypsum need not grinding can all change into qualified raw material with auxiliary material, has reduced by 30% power consumption and investment.
3. adopt 2～5 grades of compound preheating kilns to decompose gypsum raw material new technology, compare with traditional kiln, system's hear rate reduces by 30%, increases throughput, economy system investment, uses the dihydrate gypsum raw material.
4. general semi-hydrated gypsum technology raw material decomposition temperature reaches 800～1200 ℃, at the gypsum entering clinkering zone that branch ungirds and do not decompose fully, branch is ungirded and the clinkering zone coincidence, is prone to cause rotary kiln at the clinkering zone ring formation because of the gypsum fusing point is low, and operation factor is low.Raw material add the CaCl of 0.5-3%
2Or Na
2SO
4Reduce by 100～150 ℃ of gypsum decomposition temperatures, raising decomposition rate 20～30% ungirds branch and clinkering zone separates, and ungirding at branch gets into clinkering zone after gypsum decomposes fully, prevents ring formation of rotary kiln, improves running period.
5. sulfuric acid is done and is inhaled operation employing low temperature recovery technology; The sulfuric acid absorption device divides two sections absorptions, goes out tower acid temperature bottom and be 200～230 ℃ high temperature absorber portion, and top is 80～110 ℃ low temperature absorption section; Vapour generator is established in sulfuric acid outlet at the high temperature absorber portion; But compare 0.4～0.5 ton of common sulfuric acid absorption tower sulfuric acid producing steam per ton, outwards provide heat energy also can generate electricity, increase economic efficiency.
6. utilize the present invention to reduce by 25～40% with adopt the traditional method investment with scale producer; Hear rate reduces by 30%; Power consumption reduces by 20%.Cost reduces by 25～30%.
Description of drawings
Fig. 1 is gypsum system producing sulfuric acid and jointly cement industry schema.
Fig. 2 is that each equipment of the present invention connects synoptic diagram.
Wherein, 1 is the auxiliary material drying unit, and 2 is material separator, and 3 is blower fan, and 4 is the raw material stoving device; 5 is the raw material preheating unit, and 6 is the purge drying device, and 7 is conversion system, and 8 is the sulfuric acid absorption device; 9 is rotary kiln, and 10 for cement grinds device, and 11 is mechanical stirring homogenizing storehouse, 12 auxiliary material separators.
Fig. 3 is a sulfuric acid absorption apparatus structure synoptic diagram.
Wherein, 8-1 is SO
3Import, 8-2 is the outlet of high temperature sulfuric acid, and 8-3 is the import of high temperature sulfuric acid, and 8-4 is the outlet of low temperature sulfuric acid, and 8-5 is the import of low temperature sulfuric acid, and 8-6 is the tail gas outlet, and 8-7 is a scum dredger, and 8-8 is a filler, 8-9 is an acid proof lining.
Embodiment
As illustrated in fig. 1 and 2; By low temperature over dry tail gas the free-water in the dihydrate gypsum is dried in the common incoming stock drying unit 4 of 70～85 ℃ the low temperature over dry tail gas that contains the industrial by-product dihydrate gypsum of free-water and come out by sulfuric acid absorption device 8; The dihydrate gypsum that obtains free-water＜5%wt uses as raw material; Must grinding, as free-water is little then directly dries to free-water＜5% and grinding powdering with the oven dry mill because of containing with the plaster of paris.Raw material stoving device 4 can be selected the pneumatic floating dryer.Dried dihydrate gypsum is separated in the mechanical stirring homogenizing storehouse 11 through material separator 2, and waste gas is through blower fan 3 emptyings.Clay and reductive agent join in the auxiliary material drying unit 1, and thermal source adopts burn till waste heat or the contact of hot flue gas of coming out of rotary kiln 9 to carry out surface radiating and dry to moisture content≤10%wt.Perhaps adopt fluidizing furnace to provide thermal source also passable, fluidizing furnace is fuel with the coal, and the lime-ash of discharge can be as the additive of cement.Clay, reductive agent are dried grinding after 12 separation of auxiliary material separator also get in the mechanical stirring homogenizing storehouse 11.Mechanical stirring homogenizing storehouse 11 preferably adopts bottom mechanical to stir the homogenizing form.Waste gas is through blower fan 3 emptyings.Dihydrate gypsum with oven dry is that main raw material, clay, reductive agent are auxiliary material, CaCl
