CN100453450C - Coproducing cement technological method of producing acid using phosphogypsum and sulfur - Google Patents
Coproducing cement technological method of producing acid using phosphogypsum and sulfur Download PDFInfo
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- CN100453450C CN100453450C CNB2006100221461A CN200610022146A CN100453450C CN 100453450 C CN100453450 C CN 100453450C CN B2006100221461 A CNB2006100221461 A CN B2006100221461A CN 200610022146 A CN200610022146 A CN 200610022146A CN 100453450 C CN100453450 C CN 100453450C
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- 239000004568 cement Substances 0.000 title claims abstract description 46
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 title claims abstract description 39
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 23
- 239000002253 acid Substances 0.000 title claims abstract description 14
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 13
- 239000011593 sulfur Substances 0.000 title claims abstract description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 63
- 238000010521 absorption reaction Methods 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 16
- 238000000227 grinding Methods 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 32
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 24
- 239000005864 Sulphur Substances 0.000 claims description 21
- 239000001117 sulphuric acid Substances 0.000 claims description 19
- 235000011149 sulphuric acid Nutrition 0.000 claims description 19
- 239000000292 calcium oxide Substances 0.000 claims description 15
- 238000000746 purification Methods 0.000 claims description 14
- 239000000377 silicon dioxide Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000003245 coal Substances 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- 229910052731 fluorine Inorganic materials 0.000 claims description 8
- 230000002829 reductive effect Effects 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 235000019739 Dicalciumphosphate Nutrition 0.000 claims description 6
- 239000001506 calcium phosphate Substances 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- NEFBYIFKOOEVPA-UHFFFAOYSA-K dicalcium phosphate Chemical compound [Ca+2].[Ca+2].[O-]P([O-])([O-])=O NEFBYIFKOOEVPA-UHFFFAOYSA-K 0.000 claims description 6
- 229940038472 dicalcium phosphate Drugs 0.000 claims description 6
- 229910000390 dicalcium phosphate Inorganic materials 0.000 claims description 6
- BCAARMUWIRURQS-UHFFFAOYSA-N dicalcium;oxocalcium;silicate Chemical compound [Ca+2].[Ca+2].[Ca]=O.[O-][Si]([O-])([O-])[O-] BCAARMUWIRURQS-UHFFFAOYSA-N 0.000 claims description 6
- 235000019976 tricalcium silicate Nutrition 0.000 claims description 6
- 229910021534 tricalcium silicate Inorganic materials 0.000 claims description 6
- 239000012190 activator Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 238000010298 pulverizing process Methods 0.000 claims description 5
- 239000002002 slurry Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 18
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract description 3
- 238000010304 firing Methods 0.000 abstract description 3
- 238000004140 cleaning Methods 0.000 abstract 1
- 239000002893 slag Substances 0.000 abstract 1
- 239000002699 waste material Substances 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 63
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 13
- 229910004298 SiO 2 Inorganic materials 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000010790 dilution Methods 0.000 description 4
- 239000012895 dilution Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000002950 deficient Effects 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910004762 CaSiO Inorganic materials 0.000 description 1
- 239000011398 Portland cement Substances 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- AGWMJKGGLUJAPB-UHFFFAOYSA-N aluminum;dicalcium;iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Ca+2].[Ca+2].[Fe+3] AGWMJKGGLUJAPB-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical group [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- HOOWDPSAHIOHCC-UHFFFAOYSA-N dialuminum tricalcium oxygen(2-) Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[Al+3].[Al+3].[Ca++].[Ca++].[Ca++] HOOWDPSAHIOHCC-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000009955 starching Methods 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
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- Silicates, Zeolites, And Molecular Sieves (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The present invention relates to a process capable of simultaneously preparing acid and producing cement by combining phosphogypsum with sulfur. It is characterized by utilizing waste slag phosphogypsum obtained by wet process phosphoric acid production to prepare acid and produce cement. In the concrete, the invented process includes the following steps: utilizing low-concentration SO2 gas discharged out from rotary kiln of phosphogypsum acid-making system and making said kiln gas undergo the processes of washing, cleaning and drying, then be mixed with high-concentration SO2 gas discharged from sulfur acid-making system to obtain the SO2 gas whose concentration is 8-9%; and adopting an advanced two-stage two-absorption acid-making process to prepare sulfuric acid; at the same time firing the phosphogypsum in the rotary kiln to obtain cement clinker, grinding and blending so as to obtain cement.
