CN102383179A - Method of comprehensive utilization of industrial waste acid and ardealite - Google Patents
Method of comprehensive utilization of industrial waste acid and ardealite Download PDFInfo
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- CN102383179A CN102383179A CN2011103007808A CN201110300780A CN102383179A CN 102383179 A CN102383179 A CN 102383179A CN 2011103007808 A CN2011103007808 A CN 2011103007808A CN 201110300780 A CN201110300780 A CN 201110300780A CN 102383179 A CN102383179 A CN 102383179A
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- industrial waste
- calcium sulfate
- ardealite
- waste acid
- acid
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- 239000002253 acid Substances 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 35
- 239000002440 industrial waste Substances 0.000 title claims abstract description 21
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims abstract description 61
- 239000013078 crystal Substances 0.000 claims abstract description 34
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 6
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 claims description 37
- 235000011132 calcium sulphate Nutrition 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 10
- 230000006641 stabilisation Effects 0.000 claims description 9
- 238000011105 stabilization Methods 0.000 claims description 9
- 230000008030 elimination Effects 0.000 claims description 5
- 238000003379 elimination reaction Methods 0.000 claims description 5
- 239000001175 calcium sulphate Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 13
- 239000002699 waste material Substances 0.000 abstract description 12
- 239000000047 product Substances 0.000 abstract description 11
- 239000002994 raw material Substances 0.000 abstract description 8
- 238000002156 mixing Methods 0.000 abstract description 4
- 239000002910 solid waste Substances 0.000 abstract description 3
- 239000010440 gypsum Substances 0.000 abstract description 2
- 229910052602 gypsum Inorganic materials 0.000 abstract description 2
- 239000004615 ingredient Substances 0.000 abstract description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 239000000706 filtrate Substances 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 230000000087 stabilizing effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 12
- 239000000126 substance Substances 0.000 description 11
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 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 7
- 239000011507 gypsum plaster Substances 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 230000008901 benefit Effects 0.000 description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 4
- 239000000920 calcium hydroxide Substances 0.000 description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 4
- 239000000292 calcium oxide Substances 0.000 description 4
- 235000012255 calcium oxide Nutrition 0.000 description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 4
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000002686 phosphate fertilizer Substances 0.000 description 4
- 238000004062 sedimentation Methods 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QLULGSLAHXLKSR-UHFFFAOYSA-N azane;phosphane Chemical compound N.P QLULGSLAHXLKSR-UHFFFAOYSA-N 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 235000010215 titanium dioxide Nutrition 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 241000276489 Merlangius merlangus Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- YOBAEOGBNPPUQV-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe].[Fe] YOBAEOGBNPPUQV-UHFFFAOYSA-N 0.000 description 1
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 1
- 239000010808 liquid waste Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- -1 organism Inorganic materials 0.000 description 1
- 239000002367 phosphate rock Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 235000021110 pickles Nutrition 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920013657 polymer matrix composite Polymers 0.000 description 1
- 239000011160 polymer matrix composite Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The invention provides a method for preparing calcium sulfate crystal whisker with industrial waste acid and ardealite, which comprises the following steps: mixing ardealite and industrial waste acid, adjusting pH of the solution with ammonia water, and then stirring; immediately filtering the solution, cooling the filtrate, all crystal being separated out, and performing conventional stabilizing process on the surface of the crystal; and then drying, and obtaining calcium sulfate crystal whisker. The diameter of the obtained calcium sulfate crystal whisker is 1-4mum, the length is 50-200mum, the moh's hardness is 3-4, the tensile strength is 20.5Gpa, the elastic modulus is 178GPa, and the refractive index is 1.585. With the invention, industrial waste acid and solid waste ardealite can be utilized, the waste product of the two kinds of industries can be utilized, so the goal of treatment of wastes with processes of wastes against one another can be achieved; exploitation of natural gypsum can be reduced, resource can be saved, and meanwhile the production cost of calcium sulfate crystal whisker can be reduced; and the limit on the ingredients of the raw material ardealite and industrial waste acid is not strict, the application range is wide, the condition is wide, and the process is simpler.
