CN1513766A - Techlogogy for making alpha semi-water desulfur gypsum using normal pressure salt solution method - Google Patents
Techlogogy for making alpha semi-water desulfur gypsum using normal pressure salt solution method Download PDFInfo
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- CN1513766A CN1513766A CNA031426077A CN03142607A CN1513766A CN 1513766 A CN1513766 A CN 1513766A CN A031426077 A CNA031426077 A CN A031426077A CN 03142607 A CN03142607 A CN 03142607A CN 1513766 A CN1513766 A CN 1513766A
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- China
- Prior art keywords
- slurries
- tank
- desulfurated plaster
- normal pressure
- gypsum
- 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.)
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 229910052602 gypsum Inorganic materials 0.000 title abstract description 72
- 239000010440 gypsum Substances 0.000 title abstract description 72
- 238000000034 method Methods 0.000 title abstract description 52
- 239000012266 salt solution Substances 0.000 title abstract 4
- 239000002002 slurry Substances 0.000 claims abstract description 149
- 238000005406 washing Methods 0.000 claims abstract description 30
- 239000007788 liquid Substances 0.000 claims abstract description 18
- 238000000926 separation method Methods 0.000 claims abstract description 18
- GBAOBIBJACZTNA-UHFFFAOYSA-L calcium sulfite Chemical compound [Ca+2].[O-]S([O-])=O GBAOBIBJACZTNA-UHFFFAOYSA-L 0.000 claims abstract description 8
- 235000010261 calcium sulphite Nutrition 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 4
- 230000008719 thickening Effects 0.000 claims abstract description 3
- 230000003647 oxidation Effects 0.000 claims description 88
- 238000007254 oxidation reaction Methods 0.000 claims description 88
- 239000011505 plaster Substances 0.000 claims description 46
- 239000013078 crystal Substances 0.000 claims description 43
- 238000002425 crystallisation Methods 0.000 claims description 34
- 230000008025 crystallization Effects 0.000 claims description 33
- 239000003795 chemical substances by application Substances 0.000 claims description 32
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 28
- 238000005516 engineering process Methods 0.000 claims description 28
- 239000003546 flue gas Substances 0.000 claims description 28
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 24
- 150000003839 salts Chemical class 0.000 claims description 22
- 239000002562 thickening agent Substances 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 15
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 claims description 14
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 229940075507 glyceryl monostearate Drugs 0.000 claims description 7
- 239000001788 mono and diglycerides of fatty acids Substances 0.000 claims description 7
- 239000011593 sulfur Substances 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 5
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 5
- 238000012856 packing Methods 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 239000013543 active substance Substances 0.000 claims description 3
- 239000012141 concentrate Substances 0.000 claims description 3
- 239000006200 vaporizer Substances 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 229910052728 basic metal Inorganic materials 0.000 claims description 2
- 150000003818 basic metals Chemical class 0.000 claims description 2
- 230000005484 gravity Effects 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims 1
- 230000008676 import Effects 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 230000003009 desulfurizing effect Effects 0.000 abstract 1
- 239000003517 fume Substances 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 230000008569 process Effects 0.000 description 22
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 20
- 230000004048 modification Effects 0.000 description 17
- 238000012986 modification Methods 0.000 description 17
- 238000012544 monitoring process Methods 0.000 description 15
- 210000002966 serum Anatomy 0.000 description 15
- 239000007787 solid Substances 0.000 description 15
- 238000010792 warming Methods 0.000 description 15
- 238000000605 extraction Methods 0.000 description 14
- 238000006477 desulfuration reaction Methods 0.000 description 10
- 230000023556 desulfurization Effects 0.000 description 10
- 235000011187 glycerol Nutrition 0.000 description 10
- 239000004575 stone Substances 0.000 description 9
- 239000001384 succinic acid Substances 0.000 description 6
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000008901 benefit Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 150000004683 dihydrates Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 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 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000011507 gypsum plaster Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011020 pilot scale process Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Treating Waste Gases (AREA)
Abstract
A process for preparing the desulfurized alpha-semi-hydrated gypsum by ordinary-pressure salt solution method includes oxidizing the deposited calcium sulfite slurry generated by desulfurizing fume, thickening, adding salt solution, mixing, crystallizing, centrifugal solid-liquid separation washing and drying. The washing water is evaporated to obtain concentrated salt solution for reuse.
Description
Technical field
The present invention relates to the method for utilizing of flue gas desulfurization byproduct, especially relate to the technology that a kind of normal pressure salt solustion mehtod is produced α-half water desulfurated plaster.