Description
Technical field:
The present invention relates to a kind of phosphogypsum combines the relieving haperacidity jointly producing cement with sulphur processing method, is to utilize Wet-process Phosphoric Acid Production gained residue phosphogypsum to produce cement sulfuric acid, specifically is meant the low concentration SO of utilizing the phosphogypsum acid making system to go out rotary kiln
2Gas, this kiln gas are after washing, purification, drying, with the high density SO of sulphur-burning sulphuric acid system
2Gas mixes, and is made into concentration expressed in percentage by volume and is 8～9% SO
2Gas adopts advanced double conversion and double absorption relieving haperacidity flow process to make sulfuric acid, and phosphogypsum burns till in rotary kiln and is cement clinker simultaneously, makes cement through grinding batching.
Background technology:
The residue phosphogypsum major ingredient that Wet-process Phosphoric Acid Production produces is CaSO
4.2H
2O is mainly used at present and produces cement attached product sulfuric acid simultaneously, and domestic Shandong northern Shandong chemical industry and Sichuan Yin Shan chemical industry have all been realized industrialization, and its technological process of production is as follows: phosphogypsum reduces free P in the phosphogypsum through washing, purification
2O
5Content with F makes P
2O
5Content less than 1%, F content is less than 0.35%, enters water extracter and dryer then, the phosphogypsum that has removed part moisture and part fluorine enters batch bin after cooling.Hard coal, silica and various auxiliary material also enter batch bin after reaching granularity requirements through ball mill grinding, the cement slurry for preparing is calcined through adding rotary kiln after the homogenizing, and it is that reductive agent resolves into CaO and SO with carbon for about 1300 ℃ that phosphogypsum decomposes section at rotary kiln
2, CaO further generates Dicalcium Phosphate (Feed Grade) (C with the reaction of silica generation mineralising in the rotary kiln section of burning till about 1450 ℃
2S) and tricalcium silicate (C
3S) finish the reaction of burning till cement, the material that goes out rotary kiln is cement clinker, behind raw materials such as cooling adding part retardant and activator, obtains cement products by pulverizing, grinding.Contain SO
2Kiln gas be and produce vitriolic unstripped gas (general SO
2Concentration expressed in percentage by volume be about 8%, O
2Concentration expressed in percentage by volume be about 1%), unstripped gas is through dedusting, wet purification, SO
2Be dissolved in water or the dilute sulphuric acid, enter system through air bells stripping, unstripped gas is through purifying SO
2Back concentration dilution is a concentration expressed in percentage by volume about 4%, for the thermal equilibrium that guarantees to transform, adopts one to change one and inhale the relieving haperacidity flow process usually, total turnover ratio about 96%, emptying tail gas SO
2Concentration have only could qualified discharge through vent gas treatment.
The flow process of the phosphogypsum system producing sulfuric acid and jointly cement of present domestic industryization has following defective:
1. unstripped gas SO
2Concentration low, double conversion and double absorption transforms heat can not balance, can only change a suction with one, directly emptying of tail gas, running expense is higher.
2. unstripped gas SO
2Concentration low, cause the production unit production intensity low, cause sulphuric acid plant investment bigger, usefulness is low.
3. owing to the easy scaling loss of the easy ring formation of calcination process in rotary kiln, the treatment time is longer, and follow-up equipment can only be waited to produce, and causes plant factor low.Simultaneously, transform each section temperature when to be produced and descend, transform outer again heat during production and heat up, improved production cost.