2Or Na
2SO
4For stirring in the homogenizing storehouse 11 in bottom mechanical, additive is mixed with raw material.The raw material that mechanical stirring homogenizing storehouse 11 prepares get into decomposing and calcining in the rotary kiln 9 after joining the high-temperature tail gas preheating that raw material preheating unit 5 and rotary kiln 9 come out and sloughing crystal water, burn the grog that and blended material and get into cement together and grind in the device 10 and manufacture cement products.Raw material preheating unit 5 can adopt the multistage composite preheater kiln to carry out preheating.The crystal water of gypsum removes in preheater with the free-water that contains and heats in the raw material, gets into rotary kiln 9 decomposing and calcining, and under the effect of additive, raw material decomposite SO fully at 700～1050 ℃
2, solid phase becomes cement clinker 1200～1450 ℃ of calcinings, grinds into cement.Contain 10～14.5%SO
2Gas phase adopt acid-scrubbing cleaning, double conversion and double absorption, low level waste heat recovery to process sulfuric acid.That decomposes contains SO
2Gas gets in the purge drying device 6 after raw material preheating unit 5 and raw material heat exchange are lowered the temperature and gets in the conversion system 7 SO after the cooling dedusting
2Change into SO
3Get into then in the sulfuric acid absorption device 8 with purge drying device 6 in the diluted acid that produces manufacture sulfuric acid product, the reaction liberated heat is a byproduct steam, the byproduct steam power generation and heat supply.
This invention is practiced thrift hear rate 30% than other method, practices thrift power consumption 20%, practices thrift investment 25～40%, and cost reduces by 25～30%, prevents ring formation of rotary kiln, improves operation factor, no waste water, waste sludge discharge, remarkable in economical benefits.This wherein main improvement is exactly that raw material has adopted dihydrate gypsum directly to be mixed with raw material, and required bake out temperature just can be accomplished by 70～85 ℃ the over dry tail gas that sulfuric acid absorption device 8 comes out, and other processes are conventional production process.
Describe more specifically below:
1, raw material
(1) gypsum
With CaSO
4Be the natural or industry by-product gypsum of staple, comprise salt gypsum, phosphogypsum, the plaster of paris, desulfurated plaster, titanium gypsum, fluorgypsum, lemon gypsum etc., all can be used as the main raw material of producing sulfuric acid and cement clinker.Require SO
3>=32%wt, CaO>=29%wt, SiO
2≤8.0%wt, P
2O
5＜2%wt, F＜0.35%wt.
(2) reductive agent
In decomposition course, be CaSO
4The reductive agent that decomposes.With coke, refinery coke, hard coal etc. all can, require C >=60%wt, odor component Vad＜6%wt.Also tail gas SO can be substituted with industrial sulphur
2Concentration also can improve.
(3) clay
Be used for replenishing SiO
2Form required composition in grog, require SiO
2>=60%wt.
2, raw material stoving
(1) two water determination of technological
Conventional production methods all adopts half water conservancy project skill, and the present invention adopts two water conservancy projects skill, dihydrate gypsum good stability; Do not lump, the oven dry hear rate is low, and the use thermal source is a system vitriolic over dry tail gas; Save the hear rate that is heated to the hyperthermia drying more than 160 ℃, and reduce investment.Therefore the present invention confirms to adopt two water conservancy project process flows.
(2) oven dry process description
The gypsum oven dry is carried out in raw material stoving device 4, can select to adopt the pneumatic floating dryer to dry.Gypsum contacts with 70～85 ℃ over dry tail gas from sulfuric acid absorption device 8 in dryer, makes free water evaporates, obtains containing the dihydrate gypsum of free-water＜5%wt.
Subsidiary material such as reductive agent, clay advance in the auxiliary material drying unit 1, contact and dry to moisture≤10%wt with burn till waste heat or the hot flue gas that rotary kiln 9 comes out.The auxiliary material drying unit also can adopt fluidizing furnace that thermal source is provided, and fluidizing furnace is fuel with the coal, and the lime-ash of discharge is as the additive of cement.