Background technology
Calcium-based desulfurization technology is present most widely used in the world flue gas desulfurization technique, produces the insoluble calcium sulfate precipitation that is rich in calcium sulfite, the desulfurated plaster that promptly is commonly called as behind the desulphurization reaction.Calcium sulfite is a kind of strong aerobic mineral compound, and the calcium sulfite residue directly enters ecological circulation can cause secondary pollution, therefore must carry out suitable treatment and disposal to this desulfurization residue.Forced oxidation is the most direct means, and the calcium sulfate that oxidation generates has the physico-chemical property that is enhanced, and reduces as the refuse volume, and easier dehydration and extremely low oxygen requirement can realize recycling; The sulfite oxidation system has safe, nontoxic and stable characteristics simultaneously, so the oxidising process of calcium sulfite day by day is subject to people's attention.
The product that oxidation obtains is generally dihydrate gypsum, i.e. plaster stone, and crystal formation mostly is needle-like, can not satisfy the needs of practical application, therefore in Crystallization Procedure the oxidation gypsum is carried out the crystal formation modification.Generally, in six kinds of crystal habits of gypsum, alpha-semi water plaster stone is a kind of modified gypsum of excellent property, it is few to have water requirement, therefore the intensity advantages of higher is wanted the desulfurated plaster crystal habit after the controlled oxidation in Crystallization Procedure, make it to be converted into alpha-semi water plaster stone.In gypsum industry, producing alpha-semi water plaster stone has a lot of methods, and commonly used both at home and abroad have two kinds of the steam-cured method of autoclave and reactor solution methods.The steam-cured method of autoclave is after plaster stone is crushed to certain particle size, and in the steam-cured car of packing into, it is interior steam-cured to send into autoclave, and required steam is high-pressure saturated water vapor, keeps the constant voltage certain hour, generates the semi-hydrated gypsum of α-crystallization phases at last.The required pressure height of this method autoclave, hot steam thermal energy conduction speed in plaster stone is slower, and the table internal heating of plaster stone is inhomogeneous, and its plaster stone dehydration and crystal transform also slow, waste energy.
It is 50～60% slip that the reactor solution method becomes concentration with dihydrate gypsum in the slurry tank internal modulation, adds medium crystallization agent simultaneously.In order to make alpha-semi water plaster stone residual in the filtrate washing fluid can play the effect of crystal seed, slurry tank must maintain the temperature at more than 90 ℃, alternately slip is injected reactor with shurry pump.Enter by the steam spacer in the reactor or directly be blown into steam, make slurry temperature rise to 120～140 ℃.About 30～the 40min of isothermal reaction is cooled to slip rapidly about 100 ℃ again under agitation condition, makes slip all flow into whizzer.Use the hot water cleaning reaction still more than 90 ℃ then, after washing lotion also all flows into whizzer, begin the new cycle.This method former transition that is used for the plaster of paris, after be borrowed in the production of desulfurated plaster.
The general gypsum of normal pressure salts solution after transition that adopt is generally used for making products such as self-leveling material, glass reinforced material, bearing plate.In fact, normal pressure salts solution technology industrial application also seldom, be in laboratory study and a spot of pilot scale research stage at present; And abroad its processing parameter is maintained secrecy, therefore available relevant effective information is also seldom.
Summary of the invention
The invention provides a kind of can combining with flue gas desulfurization technique, the technology that adopts the normal pressure salts solution that desulfurated plaster is carried out modification, this technology investment cost and production cost are lower, but continuous operation.
A kind of normal pressure salt solustion mehtod is produced α-half water desulfurated plaster technology, comprising:
(1) precipitation of the calcium sulfite in the settling bath in sulfur removal technology slurry is sent into the flue gas of oxidation trough in dispensing air or importing sulfur removal technology and carried out abundant oxidation;
(2) the oxidation rear slurry is sent into slurry commanding tank after the thickener thickening, and the salts solution that adds certain proportioning in slurry commanding tank is made medium crystallization agent, mixes the back and forms certain density slurries;
(3) slurries that prepare are sent into crystallizer and under the certain pH value condition, carried out crystallization;
(4) crystallization of crystallizer bottom is extracted out by slush pump, deliver to supply with and enter whizzer behind the groove gravity settling and carry out solid-liquid separation;
(5) with the washing of isolated α-half water desulfurated plaster, the medium crystallization agent cyclically utilizing after washing water concentrate through vaporizer;
(6) α-half water desulfurated plaster drying, the packing after will washing.
Described thickener slurries are thickened to concentration of slurry and are (weight percent): 10～70%
The add-on of salts solution is (weight percent) in the described slurry commanding tank: 0.5～30%
The described slurry temperature scope that enters crystallizer is: 50～110 ℃
The pH of solution is in the described crystallizer: 3～8
Temperature is in the described crystallizer: 50～110 ℃, the slurries residence time is 0.5～50hr in the crystallizer.