Description
Technical field
The present invention relates to a kind of spent acid and solid slag phosphogypsum comprehensive utilization method, be specifically related to the method for a kind of industrial waste acid and preparing calcium sulphate whiskers from ardealite, belong to chemical industry comprehensive utilization of waste materials technical field.
Background technology
Phosphogypsum is that Rock Phosphate (72Min BPL) and sulfuric acid react and the industrial residue that produces in the Wet-process Phosphoric Acid Production process; Phosphoric acid by calculating 1 ton of every production will produce 4～5 tons of phosphogypsums; Phosphogypsum annual quantity discharged in the whole world reaches more than 200,000,000 ton at present; But the utilization ratio of phosphogypsum does not surpass 10%, and the processing of phosphogypsum, disposal and comprehensive utilization have become a global difficult problem.China's phosphate fertilizer production ranks first in the world, and the phosphate fertilizer of production high density (like phosphorus ammonium, coarse whiting etc.) needs a large amount of phosphoric acid by wet processes, also can produce a large amount of phosphogypsum slags thereupon.Great majority are stored up or are toppled over, and the stacking of phosphogypsum not only takies a large amount of soils, expends a huge sum of money, and sour water leakage pollution water source, form secondary pollution.The main chemical compositions of phosphogypsum is identical with the plaster of paris, is sulphur, calcium and the gypsum resource with multiple potential use, but impurity such as the phosphorus that it contained, fluorine, organism, alkali metal constitute adverse influence to comprehensive utilization.Therefore, from the angle of the environment protection and the utilization of resources, the processing of phosphogypsum slag is extremely urgent with utilization.
Simultaneously, in industrial production, it is extremely widely that the surface acid of metallic substance is handled, and produces a large amount of spent pickle liquors therefrom.In sulfate process titanium dioxide was produced, one ton of titanium white of every production was approximately discharged 8～10 tons of acid waste liquids.With these two kinds of acid waste liquids that the source is the master, all contain certain density acid.People are seeking to administer the approach that utilizes this type acid waste liquid always for a long time, but also lack economy, ideal recycling measure at present, thereby environment is caused great pollution.
At present, the main method of utilizing phosphogypsum both at home and abroad is exactly that phosphogypsum is decomposed system producing sulfuric acid and jointly cement, and it is under-supply to remedy sulfuric acid, can solve the outlet of phosphogypsum again, administers the pollution of phosphogypsum to environment.But, big, the poor product quality of current technology investment, the technical problems that also exist are difficult to utilization and extention.If can utilize industrial waste acid to make phosphogypsum become calcium sulfate crystal whiskers, then can solve two kinds of trade refuses, created new profit simultaneously and be worth.
A kind of method of utilizing industrial waste acid to handle emulsifying liquid waste water is disclosed in publication number CN1410365.This method is the spent acid solution that adds in the emulsion after use after the pickling of its volume 4～12%, stirs when adding the spent acid solution after the pickling, make its mixed solution thorough mixing after; Its mixed solution was left standstill 18～36 hours; With upper strata oil and water sepn, in isolated water, add its lime carbonate of heavy 0.8～5%, and left standstill 2～12 hours then; Adding liming then regulates pH value 7～9 or adds 0.5～5% gac or tail over activated coal; After fully stirring, leave standstill 18～36 hours after, upper water gets final product qualified discharge.But its subnatant is still acid waste liquid, is difficult to handle.
A kind of high-strength phosphogypoum building block and preparation method thereof is disclosed in publication number 02113258.5.The feed composition of building block mainly is the waste material phosphogypsum in the production of phosphate fertilizer in this method, and other feed composition comprise non-sharp method recombiner, activated compound agent, promotor and water.The main technique link of building block preparation side has, and tentatively mixing of raw material, digestion reaction, main mixing, compression moulding, vapor cure, leaves standstill and dries etc.With the building block that the present invention makes, ultimate compression strength is high, and unit weight is low, and production cost is low.Can solve the stacking occupation of land and the pollution problem of the waste material phosphogypsum in the production of phosphate fertilizer, also can solve traditional architecture and destroy arable land and pollutant atmosphere problem, have good economic benefits and social benefit with brick.