3, raw material preparation
Microcomputerized dosing, on-line analysis are adopted in the raw material preparation.Subsidiary material such as reductive agent after metering, clay are after grinding tails over below the 10%wt to fineness requirement 0.08mm square hole sieve together; In the dihydrate gypsum through metering gets into the mechanical stirring homogenizing storehouse 11 of steel cylinder system that bottom band stirs discharging, become after the homogenizing and be used for the raw material of decomposing and calcining, add 0.5～3% CaCl simultaneously preparing burden
2Or Na
2SO
4Industry by-product gypsum reaches requirement without grinding fineness, and is little then with oven dry abrasive dust mill because of free water content when using the plaster of paris.
Raw material require:
(1) lime saturation factor
KH＝(CaO-1.18P
2O
5-0.35Fe
2O
3-1.65Al
2O
3)/2.8SiO
2＝1.0±0.1
(2) silica modulus
n＝SiO
2/(Al
2O
3+Fe
2O
3)＝3.7±0.5
(3) iron rate (or aluminium rate)
P＝Al
2O
3/Fe
2O
3＝2.5±0.3
(4) C/SO
3(mol ratio)=0.70～0.80
(5) mean particle size＜60 μ m.
4, preheating, decomposition, calcining
The key equipment of gypsum system producing sulfuric acid and jointly cement is preheating, decomposition, roasting assembly.The mutual combination of novel process such as raw material preheating unit 5 can adopt that the compound or cyclone preheater of 2-5 level is generally preferable with 3 grades of preheaters, three or four air channel coal rifles and electrostatic precipitator and equipment combines with rotary kiln again; More help the calcining of gypsum dehydration, raw material, can guarantee SO in the kiln gas that rotary kiln 9 produced
2Concentration is 10～14.5%.As burn till with coal and adopt high sulphur coal, not only can reduce cost, also help and improve kiln gas SO
2Concentration.
Raw material after the homogenizing are gone in the inlet pipe of first step cyclone preheater of preheating unit 5 after metering; After the spreading plate disperses, be carried to and carry out gas solid separation in the first step preheater by hot gas flow; Gas is discharged, after the dust precipitator dedusting, is got into sulfate system through induced draft fan by air outlet tube; Solid then gets in the inlet pipe of second stage preheater, after the spreading plate disperses, is carried in the preheater of the second stage by hot gas flow.Like this, material passes through preheaters at different levels successively, after after the final stage preheater is preheating to 550～750 ℃, get in the rotary kiln 9 decompose, calcining.
The decomposition reaction formula is:
2CaSO
4+ C------→ 2CaO+2SO
2↑+CO
2↑ (at CaCl
2Or Na
2SO
4Act on the completion that ungirds in following minute)
CaO that generates and the SiO in the material
2, Al
2O
3, Fe
2O
3Deng getting into clinkering zone, the mineralising reaction takes place, form cement clinker, the calcination reaction formula is:
12CaO+2SiO
2+2Al
2O
3+Fe
2O
3→3CaO·SiO
2+2CaO·SiO
2+3CaO·Al
2O
3+4CaO·Al
2O
3·Fe
2O
3
Cement clinker send cement clinker library after cooler cooling, generation contain SO
2Be that 10～14.5% kiln gas gets into the final stage preheater from kiln tail (700～900 ℃); Behind the intermediary preheater, arrive the raw material counter current contact of first step cyclone preheater and adding successively; After carrying out heat exchange; Discharge (220～280 ℃) from first step cyclone preheater, send into sulfate system through dust precipitator by hot induced draft fan.
Each oxide compound is not to exist with independent state in the cement clinker, but exists with the synthetic compound (common name mineral) of two or more oxide junction.Therefore, the ratio in cement production process between each oxide compound of control, more even more important than the content of controlled oxidation thing, the performance that more can express cement reaches incinerating is influenced.The cement clinker controlling index requires as follows:
1. lime saturation factor
KH＝(CaO-0.35Fe
2O
3-1.65Al
2O
3-0.70SO3-0.78CaS-fCaO-1.18P
2O
5)/2.8SiO
2
＝0.84±0.5
2. silica modulus
n＝SiO
2/(Al
2O
3+Fe
2O
3)＝3.4±0.4
3. iron rate (or aluminium rate)
P＝Al
2O
3/Fe
2O
3＝2.0±0.3
④CaS＜2％、SO
3＜2％、fCaO＜2％、MgO＜2％。
SO
2Gas and cement clinker all generate in rotary kiln 9.Should make SO
2The kiln gas that content is high makes the grog that meets the cement requirement again.Except the proportioning of strictness control raw material, also must strict control kiln atmosphere.When in kiln, being reducing atmosphere, be prone to form elemental sulfur and CaS, elemental sulfur can stop up sulphuric acid device.When being oxidizing atmosphere, CaSO
4Decompose not exclusively, eutectic occurs, rotary kiln is prone to the ring formation phenomenon.So the long-pending content of the general oxysome of kiln atmosphere is controlled at 0.4～1.5%, CO≤0.5%.