Described medium crystallization agent is the aqueous solution of the soluble salt of basic metal and alkaline-earth metal, can select CaCl for use
2, MgCl
2, any or several the mixture among the KCl.
Also can add crystal formation modifying agent and stablizer in the described medium crystallization agent, the crystal formation modifying agent can be selected organic multicomponent acid and common tensio-active agent for use, organic multicomponent acid can be selected for use as Succinic Acid and citric acid, tensio-active agent can be selected for use as the Sodium dodecylbenzene sulfonate of cheapness and glyceryl monostearate, add-on is (weight percent) 0～5%, stablizer is a polyvalent alcohol, and as glycerine etc., add-on is (weight percent) 0～10%.
Technology of the present invention can be inserted in the flue gas desulfurization technique, and the precipitation of the calcium sulfite in settling bath slurry is directly entered oxidation before washing, and washing process becomes finishing operation.Unique contacting directly is that gypsum produces washing water by the flue gas desulfurization course output and from technological process of the present invention in flue gas desulfurization course and gypsum conversion process.All this contacts can by and also must cut off by surge tank.
The advantage of technology of the present invention is:
1. the technology of producing α-half water desulfurated plaster can be combined with flue gas desulfurization technique;
2. do not need high pressure, this is a part expensive in cost of investment and the running cost;
3. do not need expensive steam as thermal source;
4. adopt several crystallizer serial or parallel connections can better control conversion process, this process helps operate continuously.
5. because less press device and control easily have higher reliability;
6. when process of the present invention was worked with the flue gas desulfurization course of the closed circulation with waste evaporator plant, all predesigne showed to have minimum production cost.
Description of drawings
Fig. 1 is a process flow sheet of the present invention.
Embodiment
Embodiment 1
The gypsum of releasing from the flue gas desulphurization system settling tank is without washing, and concentration of slurry is about 10～20%, these slurries directly can be sent into oxidation trough or be utilized surge tank, then slurries is sent into the gypsum treatment process gypsum is carried out modification.Slurries at first enter oxidation trough, and pH is about 4 in the oxidation trough, and presses 40Nm
3Air/m
3The ratio of slurries is sent into air, under the condition about 40 ℃, promotes the complete oxidation of desulfurated plaster.Gypsum behind the complete oxidation enters thickener and is thickened to 50%, sends into slurry commanding tank.The liquid-solid bulk concentration of slurry commanding tank entoplasm is about 10%, and the medium crystallization agent total concn is 10%, consists of: CaCl
28%, Succinic Acid 1%, glycerine 1%.Mix after heat exchanger is warming up to the evaporator tank that enters crystallizer top after 80 ℃.Keep 80 ℃ and certain surface pressure in the evaporator tank, residence time 2hr treats that crystal habit changes, and enters downtake, sends into the crystallizer tank of bottom, makes crystal continue to grow up.Continuing controlled temperature in the crystallizer tank is 80 ℃, monitoring serum density＞1000Kg/m
3After, to extract slurries out and send into swirler and makes solid-liquid separation, the macrobead crystal of bottom can be through centrifugation, and the fresh water washing is carried packing after sending into the ebullated dryer drying.Top is separated and is contained short grained slurries and reenter crystallizer as crystal seed.Simultaneously, the medium crystallization agent cyclically utilizing after washing water concentrate through vaporizer.
Embodiment 2
The gypsum of releasing from the flue gas desulphurization system settling tank is without washing, and concentration of slurry is about 10～20%, these slurries directly can be sent into oxidation trough or be utilized surge tank, then slurries is sent into the gypsum treatment process gypsum is carried out modification.Slurries at first enter oxidation trough, and pH is about 5 in the oxidation trough, and presses 40Nm
3Air/m
3The ratio of slurries is sent into the flue gas in the sulfur removal technology, under the condition about 40 ℃, promotes the complete oxidation of desulfurated plaster.Gypsum behind the complete oxidation enters thickener and is thickened to 50%, sends into slurry commanding tank.The liquid-solid bulk concentration of slurry commanding tank entoplasm is about 10%, and the medium crystallization agent total concn is 5%, consists of: MgCl
24%, Succinic Acid 0.5%, glycerine 0.5% mixes after heat exchanger is warming up to the evaporator tank that enters crystallizer top after 80 ℃.Keep 90 ℃ and certain surface pressure in the evaporator tank, residence time 1.5hr treats that crystal habit changes, and enters downtake, sends into the crystallizer tank of bottom, makes crystal continue to grow up.Continuing controlled temperature in the crystallizer tank is 90 ℃, monitoring serum density＞1000Kg/m
3After, the extraction slurries are sent into swirler makes solid-liquid separation, and subsequent technique is with embodiment 1.