4. the operation of rotary kiln is difficult for grasping, and fluctuation of operating conditions is big, and is bigger to the sulphuric acid plant influence.When being strongly reducing atmosphere in the kiln, produce sublimed sulphur, stop up the pipeline and the equipment of purification system; Be that strong oxidizing atmosphere is right in kiln, phosphogypsum can not decompose fully, causes kiln gas SO
2Concentration is low, and is bigger to the relieving haperacidity influence, causes cement product quality defective simultaneously.
The present invention can overcome the technological deficiency or the deficiency of phosphogypsum system producing sulfuric acid and jointly cement, utilizes that roasting kiln burns the high density SO of the concentration expressed in percentage by volume about 13% that in the acid production with sulphur
2Gas is with the low concentration SO of concentration expressed in percentage by volume about 4%
2Kiln gas mixes, and is made into the SO of concentration expressed in percentage by volume 8%～9%
2Gas can adopt advanced double conversion and double absorption relieving haperacidity flow process, utilizes 900 ℃ of pyritous SO of roasting kiln
2Gas, can simplify the double conversion and double absorption heat exchange process, the tail gas of ordinary production can not treated direct emptying, and when rotary kiln broke down, sulphuric acid plant can ordinary production, the utilization ratio of device and the production intensity of equipment have been improved, after rotary kiln was repaired, system can ordinary production, has reduced the possibility of polluting, improve the utilization ratio of sulphur, thereby improved the overall efficiency of device.
Summary of the invention:
Utilize the phosphogypsum acid making system to go out the low concentration SO of rotary kiln
2Gas, this kiln gas are after washing, purification, drying, with the high density SO of sulphur-burning sulphuric acid system
2Gas mixes, and is made into the SO of concentration expressed in percentage by volume 8～9%
2Gas adopts advanced double conversion and double absorption relieving haperacidity flow process to make sulfuric acid, and phosphogypsum burns till in rotary kiln and is cement clinker simultaneously, makes cement through grinding batching.
The reaction mechanism of this invented technology process is as follows:
1, the burning of sulphur
Sulphur obtains smart sulphur through the clarification separating impurity after melting with the steam indirect heating, sprays into sulfur furnace with the sulphur pump through the sulphur rifle, with airborne oxygen generation combustion reactions, generates SO
2Gas
S+O
2→SO
2
2, the decomposition of phosphogypsum
With the carbon in the hard coal is reductive agent, and decomposing phosphogypsum is calcium oxide and sulfurous gas.
CaSO
4+2C→CaS+2CO
2
CaS+3CaSO
4→4CaO+4SO
2
Net reaction is: 2CaSO
4+ C → 2CaO+2SO
2+ CO
2
3, cement burns till
In phosphogypsum, allocate silica, sesquioxide into, both satisfied the requirement of cement clinker, can reduce the decomposition temperature of calcium sulfate again and accelerate decomposition rate.The chemical reaction that they take place is as follows:
CaSO
4+SiO
2→CaSiO
3+SO
2+0.5O
2
2CaSO
4+SiO
2→Ca
2SiO
4+2SO
2+O
2
CaSO
4+Fe
2O
3→CaO.Fe
2O
3+SO
2+0.5O
2
CaSO
4+Al
2O
3→CaO.Al
2O
3+SO
2+0.5O
2
The total reaction that cement burns till can be write as:
CaO+SiO
2+Fe
2O
3+Al
2O
3→C
3S、C
2S、C
3Al、C
4FAl
Silica in the batching, sesquioxide and CaSO
4The CaO that decomposition reaction obtains carries out mineralising reaction simultaneously and generates four kinds of main components: be i.e. Dicalcium Phosphate (Feed Grade), 2CaO.SiO
2(C
2S), tricalcium silicate, 3CaO.SiO
2(C
3S), tricalcium aluminate, 3CaO.Al
2O
3(C
3Al) and tetracalcium aluminoferrite, 4CaO.Al
2O
3.Fe
2O
3(C
4FAl).Above material mixes, and is cement clinker after the cooling, adds retardant after levigate and is cement.
4, SO
2Oxidation
SO
2Under the katalysis of catalyzer with unstripped gas in oxygen reaction, generate SO
3
SO
2+O.5O
2→SO
3
5, SO
3Absorption
SO
3Absorb with the vitriol oil, generate sulfuric acid with water reaction in the vitriol oil:
SO
3+H
2O→H
2SO
4
The present invention specifically realizes by the process technology scheme of following steps:
1, phosphogypsum reduces free P in the phosphogypsum through starching, wash, purifying
2O
5Content with F makes P
2O
5Content less than 1%, F content is less than 0.35%, enters water extracter and dryer dewatered drying then.
2, the phosphogypsum that has removed part moisture and part fluorine enters batch bin after cooling.Hard coal, silica and various auxiliary material also enter batch bin after reaching granularity requirements through ball mill grinding, and the cement slurry for preparing is carried out homogenizing.
3, the adding of the raw material after homogenizing rotary kiln is calcined, and it is that reductive agent resolves into CaO and SO with carbon for 1250～1350 ℃ that phosphogypsum decomposes section at rotary kiln
2, CaO further generates Dicalcium Phosphate (Feed Grade) (C with the reaction of silica generation mineralising in the rotary kiln section of burning till at 1400～1500 ℃
2S) and tricalcium silicate (C
3S) finish the reaction of burning till cement, the material that goes out rotary kiln is cement clinker.
4, behind raw materials such as cooling adding part retardant and activator, obtain cement products by pulverizing, grinding.
5, contain SO
2Kiln gas be and produce vitriolic unstripped gas (low concentration SO
2The gas volume percentage concentration is 5%～8%, O
2Concentration expressed in percentage by volume be 0.7～1%), kiln gas is through dedusting, wet purification, part SO
2Be dissolved in water or the dilute sulphuric acid SO in water or the dilute sulphuric acid
2Enter acid making system through air bells stripping, unstripped gas is through purifying SO
2Concentration expressed in percentage by volume dilution be about 4%.
6, the kiln gas behind the purification and impurity removal is removed moisture content by drying, enters cold and hot mixing tank through main air blower.
7, sulfur dioxide gas (the high density SO that comes out of sulphur-burning sulphuric acid system sulfur furnace
2The gas volume percentage concentration is 10～13%), carrying out high-temperature gas through gas-separating valve distributes, the hot gas that part gas comes with gas-separating valve after by residual heat boiler for exchanging heat is mixed into cold and hot gas mixer, regulates the air quantity and the sulfuring up amount of sulfur furnace, uses the SO of cold and hot mixing tank
2Gas reaches 8～9% concentration expressed in percentage by volume.
8, the tolerance of adjusting gas-separating valve is used the SO of cold and hot mixing tank
2Gas temperature reaches 420～430 ℃, enters convertor and finishes SO
2To SO
3Conversion.
9, the SO after the conversion
3Gas enters the absorption tower, and the sulfuric acid absorption with 98% generates sulfuric acid.
The employing of Technology of the present invention has overcome the defective of existing domestic current phosphogypsum relieving haperacidity production technique, has improved to enter converter SO
2Concentration can promote the production intensity of acid making system equipment, utilize 900 ℃ of high temperature SO of sulfur furnace
2Gas, can simplify the double conversion and double absorption heat exchange process, the tail gas of ordinary production can not treated direct emptying, and when rotary kiln broke down, sulphuric acid plant can ordinary production, improved the utilization ratio of device, after rotary kiln was repaired, system can ordinary production, has reduced the possibility of polluting, improve the utilization ratio of sulphur, thereby improved the overall efficiency of device.
Description of drawings
Accompanying drawing of the present invention is seen Fig. 1
Embodiment
The present invention is further illustrated below in conjunction with example:
Embodiment one
Will through wash and starch again wash, purify after, free P
2O
5Be 0.65%, F content is 0.21% phosphogypsum, sends the water extracter dehydration to and removes washing water, enters drying machine drying then.After cooling, enter batch bin.The granularity that hard coal, silica and kaolin are swept ball mill grinding and reached-200 mesh sieves through wind enters batch bin by air blast between 10～12%, the cement slurry for preparing is carried out homogenizing.Raw material after the homogenizing add rotary kiln to be calcined, and regulates by coal spouting gun and air quantity, and it is 1280～1335 ℃ that the control rotary kiln decomposes section, and the carbon in the kiln in the hard coal is reduced into CaO and SO with phosphogypsum
2, the CaO in the material is 1430～1480 ℃ the section of burning till, with silica generation mineralising reaction existence Dicalcium Phosphate (Feed Grade) (C
2S) and tricalcium silicate (C
3S) finish the reaction of burning till cement, grog obtains cement products by pulverizing, grinding after cooling adds part retardant and activator.
Concentration is 5.3% SO
2Kiln gas is through cyclone dust removal, diluted acid enclosed purification, part SO
2Be dissolved in the dilute sulphuric acid SO in the dilute sulphuric acid
2Enter acid making system through air bells stripping, kiln gas is through purifying SO
2Concentration dilution be 3.1%, moisture content is less than 0.1g/Nm after 92～95% sulfuric acid drying
3, enter cold and hot mixing tank through main air blower.
Sulphur is through fast instant sulphur device fusing, after entering that settling pond is clear and falling 36 hours, with the sulphur pump sulphur liquid sprayed into sulfur furnace through the sulphur rifle, with dry air mixed firing from drying tower, and the SO of burning generation
2Gas distributes high-temperature gas with gas-separating valve, it is about 780 ℃ that the hot gas that comes by gas after the residual heat boiler for exchanging heat and gas-separating valve this moment mixes the back temperature, temperature is that the gas about 780 ℃ enters cold and hot gas mixer, regulates the air quantity and the sulfuring up amount of sulfur furnace, uses the SO of cold and hot mixing tank
2Gas reaches 8～9% concentration, and temperature remains on 420～430 ℃.SO
2Enter convertor and under the effect of catalyzer, finish SO
2To SO
3Conversion.SO after the conversion
3Gas enter the absorption tower, generate sulfuric acid with 98% sulfuric acid absorption.
Produce the gained cement products and carry out ordinary Portland cement standard (GB 175-1999), strength grade 52.5, sulfuric acid is carried out industrial sulphuric acid quality standard (GB/T 534-2002).
Go out to grind cement product quality and detect index such as table 1:
Produce gained sulfuric acid quality detecting index such as table 2:
Embodiment two
Will through wash and starch again wash, purify after, free P
2O
5Be 0.96%, F content is 0.33% phosphogypsum, sends the water extracter dehydration to and removes washing water, enters drying machine drying then.After cooling, enter batch bin.The granularity that hard coal, silica and kaolin are swept ball mill grinding and reached-200 mesh sieves through wind enters batch bin by air blast between 10～12%, the cement slurry for preparing is carried out homogenizing.Raw material after the homogenizing add rotary kiln to be calcined, and regulates by coal spouting gun and air quantity, and it is 1280～1335 ℃ that the control rotary kiln decomposes section, and the carbon in the kiln in the hard coal is reduced into CaO and SO with phosphogypsum
2, the CaO in the material is 1430～1480 ℃ the section of burning till, with silica generation mineralising reaction existence Dicalcium Phosphate (Feed Grade) (C
2S) and tricalcium silicate (C
3S) finish the reaction of burning till cement, grog adds part retardant and activator through postcooling, obtains cement products by pulverizing, grinding.
SO
2Concentration is that 7.8% kiln gas is through cyclone dust removal, diluted acid enclosed purification, part SO
2Be dissolved in the dilute sulphuric acid SO in the dilute sulphuric acid
2Enter acid making system through air bells stripping, kiln gas is through purifying SO
2Concentration dilution be 4.9%, moisture content is less than 0.1g/Nm after 92～95% sulfuric acid drying
3, enter cold and hot mixing tank through main air blower.
Sulphur is through fast instant sulphur device fusing, after entering that settling pond is clear and falling 36 hours, with the sulphur pump sulphur liquid sprayed into sulfur furnace through the sulphur rifle, with dry air mixed firing from drying tower, and the SO of burning generation
2Gas distributes high-temperature gas with gas-separating valve, it is about 720 ℃ that the hot gas that comes by gas after the residual heat boiler for exchanging heat and gas-separating valve this moment mixes the back temperature, the gas of temperature about 720 ℃ enters cold and hot gas mixer, regulates the air quantity and the sulfuring up amount of sulfur furnace, uses the SO of cold and hot mixing tank
2Gas reaches 8～9% concentration, and temperature remains on 420～430 ℃.SO
2Enter convertor and under the effect of catalyzer, finish SO
2To SO
3Conversion.SO after the conversion
3Gas enter the absorption tower, generate sulfuric acid with 98% sulfuric acid absorption.
Go out to grind cement product quality and detect index such as table 3:
Produce gained sulfuric acid quality detecting index such as table 4:
Claims (1)
1, a kind of phosphogypsum combines the method for relieving haperacidity jointly producing cement with sulphur, it is characterized in that: utilizing the phosphogypsum acid making system to go out rotary kiln, to contain concentration expressed in percentage by volume be 5～8%SO
2With concentration expressed in percentage by volume be 0.7～1%O
2Gas, this kiln gas is through washing, purification, drying, with the sulphur-burning sulphuric acid system concentration expressed in percentage by volume be 10～13% SO
2Gas mixes, and is made into concentration expressed in percentage by volume and is 8～9% SO
2Gas adopts double conversion and double absorption relieving haperacidity flow process to make sulfuric acid, and phosphogypsum burns till in rotary kiln and is cement clinker simultaneously, makes cement through grinding batching, and this method comprises:
(1) phosphogypsum reduces free P in the phosphogypsum through washing, purification
2O
5Content with F makes P
2O
5Content less than 1%, F content is less than 0.35%, enters water extracter and dryer dewatered drying then;
(2) phosphogypsum that has removed part moisture and part fluorine enters batch bin after cooling, and hard coal, silica and auxiliary material also enter batch bin after reaching granularity requirements through ball mill grinding, and the cement slurry for preparing is carried out homogenizing;
(3) adding of the raw material after homogenizing rotary kiln is calcined, and it is that reductive agent resolves into CaO and SO with carbon for 1250～1350 ℃ that phosphogypsum decomposes section at rotary kiln
2, CaO further finishes the reaction of burning till cement with silica generation mineralising reaction generation Dicalcium Phosphate (Feed Grade) and tricalcium silicate in the rotary kiln section of burning till at 1400～1500 ℃, and the material that goes out rotary kiln is cement clinker;
(4) cement clinker obtains cement products by pulverizing, grinding after cooling adds part retardant and activator raw material;
(5) contain SO
2Kiln gas through dedusting, wet purification, purification medium is water or dilute sulphuric acid, the SO of water-soluble or dilute sulphuric acid
2Enter acid making system through air bells stripping, kiln gas dilutes and is SO after purifying
2Concentration expressed in percentage by volume is 3～5% gas;
(6) kiln gas of purification and impurity removal is removed moisture by drying, enters cold and hot mixing tank through living blower fan;
(7) SO that comes out of sulphur-burning sulphuric acid system sulfur furnace
2Gas carries out high-temperature gas through gas-separating valve and distributes a part of SO
2The hot SO that gas comes with gas-separating valve after by residual heat boiler for exchanging heat
2Gas is mixed into cold and hot gas mixer, regulates the air quantity and the sulfuring up amount of sulfur furnace, uses the SO of cold and hot mixing tank
2Gas reaches 8～9% concentration expressed in percentage by volume;
(8) tolerance of the regulating gas-separating valve temperature of using cold and hot mixing tank reaches 420～430 ℃, enters convertor and finishes SO
2To SO
3Conversion;
(9) SO after the conversion
3Gas enters the absorption tower, and the sulfuric acid absorption with 98% generates sulfuric acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101844748B (en) * | 2010-05-18 | 2011-08-24 | 云南创兴建材新技术有限公司 | Method for preparing high-concentration SO2 flue gas and active CaO by using phosphogypsum and decomposing furnace |
| CN104555946B (en) * | 2015-01-20 | 2017-01-18 | 上海三夫工程技术有限公司 | Method for jointly producing sulphuric acid and cement clinker by using sulphur gas to reduce gypsum |
| CN106082137B (en) * | 2016-06-21 | 2018-02-23 | 山东铁雄冶金科技有限公司 | A kind of system and technique for comprehensively utilizing coking low-quality sulfur and doctor solution secondary salt |
| CN107720708A (en) * | 2017-11-21 | 2018-02-23 | 宜昌鄂中化工有限公司 | A kind of acid production with sulphur waste heat is used for the device and method of ardealite comprehensive utilization |
| DE102020100254A1 (en) | 2020-01-08 | 2021-07-08 | Thyssenkrupp Ag | Integrated process for the production of a building material from phosphogypsum |
| DE102020100260A1 (en) | 2020-01-08 | 2021-07-08 | Thyssenkrupp Ag | Integrated process for the production of sulfuric acid process-suitable sulfur dioxide quality from calcium sulfate / phosphogypsum from phosphoric acid production |
| CN112250051B (en) * | 2020-10-16 | 2023-08-22 | 昆明理工大学 | Method for co-producing phosphoric acid and cement clinker by absorbing phosphogypsum roasting smoke by phosphorite slurry |
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| EP0004568A1 (en) * | 1978-04-02 | 1979-10-17 | Abdel Fattah Dr. Sabry Hosein Kamel | Process for recovering sulphuric acid from natural gypsum or phospho-gypsum |
| SU763256A1 (en) * | 1976-08-13 | 1980-09-15 | Всесоюзный научно-исследовательский и проектный институт алюминиевой, магниевой и электродной промышленности | Method of phosphogypsum processing |
| CN1227825A (en) * | 1998-11-27 | 1999-09-08 | 遵化市化肥厂 | Method for producing sulfuric acid and jointly producing cement by using anthracite cinder instead of coke breeze |
| CN1227824A (en) * | 1998-11-27 | 1999-09-08 | 遵化市化肥厂 | Improved method for producing sulfuric acid and jointly producing cement |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| SU763256A1 (en) * | 1976-08-13 | 1980-09-15 | Всесоюзный научно-исследовательский и проектный институт алюминиевой, магниевой и электродной промышленности | Method of phosphogypsum processing |
| EP0004568A1 (en) * | 1978-04-02 | 1979-10-17 | Abdel Fattah Dr. Sabry Hosein Kamel | Process for recovering sulphuric acid from natural gypsum or phospho-gypsum |
| CN1227825A (en) * | 1998-11-27 | 1999-09-08 | 遵化市化肥厂 | Method for producing sulfuric acid and jointly producing cement by using anthracite cinder instead of coke breeze |
| CN1227824A (en) * | 1998-11-27 | 1999-09-08 | 遵化市化肥厂 | Improved method for producing sulfuric acid and jointly producing cement |
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