5, sulfuric acid is produced
Main processes that sulfuric acid is produced and application number are 200810139276.2, and name is called a kind of gypsum, and to produce the method that is adopted in the patented claim of improvement production technique of sulfuric acid and cement consistent.
In this operation, the present invention is 200810139276.2 for application number mainly, and name is called the sulfuric acid absorption operation that a kind of gypsum produces in the patented claim of improvement production technique of sulfuric acid and cement and improves.Described sulfuric acid absorption device 8 is divided into three parts by ball collar up and down, and middle part and bottom are 200～240 ℃ high temperature absorber portions, and top is 85～110 ℃ low temperature absorption section, is provided with SO in the bottom
3Import 8-1 and high temperature sulfuric acid outlet 8-2; Be provided with high temperature sulfuric acid import 8-3 at the middle part near the place of low temperature absorption section, be provided with low temperature sulfuric acid import 8-5 at the top of low temperature absorption section, be provided with low temperature sulfuric acid outlet 8-4 in the bottom of low temperature absorption section and be provided with scum dredger 8-7 at the top of sulfuric acid absorption device; On scum dredger, be provided with tail gas outlet 8-6; Be filled with acid resistance filler 8-8 in low temperature absorption section and high temperature absorber portion, the shell of said sulfuric acid absorption device 8 is a round shape, liner acid proof lining 8-9.Described high temperature sulfuric acid outlet 8-2 place is provided with vapour generator.
By the SO that contains that transforms workshop section
3The reforming gas first time get into and to divide two sections absorptions in the sulfuric acid absorption device 8, the bottom is that high temperature absorbs, top is low temperature absorption, all use the sulfuric acid circulated sprinkling absorption of 98%wt concentration, makes sulfuric acid.By shown in Figure 3, contain SO
3Gas is through SO
3Import 8-1 gets into sulfuric acid absorption device 8 and contacts the higher sulfuric acid of the generation denseer temperature of concentration with the sulfuric acid that gets into from high temperature sulfuric acid import 8-3; Sulfuric acid gets into vapour generator generation byproduct steam from high temperature sulfuric acid outlet 8-2 and lowers the temperature simultaneously after pump is squeezed into high temperature sulfuric acid import 8-3; Gas after the absorption gets into the top of sulfuric acid absorption device 8, contacts and absorbs into sulfuric acid again with low temperature sulfuric acid import 8-5, low temperature sulfuric acid outlet 8-4.Contain SO
3Gas absorbs SO through two sections
3After removing the disacidify foam, scum dredger 8-7 discharges from tail gas outlet 8-6.Place two-layer acid resistance filler 8-8 in the sulfuric acid absorption device 8 and supported by ball collar, shell rolls with steel plate, liner acid proof lining 8-9.
Further illustrate below in conjunction with specific embodiment.In following examples, 70～85 ℃ the over dry tail gas that the sulfuric acid absorption tower that two used water base gypsum all are to use comes out is dried, and obtains the dihydrate gypsum of free water content＜5%wt, then with clay and reductive agent and CaCl
2Or Na
2SO
4Being mixed together homogenizing is raw material.
Embodiment 1 (doing raw material) with phosphogypsum:
1, the composition of main raw material phosphogypsum, clay, coke, coal is following:
(1) phosphogypsum (two is water base) main chemical compositions
| Phosphogypsum | LOSS | SiO 2 | Fe 2O 3 | Al 2O 3 | CaO | MgO | SO 3 | P 2O 5 | F - | ∑ |
| Wt，％ | 19.03 | 4.41 | 0.31 | 0.26 | 30.23 | 0.34 | 43.20 | 0.62 | 0.17 | 98.57 |
(2) clay main chemical compositions
| Clay | LOSS | SiO 2 | Fe 2O 3 | Al 2O 3 | CaO | MgO | ∑ |
| Wt，％ | 9.09 | 63.18 | 4.05 | 12.38 | 6.49 | 2.07 | 97.26 |
[0082](3) hard coal technical analysis, ash content analysis
(4) burn till with proximate analysis of coal, ash content analysis
2, the proportioning of raw material, staple and rate value
(1) proportioning of raw material is controlled to be: phosphogypsum 87.5%; Clay 7.0%; Hard coal 5.5%.