Embodiment 3
The gypsum of releasing from the flue gas desulphurization system settling tank is without washing, and concentration of slurry is about 10～20%, these slurries directly can be sent into oxidation trough or be utilized surge tank, then slurries is sent into the gypsum treatment process gypsum is carried out modification.Slurries at first enter oxidation trough, and pH is about 6 in the oxidation trough, and presses 40Nm
3Air/m
3The ratio of slurries is sent into air, under the condition about 40 ℃, promotes the complete oxidation of desulfurated plaster.Gypsum behind the complete oxidation enters thickener and is thickened to 50%, sends into slurry commanding tank.The liquid-solid bulk concentration of slurry commanding tank entoplasm is about 10%, and the medium crystallization agent total concn is 15%, consists of: KCl 11%, and Succinic Acid 4% mixes after heat exchanger is warming up to the evaporator tank that enters crystallizer top after 60 ℃.Keep 60 ℃ and certain surface pressure in the evaporator tank, residence time 3hr treats that crystal habit changes, and enters downtake, sends into the crystallizer tank of bottom, makes crystal continue to grow up.Continuing controlled temperature in the crystallizer tank is 80 ℃, monitoring serum density＞1000Kg/m
3After, the extraction slurries are sent into swirler makes solid-liquid separation, and subsequent technique is with embodiment 1.
Embodiment 4
The gypsum of releasing from the flue gas desulphurization system settling tank is without washing, and concentration of slurry is about 10～20%, these slurries directly can be sent into oxidation trough or be utilized surge tank, then slurries is sent into the gypsum treatment process gypsum is carried out modification.Slurries at first enter oxidation trough, and pH is about 7 in the oxidation trough, and presses 40Nm
3Air/m
3The ratio of slurries is sent into the flue gas in the sulfur removal technology, under the condition about 40 ℃, promotes the complete oxidation of desulfurated plaster.Gypsum behind the complete oxidation enters thickener and is thickened to 50%, sends into slurry commanding tank.The liquid-solid bulk concentration of slurry commanding tank entoplasm is about 10%, and the medium crystallization agent total concn is 26%, consists of: CaCl
220%, glycerine 6% mixes after heat exchanger is warming up to the evaporator tank that enters crystallizer top after 80 ℃.Keep 100 ℃ and certain surface pressure in the evaporator tank, residence time 1hr treats that crystal habit changes, and enters downtake, sends into the crystallizer tank of bottom, makes crystal continue to grow up.Continuing controlled temperature in the crystallizer tank is 100 ℃, monitoring serum density＞1000Kg/m
3After, the extraction slurries are sent into swirler makes solid-liquid separation, and subsequent technique is with embodiment 1.
Embodiment 5
The gypsum of releasing from the flue gas desulphurization system settling tank is without washing, and concentration of slurry is about 10～20%, these slurries directly can be sent into oxidation trough or be utilized surge tank, then slurries is sent into the gypsum treatment process gypsum is carried out modification.Slurries at first enter oxidation trough, and pH is about 8 in the oxidation trough, and presses 40Nm
3Air/m
3The ratio of slurries is sent into air, under the condition about 40 ℃, promotes the complete oxidation of desulfurated plaster.Gypsum behind the complete oxidation enters thickener and is thickened to 50%, sends into slurry commanding tank.The liquid-solid bulk concentration of slurry commanding tank entoplasm is about 10%, and the medium crystallization agent total concn is about 1%, consists of: CaCl
20.9%, citric acid 0.05%, glycerine 0.05%, and the Sodium dodecylbenzene sulfonate of trace mixes after heat exchanger is warming up to the evaporator tank that enters crystallizer top after 80 ℃.Keep 50 ℃ and certain surface pressure in the evaporator tank, residence time 20hr treats that crystal habit changes, and enters downtake, sends into the crystallizer tank of bottom, makes crystal continue to grow up.Continuing controlled temperature in the crystallizer tank is 50 ℃, monitoring serum density＞1000Kg/m
3After, the extraction slurries are sent into swirler makes solid-liquid separation, and subsequent technique is with embodiment 1.