A kind of treatment process of phosphogypsum is disclosed in publication number CN1424273.This method utilizes settling methods to handle the method for formed phosphogypsum sub product in phosphorus ammonium and the secondary calcium phosphate production process, and process step comprises: grinding, dilution, sedimentation and oven dry is characterized in that: the sedimentation operation after the dilution operation has first grade subsides, secondary sedimentation, three grades of sedimentations; And one, two, three settling tank is arranged continuously; The present invention had both solved the pollution problem of phosphogypsum, and the various handled things with gained are applied to respectively turn bane into boon in the different industrial production again; Simultaneously; This method is simple, and cost is low, has higher economic value.
A kind of method for preparing blue copperas and co-producing calcium hydroxide with phosphogypsum is disclosed in publication number CN101844788A.The concrete steps of this method are (1) the first amount of the pure substance calcium sulfate that contained of the industrial phosphogypsum product of conversion; With phosphogypsum and verditer solution according to the amount of calcium sulfate and verditer pure substance through being in the reactor drum put into of 1 ︰ 0.52～0.92, carry out chemical reaction under slowly stirring; (2) and instead with reaction product suction filtration in the suction filtration machine of step (1) gained, obtain clarifying cupric sulfate pentahydrate and calcium hydroxide filter cake; (3) the clarifying cupric sulfate pentahydrate solution of step (2) gained is sent in the underpressure distillation device, when underpressure distillation is separated out to cupric sulfate pentahydrate simultaneously, all entered and cool off normal temperature in the water cooler, pulverize through first kibbler, thereby obtain the cupric sulfate pentahydrate product; (4) said calcium hydroxide filter cake with water washing after, centrifugal through whizzer, solid-liquid separation, solid is dry through moisture eliminator, pulverize through second kibbler again, obtain the calcium hydroxide product.
Up to now, do not see with the relevant report of industrial waste acid with the phosphogypsum comprehensive utilization.Calcium sulfate crystal whiskers adds in the high molecular polymer, can strengthen many performances such as polymkeric substance mechanical property, thermotolerance, is widely used at Aeronautics and Astronautics and numerous civilian industries field; It adds in the plastic, rubber; Can improve tensile strength, flexural strength, spring rate and the heat-drawn wire etc. of matrix material; It is medium to replace asbestos to add abrasives, material of construction, lagging material to, can be used as reinforcing filler and is used for industries such as polymer matrix composites, sticker.Calcium sulfate crystal whiskers excellent property, cheap, environmental protection have wide application and market outlook.
Summary of the invention
The purpose of this invention is to provide a kind of is the method for feedstock production calcium sulfate crystal whiskers with industrial waste acid and phosphogypsum, solves the problem of environmental pollution that is brought of storing up of industrial waste acid and phosphogypsum, can also reduce the exploitation of the plaster of paris, economizes on resources.
The present invention realizes through following technical proposal: the method for a kind of industrial waste acid and preparing calcium sulphate whiskers from ardealite, and following each step of process:
A. be 1 ︰ 0.5～75 by solid-to-liquid ratio, phosphogypsum is mixed with industrial waste acid, and to use the pH value of ammoniacal liquor regulator solution be 2～6, in 30～80 ℃ of stirring 20～40min down;
B. step B gained solution is filtered immediately, discard filter residue, obtain filtrating;
C. step B gained filtrating is at room temperature cooled off 10～30min, crystal is all separated out, the elimination spent acid;
D. conventional stabilization treatment is carried out on step C gained crystalline surface;
E. step D gained crystal is dried to water cut less than 0.3% under 80～300 ℃, promptly obtains calcium sulfate crystal whiskers.
The steps A that is back to the spent acid of said step C continues to recycle, and can reuse 3～8 times.