(2) the raw material main chemical compositions that generates
| Raw material | LOSS | SiO 2 | Fe 2O 3 | Al 2O 3 | CaO | C | SO 3 | P 2O 5 | F - | ∑ |
| Wt，％ | 17.28 | 8.68 | 0.60 | 1.50 | 26.84 | 4.27 | 37.58 | 0.56 | 0.15 | 97.75 |
(3) the rate value of raw material is: KH (lime saturation factor)=1.00; N (silica modulus)=4.13; P (iron rate)=2.50.
(4) fixed carbon C is 4.27%; C/SO
3(mol ratio) is 0.75.
3, the main operation index of cement rotary kiln
4, the staple of grog, rate value, mineral composition
The main chemical compositions of the grog that (1) generates
| Grog | LOSS | SiO 2 | Fe 2O 3 | Al 2O 3 | CaO | SO 3 | P 2O 5 | F - | ∑ |
| Wt，％ | -0.40 | 21.82 | 1.96 | 3.95 | 65.48 | 0.81 | 1.81 | 0.28 | 95.71 |
(2) the rate value of grog is: KH (lime saturation factor)=0.86; N (silica modulus)=3.69; P (iron rate)=2.0.
(3) mineral composition of grog: CaS is 1.08%; FCaO is 0.92%; C
3S is 45.64%; C
2S is 29.06%; C
3A is 7.81%; C
4AF is 6.01%.
5, the main operation index of sulfuric acid apparatus
6, cement grinds the proportioning of blended material and gypsum: the blended material addition content is 15%; Gypsum (two is water base) addition content is 3%.
7, quality product
(1) sulfuric acid quality: concentration 92.62; Ignition residue 0.049%.(2) cement reaches GB ordinary Portland cement standard.
8, main consumption indicators
Embodiment 2 (doing raw material) with desulfurated plaster:
1, the composition of main raw material desulfurated plaster, clay, coke, coal is following:
(1) desulfurated plaster (two is water base) main chemical compositions
| Phosphogypsum | LOSS | SiO 2 | Fe 2O 3 | Al 2O 3 | CaO | MgO | SO 3 | ∑ |
| Wt，％ | 18.22 | 0.85 | 0.23 | 0.29 | 32.02 | 1.15 | 45.36 | 98.12 |
(2) clay main chemical compositions
| Clay | LOSS | SiO 2 | Fe 2O 3 | Al 2O 3 | CaO | MgO | ∑ |
| Wt，％ | 7.00 | 71.11 | 3.10 | 10.06 | 5.38 | 1.55 | 98.20 |
(3) proximate analysis of coke, ash content analysis
(4) burn till with proximate analysis of coal, ash content analysis
2, the proportioning of raw material, staple and rate value
(1) proportioning of raw material is controlled to be: desulfurated plaster 84%; Clay 10.%; Coke 6.0%.
(2) the raw material main chemical compositions that generates
(3) the rate value of raw material is: KH (lime saturation factor)=1.01; N (silica modulus)=3.20; P (iron rate)=2.56.
(4) fixed carbon C is 4.47%; C/SO
3(mol ratio) is 0.78.
3, the main operation index of cement rotary kiln
4, the staple of grog, rate value, mineral composition
The main chemical compositions of the grog that (1) generates
| Grog | LOSS | SiO 2 | Fe 2O 3 | Al 2O 3 | CaO | MgO | SO 3 | ∑ |
| Wt.％ | -0.69 | 22.11 | 1.97 | 4.18 | 65.78 | 2.23 | 1.27 | 96.74 |
(2) the rate value of grog is: KH (lime saturation factor)=0.86; N (silica modulus)=3.59; P (iron rate)=2.12.
(3) mineral composition of grog: CaS is 1.86%; FCaO is 1.60%; C
3S is 45.76%; C
2S is 28.03%; C
3A is 7.49%; C
4AF is 6.19%.
5, the main operation index of sulfuric acid apparatus
6, cement grinds the proportioning of blended material and gypsum: the blended material addition content is 15%; Gypsum (two is water base) addition content is 3%.