Embodiment 6
The gypsum of releasing from the flue gas desulphurization system settling tank is without washing, and concentration of slurry is about 10～20%, these slurries directly can be sent into oxidation trough or be utilized surge tank, then slurries is sent into the gypsum treatment process gypsum is carried out modification.Slurries at first enter oxidation trough, and pH is about 4 in the oxidation trough, and presses 50Nm
3Air/m
3The ratio of slurries is sent into air, under the condition about 50 ℃, promotes the complete oxidation of desulfurated plaster.Gypsum behind the complete oxidation enters thickener and is thickened to 40%, sends into slurry commanding tank.The liquid-solid bulk concentration of slurry commanding tank entoplasm is about 15%, and the medium crystallization agent total concn is about 5%, consists of: CaCl
21%, MgCl
21%, KCl 1%, citric acid 1%, glycerine 1%, and the glyceryl monostearate of trace.Mix after heat exchanger is warming up to the evaporator tank that enters crystallizer top after 70 ℃.Keep 70 ℃ and certain surface pressure in the evaporator tank, residence time 15hr treats that crystal habit changes, and enters downtake, sends into the crystallizer tank of bottom, makes crystal continue to magnify.Continuing controlled temperature in the crystallizer tank is 70 ℃, monitoring serum density＞1000Kg/m
3After, the extraction slurries are sent into swirler makes solid-liquid separation, and subsequent technique is with embodiment 1.
Embodiment 7
The gypsum of releasing from the flue gas desulphurization system settling tank is without washing, and concentration of slurry is about 10～20%, these slurries directly can be sent into oxidation trough or be utilized surge tank, then slurries is sent into the gypsum treatment process gypsum is carried out modification.Slurries at first enter oxidation trough, and pH is about 5 in the oxidation trough, and presses 50Nm
3Air/m
3The ratio of slurries is sent into air, under the condition about 50 ℃, promotes the complete oxidation of desulfurated plaster.Gypsum behind the complete oxidation enters thickener and is thickened to 40%, sends into slurry commanding tank.The liquid-solid bulk concentration of slurry commanding tank entoplasm is about 15%, and the medium crystallization agent total concn is about 20%, consists of: CaCl
25%, MgCl
25%, KCl 5%, citric acid 3%, glycerine 2%, and the glyceryl monostearate of trace.Mix after heat exchanger is warming up to the evaporator tank that enters crystallizer top after 70 ℃.Keep 70 ℃ and certain surface pressure in the evaporator tank, residence time 15hr treats that crystal habit changes, and enters downtake, sends into the crystallizer tank of bottom, makes crystal continue to grow up.Continuing controlled temperature in the crystallizer tank is 70 ℃, monitoring serum density＞1000Kg/m
3After, the extraction slurries are sent into swirler makes solid-liquid separation, and subsequent technique is with embodiment 1.
Embodiment 8
The gypsum of releasing from the flue gas desulphurization system settling tank is without washing, and concentration of slurry is about 10～20%, these slurries directly can be sent into oxidation trough or be utilized surge tank, then slurries is sent into the gypsum treatment process gypsum is carried out modification.Slurries at first enter oxidation trough, and pH is about 6 in the oxidation trough, and presses 50Nm
3Air/m
3The ratio of slurries is sent into air, under the condition about 50 ℃, promotes the complete oxidation of desulfurated plaster.Gypsum behind the complete oxidation enters thickener and is thickened to 40%, sends into slurry commanding tank.The liquid-solid bulk concentration of slurry commanding tank entoplasm is about 15%, and the medium crystallization agent total concn is about 28%, consists of: CaCl
26%, MgCl
26%, KCl 6%, citric acid 2%, glycerine 8%, and the glyceryl monostearate of trace.Mix after heat exchanger is warming up to the evaporator tank that enters crystallizer top after 70 ℃.Keep 70 ℃ and certain surface pressure in the evaporator tank, residence time 15hr treats that crystal habit changes, and enters downtake, sends into the crystallizer tank of bottom, makes crystal continue to grow up.Continuing controlled temperature in the crystallizer tank is 70 ℃, monitoring serum density＞1000Kg/m
3After, the extraction slurries are sent into swirler makes solid-liquid separation, and subsequent technique is with embodiment 1.
Embodiment 9
The gypsum of releasing from the flue gas desulphurization system settling tank is without washing, and concentration of slurry is about 10～20%, these slurries directly can be sent into oxidation trough or be utilized surge tank, then slurries is sent into the gypsum treatment process gypsum is carried out modification.Slurries at first enter oxidation trough, and pH is about 7 in the oxidation trough, and presses 50Nm
3Air/m
3The ratio of slurries is sent into air, under the condition about 50 ℃, promotes the complete oxidation of desulfurated plaster.Gypsum behind the complete oxidation enters thickener and is thickened to 40%, sends into slurry commanding tank.The liquid-solid bulk concentration of slurry commanding tank entoplasm is about 15%, and the medium crystallization agent total concn is about 3%, consists of: CaCl
20.8%, MgCl
20.8%, KCl 0.8%, Succinic Acid 0.2%, citric acid 0.2%, glycerine 0.2%, and the Sodium dodecylbenzene sulfonate and the glyceryl monostearate of trace.Mix after heat exchanger is warming up to the evaporator tank that enters crystallizer top after 70 ℃.Keep 70 ℃ and certain surface pressure in the evaporator tank, residence time 15hr treats that crystal habit changes, and enters downtake, sends into the crystallizer tank of bottom, makes crystal continue to grow up.Continuing controlled temperature in the crystallizer tank is 70 ℃, monitoring serum density＞1000Kg/m
3After, the extraction slurries are sent into swirler makes solid-liquid separation, and subsequent technique is with embodiment 1.
Embodiment 10
The gypsum of releasing from the flue gas desulphurization system settling tank is without washing, and concentration of slurry is about 10～20%, these slurries directly can be sent into oxidation trough or be utilized surge tank, then slurries is sent into the gypsum treatment process gypsum is carried out modification.Slurries at first enter oxidation trough, and pH is about 8 in the oxidation trough, and presses 50Nm
3Air/m
3The ratio of slurries is sent into air, under the condition about 50 ℃, promotes the complete oxidation of desulfurated plaster.Gypsum behind the complete oxidation enters thickener and is thickened to 40%, sends into slurry commanding tank.The liquid-solid bulk concentration of slurry commanding tank entoplasm is about 15%, and the medium crystallization agent total concn is about 20%, consists of: CaCl
25%, MgCl
25%, KCl 5%, Succinic Acid 1%, citric acid 1%, glycerine 3%, and the Sodium dodecylbenzene sulfonate and the glyceryl monostearate of trace.Mix after heat exchanger is warming up to the evaporator tank that enters crystallizer top after 50 ℃.Keep 50 ℃ and certain surface pressure in the evaporator tank, residence time 40hr treats that crystal habit changes, and enters downtake, sends into the crystallizer tank of bottom, makes crystal continue to grow up.Continuing controlled temperature in the crystallizer tank is 70 ℃, monitoring serum density＞1000Kg/m
3After, the extraction slurries are sent into swirler makes solid-liquid separation, and subsequent technique is with embodiment 1.
Embodiment 11
The gypsum of releasing from the flue gas desulphurization system settling tank is without washing, and concentration of slurry is about 10～20%, these slurries directly can be sent into oxidation trough or be utilized surge tank, then slurries is sent into the gypsum treatment process gypsum is carried out modification.Slurries at first enter oxidation trough, and pH is about 4 in the oxidation trough, and presses 60Nm
3Air/m
3The ratio of slurries is sent into air, under the condition about 60 ℃, promotes the complete oxidation of desulfurated plaster.Gypsum behind the complete oxidation enters thickener and is thickened to 50%, sends into slurry commanding tank.The liquid-solid bulk concentration of slurry commanding tank entoplasm is about 20%, and the medium crystallization agent total concn is 10%, consists of: CaCl
23.5%, MgCl
23.5%, KCl 3%.Mix after heat exchanger is warming up to the evaporator tank that enters crystallizer top after 100 ℃.Keep 100 ℃ and certain surface pressure in the evaporator tank, residence time 1hr treats that crystal habit changes, and enters downtake, sends into the crystallizer tank of bottom, makes crystal continue to grow up.Continuing controlled temperature in the crystallizer tank is 100 ℃, monitoring serum density＞1000Kg/m
3After, the extraction slurries are sent into swirler makes solid-liquid separation, and subsequent technique is with embodiment 1.
Embodiment 12
The gypsum of releasing from the flue gas desulphurization system settling tank is without washing, and concentration of slurry is about 10～20%, these slurries directly can be sent into oxidation trough or be utilized surge tank, then slurries is sent into the gypsum treatment process gypsum is carried out modification.Slurries at first enter oxidation trough, and pH is about 5 in the oxidation trough, and presses 60Nm
3Air/m
3The ratio of slurries is sent into air, under the condition about 60 ℃, promotes the complete oxidation of desulfurated plaster.Gypsum behind the complete oxidation enters thickener and is thickened to 50%, sends into slurry commanding tank.The liquid-solid bulk concentration of slurry commanding tank entoplasm is about 20%, and the medium crystallization agent total concn is 26%, consists of: CaCl
29%, MgCl
29%, KCl 8%.Mix after heat exchanger is warming up to the evaporator tank that enters crystallizer top after 100 ℃.Keep 100 ℃ and certain surface pressure in the evaporator tank, residence time 1hr treats that crystal habit changes, and enters downtake, sends into the crystallizer tank of bottom, makes crystal continue to grow up.Continuing controlled temperature in the crystallizer tank is 100 ℃, monitoring serum density＞1000Kg/m
3After, the extraction slurries are sent into swirler makes solid-liquid separation, and subsequent technique is with embodiment 1.
Embodiment 13
The gypsum of releasing from the flue gas desulphurization system settling tank is without washing, and concentration of slurry is about 10～20%, these slurries directly can be sent into oxidation trough or be utilized surge tank, then slurries is sent into the gypsum treatment process gypsum is carried out modification.Slurries at first enter oxidation trough, and pH is about 6 in the oxidation trough, and presses 60Nm
3Air/m
3The ratio of slurries is sent into air, under the condition about 60 ℃, promotes the complete oxidation of desulfurated plaster.Gypsum behind the complete oxidation enters thickener and is thickened to 50%, sends into slurry commanding tank.The liquid-solid bulk concentration of slurry commanding tank entoplasm is about 20%, and the medium crystallization agent total concn is 10%, consists of: CaCl
210%.Mix after heat exchanger is warming up to the evaporator tank that enters crystallizer top after 100 ℃.Keep 100 ℃ and certain surface pressure in the evaporator tank, residence time 1hr treats that crystal habit changes, and enters downtake, sends into the crystallizer tank of bottom, makes crystal continue to grow up.Continuing controlled temperature in the crystallizer tank is 100 ℃, monitoring serum density＞1000Kg/m
3After, the extraction slurries are sent into swirler makes solid-liquid separation, and subsequent technique is with embodiment 1.
Embodiment 14
The gypsum of releasing from the flue gas desulphurization system settling tank is without washing, and concentration of slurry is about 10～20%, these slurries directly can be sent into oxidation trough or be utilized surge tank, then slurries is sent into the gypsum treatment process gypsum is carried out modification.Slurries at first enter oxidation trough, and pH is about 7 in the oxidation trough, and presses 60Nm
3Air/m
3The ratio of slurries is sent into air, under the condition about 60 ℃, promotes the complete oxidation of desulfurated plaster.Gypsum behind the complete oxidation enters thickener and is thickened to 50%, sends into slurry commanding tank.The liquid-solid bulk concentration of slurry commanding tank entoplasm is about 20%, and the medium crystallization agent total concn is 20%, consists of: MgCl
220%.Mix after heat exchanger is warming up to the evaporator tank that enters crystallizer top after 100 ℃.Keep 100 ℃ and certain surface pressure in the evaporator tank, residence time 1hr treats that crystal habit changes, and enters downtake, sends into the crystallizer tank of bottom, makes crystal continue to grow up.Continuing controlled temperature in the crystallizer tank is 100 ℃, monitoring serum density＞1000Kg/m
3After, the extraction slurries are sent into swirler makes solid-liquid separation, and subsequent technique is with embodiment 1.
Embodiment 15
The gypsum of releasing from the flue gas desulphurization system settling tank is without washing, and concentration of slurry is about 10～20%, these slurries directly can be sent into oxidation trough or be utilized surge tank, then slurries is sent into the gypsum treatment process gypsum is carried out modification.Slurries at first enter oxidation trough, and pH is about 8 in the oxidation trough, and presses 60Nm
3Air/m
3The ratio of slurries is sent into the flue gas in the sulfur removal technology, under the condition about 60 ℃, promotes the complete oxidation of desulfurated plaster.Gypsum behind the complete oxidation enters thickener and is thickened to 50%, sends into slurry commanding tank.The liquid-solid bulk concentration of slurry commanding tank entoplasm is about 20%, and the medium crystallization agent total concn is 5%, consists of: KCl5%.Mix after heat exchanger is warming up to the evaporator tank that enters crystallizer top after 100 ℃.Keep 100 ℃ and certain surface pressure in the evaporator tank, residence time 1hr treats that crystal habit changes, and enters downtake, sends into the crystallizer tank of bottom, makes crystal continue to grow up.Continuing controlled temperature in the crystallizer tank is 100 ℃, monitoring serum density＞1000Kg/m
3After, the extraction slurries are sent into swirler makes solid-liquid separation, and subsequent technique is with embodiment 1.
Claims (10)
1. a normal pressure salt solustion mehtod is produced α-half water desulfurated plaster technology, comprising:
(1) the precipitation slurry of the calcium sulfite in the settling bath in the sulfur removal technology is sent into oxidation trough at the dispensing air or import under the condition of the flue gas in the sulfur removal technology and carry out abundant oxidation;
(2) the oxidation rear slurry is sent into slurry commanding tank after the thickener thickening, and the salts solution that adds certain proportioning in slurry commanding tank is made medium crystallization agent, mixes the back and forms certain density slurries;
(3) slurries that prepare are sent into crystallizer and under the certain pH value condition, carried out crystallization;
(4) crystallization of crystallizer bottom is extracted out by slush pump, deliver to supply with and enter whizzer behind the groove gravity settling and carry out solid-liquid separation;
(5) with the washing of isolated α-half water desulfurated plaster, the medium crystallization agent cyclically utilizing after washing water concentrate through vaporizer;
(6) α-half water desulfurated plaster drying, the packing after will washing.
2. normal pressure salt solustion mehtod according to claim 1 is produced α-half water desulfurated plaster technology, it is characterized in that: described thickener slurries are thickened to concentration of slurry and are (weight percent): 10～70%.
3. normal pressure salt solustion mehtod according to claim 1 is produced α-half water desulfurated plaster technology, it is characterized in that: the add-on of salts solution is (weight percent) in the described slurry commanding tank: 0.5～30%.
4. normal pressure salt solustion mehtod according to claim 1 is produced α-half water desulfurated plaster technology, it is characterized in that: the slurry temperature scope in the described crystallizer is: 50～110 ℃, the pH value of slurries is: 3～8.
5. normal pressure salt solustion mehtod according to claim 1 is produced α-half water desulfurated plaster technology, it is characterized in that: the slurries residence time is 0.5～50hr in the crystallizer.
6. normal pressure salt solustion mehtod according to claim 1 is produced α-half water desulfurated plaster technology, and it is characterized in that: described medium crystallization agent is the aqueous solution of the soluble salt of basic metal and alkaline-earth metal, and total add-on is (weight percent): 0.5～30%.
7. normal pressure salt solustion mehtod according to claim 6 is produced α-half water desulfurated plaster technology, and it is characterized in that: described medium crystallization agent is CaCl
2, MgCl
2, any or several the solution mixture among the KCl.
8. normal pressure salt solustion mehtod according to claim 6 is produced α-half water desulfurated plaster technology, it is characterized in that: also can add the crystal formation modifying agent in the described medium crystallization agent, the crystal formation modifying agent is a kind of in organic multicomponent acid, the tensio-active agent or several mixture, and total add-on is (weight percent): 0～5%.
9. normal pressure salt solustion mehtod according to claim 8 is produced α-half water desulfurated plaster technology, it is characterized in that: described crystal formation modifying agent is a kind of in Succinic Acid, citric acid, Sodium dodecylbenzene sulfonate, the glyceryl monostearate or several mixture.
10. normal pressure salt solustion mehtod according to claim 6 is produced α-half water desulfurated plaster technology, it is characterized in that: also can add stablizer in the described medium crystallization agent, stablizer is a polyvalent alcohol, and add-on is (weight percent): 0～10%.
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| CNB031426077A CN100382873C (en) | 2003-06-06 | 2003-06-06 | Techlogogy for making alpha semi-water desulfur gypsum using normal pressure salt solution method |
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|---|---|---|---|
| CNB031426077A CN100382873C (en) | 2003-06-06 | 2003-06-06 | Techlogogy for making alpha semi-water desulfur gypsum using normal pressure salt solution method |
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| Publication Number | Publication Date |
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| CN1513766A true CN1513766A (en) | 2004-07-21 |
| CN100382873C CN100382873C (en) | 2008-04-23 |
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| CN1325419C (en) * | 2005-12-19 | 2007-07-11 | 北京朗新明环保科技有限公司 | Dehydration method and apparatus of flue gas desulfurization gypsum slurry |
| CN100371279C (en) * | 2006-06-06 | 2008-02-27 | 宁夏建筑材料研究院 | Method for producing alpha semi-hydrated gypsum in high intensity, and low expansion |
| CN102173621A (en) * | 2011-01-31 | 2011-09-07 | 上海市建筑科学研究院(集团)有限公司 | Short column-shaped high-strength desulfurized alpha-gypsum |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5140399A (en) * | 1974-10-03 | 1976-04-05 | Taki Chemical | Aryusankarushiumuno shorihoho |
| US5312609A (en) * | 1992-12-31 | 1994-05-17 | Dravo Lime Company | Method of sulfur dioxide removal from gaseous streams with α-hemihydrate gypsum product formation |
| US6197200B1 (en) * | 1999-05-11 | 2001-03-06 | Eastroc Llc | Method of purifying flue gas waste slurries for use in gypsum production |
| US6254843B1 (en) * | 1999-11-19 | 2001-07-03 | Marsulex Environmental Technologies, Llc | Process for the reclamation of calcium sulfite produced by a calcium-based FGD system |
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2003
- 2003-06-06 CN CNB031426077A patent/CN100382873C/en not_active Expired - Lifetime
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