The conventional stabilization treatment of said step D is carried out stabilization treatment for utilizing conventional physics, chemistry or mechanical means to the crystalline surface.
The raw materials used chemical ingredients of said steps A is:
The main chemical compositions mass percent of raw material phosphogypsum is: quicklime 30～47%, sulfurous gas 45～51%, red oxide of iron 0.08～5.31%; Aluminium sesquioxide 0.12～2.65%; Vanadium Pentoxide in FLAKES 0.47～6.28%, fluorine 0.05～0.26%, silicon-dioxide 0.20～5.38%;
Primary industry spent acid volumetric concentration is 2～10%.
Effect that the present invention possesses and advantage:
Gained calcium sulfate crystal whiskers diameter of the present invention is 1～4 μ m, length 50～200 μ m, and Mohs' hardness is 3～4, and tensile strength is 20.5Gpa, and Young's modulus is 178GPa, refractive index 1.585.
(1) utilized industrial waste acid and solid waste phosphogypsum, the refuse in two kinds of industry all obtains utilizing, and reaches the purpose of the treatment of wastes with processes of wastes against one another;
(2) the utilizing in the process of trade refuse, output the high product of added value, carry and led economic benefit, let solid waste become real resource and be used;
(3) product calcium sulfate crystal whiskers is compared with high-quality acid-respons produces with the plaster of paris, and diameter, length is even, quality is the same, has reduced the exploitation of the plaster of paris, has practiced thrift resource, has also reduced the production cost of calcium sulfate crystal whiskers simultaneously;
(4) this technology does not have strict restriction for the composition of raw material phosphogypsum and industrial waste acid, and is applied widely, condition is wide, and technology is fairly simple, is easy to carry out suitability for industrialized production.
Embodiment
To combine embodiment further to illustrate content of the present invention below, but these instances do not limit protection scope of the present invention.
Embodiment 1
A. being 1 ︰ 15 by solid-to-liquid ratio, is that 5% industrial waste acid mixes with 100g phosphogypsum and 1500mL volumetric concentration, and to use the pH value of ammoniacal liquor regulator solution be 3.5, in 60 ℃ of stirring 30min down; Wherein, the main chemical compositions mass percent of raw material phosphogypsum is: CaO=39.35, SO
2=50.86, Fe
2O
3=4.83, Al
2O
3=2.56, P
2O
5=1.87, F=0.21, SiO
2=0.32;
B. step B gained solution is filtered immediately, discard filter residue, obtain filtrating;
C. step B gained filtrating is at room temperature cooled off 25min, crystal is all separated out, the elimination spent acid; The steps A that is back to spent acid continues to recycle, and can reuse 3 times;
D. the conventional physics method of step C gained crystalline surface by utilizing is carried out stabilization treatment;
E. step D gained crystal being dried to water cut under 220 ℃ is 0.2%, promptly obtains calcium sulfate crystal whiskers.
With ESEM product is detected, the result shows that the diameter of calcium sulfate crystal whiskers is that 1～4 μ m and length are 50～200 μ m.Suitable with the calcium sulfate crystal whiskers quality that makes with the plaster of paris and high-quality acid.
Embodiment 2
A. being 1 ︰ 0.5 by solid-to-liquid ratio, is that 2% industrial waste acid mixes with 80g phosphogypsum and 40mL volumetric concentration, and to use the pH value of ammoniacal liquor regulator solution be 2, in 30 ℃ of stirring 40min down; Wherein, the main chemical compositions mass percent of raw material phosphogypsum is: CaO=44.21, SO
2=50.03, Fe
2O
3=2.24, Al
2O
3=2.25, P
2O
5=0.78, F=0.12, SiO
2=0.37;
B. step B gained solution is filtered immediately, discard filter residue, obtain filtrating;
C. step B gained filtrating is at room temperature cooled off 30min, crystal is all separated out, the elimination spent acid; The steps A that is back to spent acid continues to recycle, and can reuse 5 times;
D. step C gained crystalline surface by utilizing conventional chemical method is carried out stabilization treatment;
E. step D gained crystal being dried to water cut under 300 ℃ is 0.1%, promptly obtains calcium sulfate crystal whiskers.
With ESEM product is detected, the result shows that the diameter of calcium sulfate crystal whiskers is that 1～4 μ m and length are 50～200 μ m.Suitable with the calcium sulfate crystal whiskers quality that makes with the plaster of paris and high-quality acid.
Embodiment 3
A. being 1 ︰ 75 by solid-to-liquid ratio, is that 10% industrial waste acid mixes with 60g phosphogypsum and 4500mL volumetric concentration, and to use the pH value of ammoniacal liquor regulator solution be 6, in 80 ℃ of stirring 20min down; Wherein, the main chemical compositions mass percent of raw material phosphogypsum is: CaO=46.56, SO
2=45.27, Fe
2O
3=4.24, Al
2O
3=0.29, P
2O
5=2.13, F=0.2, SiO
2=1.31;
B. step B gained solution is filtered immediately, discard filter residue, obtain filtrating;
C. step B gained filtrating is at room temperature cooled off 10min, crystal is all separated out, the elimination spent acid; The steps A that is back to spent acid continues to recycle, and can reuse 8 times;
D. step C gained crystalline surface by utilizing conventional mechanical method is carried out stabilization treatment;
E. step D gained crystal being dried to water cut under 80 ℃ is 0.28%, promptly obtains calcium sulfate crystal whiskers.
With ESEM product is detected, the result shows that the diameter of calcium sulfate crystal whiskers is that 1～4 μ m and length are 50～200 μ m.Suitable with the calcium sulfate crystal whiskers quality that makes with the plaster of paris and high-quality acid.
Claims (3)
1. the method for industrial waste acid and preparing calcium sulphate whiskers from ardealite is characterized in that through following each step:
A. be 1 ︰ 0.5～75 by solid-to-liquid ratio, phosphogypsum is mixed with industrial waste acid, and to use the pH value of ammoniacal liquor regulator solution be 2～6, in 30～80 ℃ of stirring 20～40min down;
B. step B gained solution is filtered immediately, discard filter residue, obtain filtrating;
C. step B gained filtrating is at room temperature cooled off 10～30min, crystal is all separated out, the elimination spent acid;
D. conventional stabilization treatment is carried out on step C gained crystalline surface;
E. step D gained crystal is dried to water cut less than 0.3% under 80～300 ℃, promptly obtains calcium sulfate crystal whiskers.
2. method according to claim 1 is characterized in that: the spent acid of said step C is back to steps A to be continued to recycle, and can reuse 3～8 times.
3. method according to claim 1 and 2 is characterized in that: the conventional stabilization treatment of said step D is carried out stabilization treatment for utilizing conventional physics, chemistry or mechanical means to the crystalline surface.
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| CN201110300780.8A CN102383179B (en) | 2011-10-09 | 2011-10-09 | A kind of method that industrial waste acid and phosphogypsum fully utilize |
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|---|---|---|---|
| CN201110300780.8A CN102383179B (en) | 2011-10-09 | 2011-10-09 | A kind of method that industrial waste acid and phosphogypsum fully utilize |
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| CN102383179B CN102383179B (en) | 2015-09-09 |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102634843A (en) * | 2012-04-27 | 2012-08-15 | 昆明理工大学 | Method for preparing micron-sized calcium sulfate particles and crystal whiskers from phosphogypsum |
| CN103696014A (en) * | 2013-12-12 | 2014-04-02 | 宁夏贝利特化工有限公司 | Method for producing calcium sulfate whisker and calcium sulfate by using wastes produced during production of nitroguanidine and dicyandiamide |
| CN103938263A (en) * | 2014-04-09 | 2014-07-23 | 江苏诺姆化学有限公司 | Technology for preparing calcium sulfate whisker from dimethyl cyanoamino di-tyiocarbonate wastewater |
| CN105332058A (en) * | 2015-11-06 | 2016-02-17 | 云南力达一矿物技术有限公司 | Method for preparing gypsum whiskers for papermaking from phosphogypsum under normal pressure in circulating dissolving method |
| CN105603505A (en) * | 2016-01-06 | 2016-05-25 | 昆明理工大学 | Method for hydrothermal synthesis of high-draw-ratio calcium sulfate whiskers with ardealite |
| CN105755543A (en) * | 2016-04-12 | 2016-07-13 | 包头稀土研究院 | Method for producing calcium sulfate whisker by utilizing baotite transformation magnesium sulfate waste water |
| CN106698497A (en) * | 2017-01-22 | 2017-05-24 | 武汉工程大学 | Method for preparing calcium sulfate from ardealite |
| CN108277537A (en) * | 2018-01-26 | 2018-07-13 | 黑龙江科技大学 | A method of preparing hemihydrate calcium sulfate crystal whisker using expanded graphite production waste water |
| CN108516713A (en) * | 2018-03-16 | 2018-09-11 | 中南大学 | A kind of pretreatment of ardealite and application process |
| CN113774716A (en) * | 2021-09-08 | 2021-12-10 | 福泉环保城发展有限公司 | Multifunctional auxiliary agent for improving paper strength and preparation method thereof |
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| CN102634843A (en) * | 2012-04-27 | 2012-08-15 | 昆明理工大学 | Method for preparing micron-sized calcium sulfate particles and crystal whiskers from phosphogypsum |
| CN103696014A (en) * | 2013-12-12 | 2014-04-02 | 宁夏贝利特化工有限公司 | Method for producing calcium sulfate whisker and calcium sulfate by using wastes produced during production of nitroguanidine and dicyandiamide |
| CN103696014B (en) * | 2013-12-12 | 2015-12-30 | 宁夏贝利特化工有限公司 | By the method for producing nitroguanidine, the waste of Dyhard RU 100 produces calcium sulfate crystal whiskers and calcium sulfate |
| CN103938263A (en) * | 2014-04-09 | 2014-07-23 | 江苏诺姆化学有限公司 | Technology for preparing calcium sulfate whisker from dimethyl cyanoamino di-tyiocarbonate wastewater |
| CN105332058A (en) * | 2015-11-06 | 2016-02-17 | 云南力达一矿物技术有限公司 | Method for preparing gypsum whiskers for papermaking from phosphogypsum under normal pressure in circulating dissolving method |
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| CN105603505B (en) * | 2016-01-06 | 2018-05-11 | 昆明理工大学 | A kind of method that ardealite hydro-thermal prepares high length-diameter ratio calcium sulfate crystal whiskers |
| CN105603505A (en) * | 2016-01-06 | 2016-05-25 | 昆明理工大学 | Method for hydrothermal synthesis of high-draw-ratio calcium sulfate whiskers with ardealite |
| CN105755543A (en) * | 2016-04-12 | 2016-07-13 | 包头稀土研究院 | Method for producing calcium sulfate whisker by utilizing baotite transformation magnesium sulfate waste water |
| CN105755543B (en) * | 2016-04-12 | 2018-06-22 | 包头稀土研究院 | Utilize the method for baotite transition magnesium sulfate waste water production calcium sulfate crystal whiskers |
| CN106698497A (en) * | 2017-01-22 | 2017-05-24 | 武汉工程大学 | Method for preparing calcium sulfate from ardealite |
| CN108277537A (en) * | 2018-01-26 | 2018-07-13 | 黑龙江科技大学 | A method of preparing hemihydrate calcium sulfate crystal whisker using expanded graphite production waste water |
| CN108516713A (en) * | 2018-03-16 | 2018-09-11 | 中南大学 | A kind of pretreatment of ardealite and application process |
| CN113774716A (en) * | 2021-09-08 | 2021-12-10 | 福泉环保城发展有限公司 | Multifunctional auxiliary agent for improving paper strength and preparation method thereof |
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