7, quality product
(1) sulfuric acid quality: concentration 92.68; Ignition residue 0.048%.
(2) go out to grind cement quality and meet GB ordinary Portland cement standard.
8, main consumption indicators
Claims (7)
1. the improvement production technique of gypsum system sulfuric acid and cement, raw material comprises dihydrate gypsum, clay and reductive agent, through raw material stoving, independent grinding, mechanical stirring homogenizing, raw material preheating, rotary kiln decomposing and calcining, kiln gas acid-scrubbing cleaning, SO
2Drying, double conversion and double absorption technology, the cement process of grinding make sulfuric acid and cement products; It is characterized in that; Adopt dihydrate gypsum technology; Raw material stoving is to adopt the dihydrate gypsum that is obtained free water content＜5wt% by 70～85 ℃ that come out in the sulfuric acid absorption device (8) over dry tail gas drying material, and then with clay and reductive agent at CaCl
2Or Na
2SO
4Existence under direct homogenizing be raw material.
2. the improvement production technique of gypsum system sulfuric acid and cement according to claim 1 is characterized in that described CaCl
2Or Na
2SO
4Add-on account for 0.5～3% of raw material gross weight.
3. the improvement production technique of gypsum system sulfuric acid and cement according to claim 1 is characterized in that, described reductive agent is any one in the coke, refinery coke, hard coal of sulphur or C >=60wt%, odor component Vad＜6wt%.
4. the improvement production technique of gypsum system sulfuric acid and cement according to claim 1 is characterized in that, described mechanical stirring homogenizing adopts bottom mechanical to stir the homogenizing storehouse.
5. the improvement production technique of gypsum system sulfuric acid and cement according to claim 1 is characterized in that, preheating adopts 2～5 grades of compound preheating rotary kilns to carry out preheating.
6. the improvement production technique of gypsum system sulfuric acid and cement according to claim 1 is characterized in that said gypsum is the industry by-product gypsum waste residue or the plaster of paris, SO
3>=32wt%, CaO>=29wt%, SiO
2≤8.0wt%, P
2O
5＜2wt%, F＜0.35wt%.
7. the improvement production technique of gypsum system sulfuric acid and cement according to claim 1; It is characterized in that; Adopt the low-temperature heat recovery technology during described double conversion and double absorption, sulfuric acid absorption device (8) divides two sections absorptions, and the bottom is 200～240 ℃ a high temperature absorber portion; Top is 85～110 ℃ low temperature absorption section, establishes vapour generator in the high temperature sulfuric acid exit of high temperature absorber portion.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105366232A CN102020251B (en) | 2010-11-08 | 2010-11-08 | Improved production process for preparing sulfuric acid and cement from gypsum |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105366232A CN102020251B (en) | 2010-11-08 | 2010-11-08 | Improved production process for preparing sulfuric acid and cement from gypsum |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102020251A CN102020251A (en) | 2011-04-20 |
| CN102020251B true CN102020251B (en) | 2012-07-04 |
Family
ID=43862082
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010105366232A Active CN102020251B (en) | 2010-11-08 | 2010-11-08 | Improved production process for preparing sulfuric acid and cement from gypsum |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102020251B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102502524B (en) * | 2011-10-28 | 2014-05-07 | 云南云天化国际化工股份有限公司 | Method for producing sulfur dioxide from calcium sulfate and sulfur |
| CN102530884A (en) * | 2011-12-19 | 2012-07-04 | 刘立文 | Method for preparing sulfuric acid and cement with fluorine gypsum |
| CN102863061B (en) * | 2012-09-24 | 2013-10-23 | 长沙理工大学 | Device and method for dry and energy-saving production of polyaluminum chloride water purifying agent |
| CN103058150B (en) * | 2012-12-12 | 2015-03-11 | 刘立文 | Producing method of sulfuric acid by using calcium sulfate under high temperature and high pressure |
| CN103241717B (en) * | 2013-04-28 | 2015-06-24 | 天津水泥工业设计研究院有限公司 | Drying and calcining process and device for coproduction of sulfuric acid and cement from gypsum |
| CN104129761A (en) * | 2014-08-20 | 2014-11-05 | 攀枝花圣地元科技有限责任公司 | Method for applying absolute dry gas in sulfuric acid process to drying of minerals |
| CN115073027A (en) * | 2022-07-26 | 2022-09-20 | 武汉德毅天材科技开发有限公司 | Method and device for preparing sulfuric acid and co-producing cement clinker from industrial byproduct gypsum |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4608238A (en) * | 1984-07-27 | 1986-08-26 | Wilson Sr Eddie K | Process for treating phospho-gypsum waste product from wet-acid process of making phosphoric acid |
| CN101343047A (en) * | 2008-08-26 | 2009-01-14 | 山东鲁北企业集团总公司 | Improved preparation technique for preparing sulphuric acid and cement with gypsum |
| CN101844879A (en) * | 2010-02-04 | 2010-09-29 | 南京创能电力科技开发有限公司 | Device for producing sulfuric acid and cement by decomposing and calcining gypsum |
-
2010
- 2010-11-08 CN CN2010105366232A patent/CN102020251B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4608238A (en) * | 1984-07-27 | 1986-08-26 | Wilson Sr Eddie K | Process for treating phospho-gypsum waste product from wet-acid process of making phosphoric acid |
| CN101343047A (en) * | 2008-08-26 | 2009-01-14 | 山东鲁北企业集团总公司 | Improved preparation technique for preparing sulphuric acid and cement with gypsum |
| CN101844879A (en) * | 2010-02-04 | 2010-09-29 | 南京创能电力科技开发有限公司 | Device for producing sulfuric acid and cement by decomposing and calcining gypsum |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102020251A (en) | 2011-04-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101343047B (en) | Improved preparation technique for preparing sulphuric acid and cement with gypsum | |
| CN102020251B (en) | Improved production process for preparing sulfuric acid and cement from gypsum | |
| CN103771734B (en) | A kind of mass-producing calcination processing utilizes the method for electrolytic manganese residues | |
| CN111559879B (en) | Method for preparing sulphoaluminate cement and co-producing sulfuric acid by reducing gypsum with sulfur gas | |
| CN102502524B (en) | Method for producing sulfur dioxide from calcium sulfate and sulfur | |
| US5049198A (en) | Calcium sulfate process for the coproduction of Portland cement clinker and concentrated sulfur dioxide adequate to manufacture sulfuric acid | |
| CN111233356B (en) | Method and system for preparing sulphoaluminate cement from all solid waste of aluminum ash pretreatment | |
| CN104555946B (en) | Method for jointly producing sulphuric acid and cement clinker by using sulphur gas to reduce gypsum | |
| US20220204403A1 (en) | Production method for producing cement and co-producing sulfuric acid from phosphogypsum | |
| CN106904849A (en) | The system and method that a kind of utilization Industrial Solid Waste produces sulphate aluminium cement co-producing sulfuric acid | |
| CN107056102A (en) | A kind of system and method for utilization desulfurated plaster and aluminium ash production sulphate aluminium cement coproduction sulphur | |
| CN101318632B (en) | Method for decomposing phosphogypsum to produce sulphuric acid and cement with suspended state | |
| CN109809456A (en) | A kind of system and method for coal gasification collaboration gypsum calcining coproduction calcium oxide and sulphur | |
| CN103964715B (en) | Energy-saving and cost-reducing gypsum produces the method for cement joint production sulfuric acid | |
| CN101955166B (en) | Method for decomposing semi-hydrated phosphogypsum | |
| CN211770962U (en) | System for preparing sulphoaluminate cement by using all solid wastes of aluminum ash pretreatment | |
| CN107056100A (en) | A kind of preparation method of clinker | |
| CN111574080B (en) | Method for preparing belite sulphoaluminate cement and co-producing sulfuric acid by reducing gypsum with sulfur gas | |
| CN100453450C (en) | Coproducing cement technological method of producing acid using phosphogypsum and sulfur | |
| CN102775082A (en) | Production method of white cement and sulfuric acid | |
| CN105152141B (en) | A kind of gypsum relieving haperacidity thermal technology and device | |
| CN103072949B (en) | Method for preparing calcium sulfide through reductive decomposition of phosphogypsum by fluidized bed | |
| CN105110666A (en) | Production method for cement clinker by utilizing waste materials from calcium carbide production | |
| CN105217581B (en) | A kind of method of chemical gypsum and carbide slag comprehensive utilization | |
| CN101239706B (en) | Method for producing calcium sulfide from calcium sulfate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |