CN103588237B - Decoloring and purifying method for flue gas desulfurization gypsum - Google Patents
Decoloring and purifying method for flue gas desulfurization gypsum Download PDFInfo
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- CN103588237B CN103588237B CN201310581650.5A CN201310581650A CN103588237B CN 103588237 B CN103588237 B CN 103588237B CN 201310581650 A CN201310581650 A CN 201310581650A CN 103588237 B CN103588237 B CN 103588237B
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- 238000000034 method Methods 0.000 title claims abstract description 52
- 229910052602 gypsum Inorganic materials 0.000 title claims abstract description 47
- 239000010440 gypsum Substances 0.000 title claims abstract description 47
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title abstract description 8
- 239000003546 flue gas Substances 0.000 title abstract description 8
- 238000006477 desulfuration reaction Methods 0.000 title abstract description 6
- 230000023556 desulfurization Effects 0.000 title abstract description 6
- 239000012452 mother liquor Substances 0.000 claims abstract description 57
- 239000012535 impurity Substances 0.000 claims abstract description 41
- 238000005406 washing Methods 0.000 claims abstract description 32
- 239000013078 crystal Substances 0.000 claims abstract description 29
- 239000002994 raw material Substances 0.000 claims abstract description 23
- 239000002002 slurry Substances 0.000 claims description 110
- 239000007788 liquid Substances 0.000 claims description 62
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 60
- 239000000725 suspension Substances 0.000 claims description 54
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 41
- 239000007787 solid Substances 0.000 claims description 36
- 239000011505 plaster Substances 0.000 claims description 33
- 230000007704 transition Effects 0.000 claims description 19
- 239000000126 substance Substances 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000012153 distilled water Substances 0.000 claims description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 14
- 238000000746 purification Methods 0.000 claims description 12
- 238000000605 extraction Methods 0.000 claims description 10
- 238000004042 decolorization Methods 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 239000003350 kerosene Substances 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 4
- 238000004064 recycling Methods 0.000 abstract description 10
- 239000002245 particle Substances 0.000 abstract description 4
- 238000009825 accumulation Methods 0.000 abstract description 2
- 239000010419 fine particle Substances 0.000 abstract description 2
- 238000000053 physical method Methods 0.000 abstract description 2
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 abstract 3
- 229910004815 CaSO4.0.5H2O Inorganic materials 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 76
- 239000000243 solution Substances 0.000 description 30
- 239000012065 filter cake Substances 0.000 description 25
- 239000012071 phase Substances 0.000 description 13
- 239000007790 solid phase Substances 0.000 description 12
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Inorganic materials [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 8
- 239000010413 mother solution Substances 0.000 description 7
- 239000006227 byproduct Substances 0.000 description 4
- 235000011132 calcium sulphate Nutrition 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 150000004683 dihydrates Chemical class 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000004567 concrete Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000011507 gypsum plaster Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 235000007926 Craterellus fallax Nutrition 0.000 description 1
- 240000007175 Datura inoxia Species 0.000 description 1
- 235000001018 Hibiscus sabdariffa Nutrition 0.000 description 1
- 101000993059 Homo sapiens Hereditary hemochromatosis protein Proteins 0.000 description 1
- 235000005291 Rumex acetosa Nutrition 0.000 description 1
- 240000007001 Rumex acetosella Species 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
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001175 calcium sulphate Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000000887 hydrating effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 235000003513 sheep sorrel Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000013268 sustained release Methods 0.000 description 1
- 239000012730 sustained-release form Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Landscapes
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention discloses a decoloring and purifying method for flue gas desulfurization gypsum. The decoloring and purifying method is realized through four steps of raw material washing, crystal form converting, product washing and drying, and mother liquor recycling. By virtue of the characteristics of CaSO4.2H2O capable of being converted to CaSO4.0.5H2O with fine particles at 100 DEG C and converted to CaSO4.2H2O with large particles at the normal temperature, the original CaSO4.2H2O crystals are damaged so as to expose out and separate impurities in the crystals through a common physical method. After the colored impurities are separated, the purpose of decoloring and purifying the flue gas desulfurization gypsum can be achieved, so that the problems of secondary pollution and economic burden caused by accumulation of a large quantity of flue gas desulfurization gypsum are solved.
Description
Technical field
The present invention relates to a kind of method making desulfurated plaster decolouring obtain higher whiteness gypsum in normal pressure salts solution.
Technical background
Due to coal resources in China comparatively horn of plenty and oil and natural gas resource is relatively deficient, therefore coal becomes the main energy sources of China.In coal, sulphur content is higher, produces a large amount of sulfurous gas in combustion processes.Due to the importance of environment protection, the wet desulphurization device that the coal-burning power plant of China more than 80% all adopts is to flue gas desulfurization, and Wet Flue Gas Desulfurization Technology produces a large amount of desulfurizing byproduct and desulfurated plaster.China produces industrial by-product desulfurated plaster about 4,300 ten thousand tons per year, and comprehensive utilization ratio is about 50%.The bulk deposition of desulfurated plaster not only takies a large amount of soil and factory building, and can form secondary pollution, has caused serious Environmental and ecological problems and economical load.In February, 2011, Ministry of Industry and Information issued " instruction about industry by-product gypsum comprehensive utilization ", suggestion requires that desulfurated plaster comprehensive utilization ratio in 2015 will reach 80%, industry by-product gypsum high value added utilization is encouraged in the exploitation of restriction plaster of paris ore deposit, and research desulfurated plaster recycling has been the task of top priority.
Calcium sulphate content in desulfurated plaster, more than 70%, is good gypsum resource.But desulfurized gesso of flue gas is often containing the dust impurities in more flue gas, and mainly flyash, silicon-dioxide and iron containing compounds, thus its whiteness is lower.Impurity in desulfurated plaster reduces hydrating capacity and the whiteness of gypsum, has had a strong impact on the range of application departing from gypsum.Desulfurated plaster has huge applications potentiality, can produce the plaster of Paris, paper panel gypsum, gypsum block, plaster hollow board, brushing gypsum, water-setting sustained release dosage etc. at building materials field; Agricultural aspect can be used for producing chemical fertilizer and alkali soil improvement etc.; Desulfurated plaster after process also can be used for producing high-strength semi-hydrated gypsum, calcium sulfate crystal whiskers etc. and has high value added product.
Purification at present to desulfurated plaster, in US Patent No. P5215672 and USP5500197, have employed the purification that multi-stage water power swirler technique and fine particle stage trapping technique carry out gypsum slurries respectively, that physical means is purified completely, but because the impurity portion in gypsum is also present in calcium sulfate particle inside, the method gypsum product quality obtained of purifying is lower.In patent CN101870494A, adopt chemical process to purify to disengaging gypsum, key step is: pickling post-heating, the impurity of solid-liquid separation removing while hot, by liquid phase recrystallization under lesser temps, then solid-liquid separation, filter cake is washed oven dry and obtains product.But the gypsum output of this technique unit volume mother liquor is lower, and the dissolution process time is longer, compares power consumption.Therefore, the recycling in order to realize desulfurated plaster is badly in need of that a kind of energy consumption is low, product whiteness is high desulfurated plaster is purified, decoloration process.The essential property of the desulfurated plaster raw material that the present invention is used is as follows:
Summary of the invention
The object of the invention is the whiteness and the purity that improve desulfurated plaster more efficiently, to expand its Application Areas.The present invention utilizes CaSO
42H
2o can be converted into the tiny CaSO of particle 100 DEG C time
40.5H
2o and CaSO at normal temperatures
40.5H
2o can be converted into again the thick CaSO of particle
42H
2the characteristic of O is by original CaSO
42H
2o crystal damage makes the impurity being present in crystals come out and then can utilize common physical method for separation impurity.Foreign pigment just can reach the decolouring of desulfurated plaster and the object of purification after being separated.Thus solve the problem that the accumulation of a large amount of desulfurated plaster causes secondary pollution and economical load.
Technical scheme of the present invention is:
A method for desulfurated plaster decolorization and purification, comprises the following steps:
(1). raw material is washed:
A. according to quality than desulfurated plaster: water=1 ~ 3:10, is positioned in container together, stir 30 ~ 90min, then leave standstill 1 ~ 3min, make its layering;
B. the suspension liquid on the top after layering in a being poured into the degree of depth is in the disk container of 25 ~ 50mm, leaves standstill 1 ~ 3min, makes its layering; Lower floor in a after layering abandons;
C. slowly poured out on the upper strata (suspension liquid) after layering in b, in disk container, remaining lower floor is exactly comparatively pure middle level gypsum;
D. c is walked the suspension liquid poured out and carry out solid-liquid separation, removing suspended substance, the water obtained can be used as a step in next circulation to be continued to use;
(2). crystal transition:
A. be: concentrated hydrochloric acid: solvent=1:7.5 ~ 12.5 that mass ratio is CaCl according to volume ratio
2=middle level gypsum (in butt, namely removing the quality after free water)=1:1.75 ~ 15, every 7 ~ 15g middle level gypsum adds concentrated hydrochloric acid 8 ~ 12ml, preparation reacting slurry, and slurries is heated to 90 ~ 100 DEG C of reaction 1 ~ 5h;
B. a gained slurries constant temperature at 10 DEG C ~ 40 DEG C is left standstill 8h;
C. gained slurries in b taken out and stir, then leaving standstill and separate into after solid and suspension liquid two-phase until slurries, suspension liquid is poured out; The suspended impurity filtered out in suspension liquid obtains solution, and solution forms slurries with solids mixing again;
D. repeat c operation 5 ~ 7 times, finally obtain solid matter and the mother liquor of white;
(3) product washing: the product distilled water wash that (2) step is obtained 3 ~ 5 times;
(4) dry: by (3) step to product at 45 DEG C ± 1 DEG C, dry 8 ~ 10h can obtain the finished product.
The mother liquor that in described step (2), in crystal transition process, the solvent described in a is water or obtains in previously producing, or the mixture of the two.
The method of described desulfurated plaster decolorization and purification, further comprising the steps of: in step (2) crystal transition, d walks the mother liquor obtained, as wherein H
+concentration is lower than adding concentrated hydrochloric acid (12mol/L) during 1.44mol/L again by H
+reusable after being supplemented to 1.44mol/L; Can by Fe by the three grades of extractions of TBP-kerosene after the iron in solution runs up to 20mmol/L
3+concentration controls at below 0.6mmol/L; The TBP-kerosene water extracting iron later can reclaim through secondary back extraction.
Beneficial effect of the present invention is: the present invention utilizes dihydrate gypsum can change into semi-hydrated gypsum at relatively high temperatures, realizes the transformation of gypsum crystal type, thus is separated by the solid impurity of gypsum crystal granule interior, then utilizes CaSO
40.5H
2the aquation of O crystal and CaSO
42H
2o acting in conjunction of crystallization from solution obtains the dihydrate gypsum crystal that volume enlarges markedly, thus is convenient to and tiny impurity (SiO
2take on a red color, brown or sorrel) be separated, and then realize purification and the decolouring of desulfurated plaster.HCl consumption (HCl main with a small amount of calcium carbonate reaction consumption in raw material with volatilize on a small quantity) between 26% ~ 17% in operating process, so mother liquor just can be reused after only needing to supplement HCl on a small quantity.By crystallization control process, feed molar ratio can by desulfurated plaster whiteness by 33.98% bring up to 90% and purity bring up to 97% by 96%.In slurries of the present invention, solid load is greatly the product that every 100ml mother liquor can obtain more than 6g, in patent CN101870494A, recrystallization method is only up to 3.776g, and the reaction times of the present invention is short, and namely the shortest time is only 10h(example 8 ~ 10), and in patent CN101870494A the time in reaction times of recrystallization method be 22h, so the present invention is more energy-conservation, the production capacity of unit time is larger.
Accompanying drawing explanation
Fig. 1 is the decolourizing extracting technique schematic flow sheet of embodiment 1.
Fig. 2 is the XRD figure of desulfurated plaster raw material in embodiment 1.
Fig. 3 is the XRD figure of middle level gypsum after washing in embodiment 1.
Fig. 4 is the XRD figure of product after purification decolouring in embodiment 1.
Fig. 5 is the XRD figure of the isolated impurity of decolorization of purifying in embodiment 1.
Embodiment
After now specific examples of the present invention being described in.
Embodiment 1: concrete operations are as follows
(1) raw material washing:
A. taking 100.0g desulfurated plaster (XRD characterization result is shown in accompanying drawing 2) and 1000.0ml water, to be positioned over capacity be together in the beaker of 1L.Stir 30min, solid-liquid is fully mixed; Then leave standstill 1min, make it be layered as the suspension liquid on top and the solid of bottom, bottom solid is impurity.Can find out that the impurity contained in raw material is CaCO by accompanying drawing 2 desulfurated plaster raw material XRD phenogram
3, SiO
2; Desulfurated plaster main component is CaSO
42H
2o.
B. pouring the top suspension liquid after layering in a into 150mm × 200mm × 30mm(degree of depth is 30mm) disk container in, lower floor's solid abandons.Suspension liquid in disk container leaves standstill 3min, makes it be layered as suspension liquid (upper strata) and solid (lower floor).
C. the suspension liquid after layering in b is slowly poured out, in dish row container remaining lower floor be exactly raw material water-washing step object product--comparatively pure middle level gypsum 80g(is in butt, namely the quality after free water is removed), whiteness is increased to 45.39%, as the raw material of crystal transition operation.Washing after obtain middle level gypsum XRD figure spectrum see accompanying drawing 3. as can be seen from Figure raw material main component be still CaSO
42H
2o.
D. the suspension liquid poured out obtains 900ml water after filtering out suspended substance, can be used as a step in next circulation and continues to use.
(2) crystal transition:
A. according to water: concentrated hydrochloric acid (12mol/L): CaCl
2: the proportioning preparation reacting slurry of middle level gypsum (in butt, namely removing the quality after free water)=100ml:8ml:1g:10g, then moves into slurries in round-bottomed flask, slurries is heated to 100 DEG C of reaction 285min.
B. a gained slurries to be moved in beaker and at beaker is placed in 10 DEG C, constant temperature leaves standstill 8h.
C. beaker in b and slurries taken out and stir slurries gently, then leaving standstill and separate into after solid (lower floor) and suspension liquid (upper strata) two-phase until slurries, suspension liquid is poured out; The suspended substance (impurity) filtered out in suspension liquid obtains solution, and solution forms slurries with solid phase mixing again.The XRD of the impurity that accompanying drawing 5. obtains for this step characterizes spectrogram, and this impurity is SiO as seen
2.
D. repetition c operates 6 times and washes away impurity, obtains solid matter and the mother liquor (mother liquor composition is in table 1) of white.
(3) product washing: the normal-temperature distilled water of the product that (2) step obtains washs rapidly 4 times (using water 75ml) at every turn, filters, obtains filter cake.
(4) dry: by (3) step to filter cake at 45 DEG C ± 1 DEG C, dry 8h namely obtain the finished product.Quality product is 7.08g, and the R457 whiteness value (Wr) recording product with reference to method in GB/T5950-2008 is 90.21%.Decolouring of purifying obtains the spectrogram of the XRD product of the finished product as Fig. 4. and visible product is CaSO
42H
2o.
Embodiment 2:
(1) raw material washing: working method is with step (1) in example 1.
(2) crystal transition:
A. according to water: concentrated hydrochloric acid (12mol/L): CaCl
2: the proportioning preparation reacting slurry of middle level gypsum (in butt, namely removing the quality after free water)=100.0ml:8.0ml:1.0g:10.0g, then moves into slurries in round-bottomed flask, slurries is heated to 100 DEG C of reaction 285min.
B. a gained slurries to be moved in beaker and at beaker is placed in 25 DEG C, constant temperature leaves standstill 8h.
C. beaker in b and slurries taken out and stir slurries gently, then leaving standstill and separate into after solid (lower floor) and suspension liquid two-phase until slurries, suspension liquid is poured out; The suspended substance (impurity) filtered out in suspension liquid obtains solution, and solution forms slurries with solid phase mixing again.
D. repetition c operates 6 times and washes away impurity, obtains solid matter and the mother liquor of white.And collect mother liquor (mother liquor composition is in table 1).
(3) product washing: the normal-temperature distilled water of the product that (2) step obtains washs rapidly 4 times (using water 75ml) at every turn, filters, obtains filter cake.
(4) dry: by (3) step to filter cake at 45 DEG C ± 1 DEG C, dry 8h namely obtain the finished product.Quality product is 6.95g, and the R457 whiteness value (Wr) recording product with reference to method in GB/T5950-2008 is 91.40%.
Embodiment 3:
(1) raw material washing: working method is with step (1) in example 1.
(2) crystal transition:
A. according to water: concentrated hydrochloric acid (12mol/L): CaCl
2: the proportioning preparation reacting slurry of middle level gypsum (in butt, namely removing the quality after free water)=100.0ml:8.0ml:1.0g:10.0g, then moves into slurries in round-bottomed flask, slurries is heated to 100 DEG C of reaction 285min.
B. a gained slurries to be moved in beaker and at beaker is placed in 40 DEG C, constant temperature leaves standstill 8h.
C. beaker in b and slurries taken out and stir slurries gently, then leaving standstill and separate into after solid (lower floor) and suspension liquid two-phase until slurries, suspension liquid is poured out; The suspended substance (impurity) filtered out in suspension liquid obtains solution, and solution forms slurries with solid phase mixing again.
D. repetition c operates 6 times and washes away impurity, obtains solid matter and the mother liquor of white.And collect mother liquor (mother liquor composition is in table 1).
(3) product washing: the normal-temperature distilled water of the product that (2) step obtains washs rapidly 4 times (using water 75ml) at every turn, filters, obtains filter cake.
(4) dry: by (3) step to filter cake at 45 DEG C ± 1 DEG C, dry 8h namely obtain the finished product.Quality product is 6.85g, and the R457 whiteness value (Wr) recording product with reference to method in GB/T5950-2008 is 90.32%.
Embodiment 4:
(1) raw material washing: working method is with step (1) in example 1.
(2) crystal transition:
A. according to water: concentrated hydrochloric acid (12mol/L): CaCl
2: the proportioning preparation reacting slurry of middle level gypsum (in butt, namely removing the quality after free water)=100.0ml:8.0ml:2.0g:10.0g, then moves into slurries in round-bottomed flask, slurries is heated to 100 DEG C of reaction 240min.
B. a gained slurries to be moved in beaker and at beaker is placed in 25 DEG C, constant temperature leaves standstill 8h.
C. beaker in b and slurries taken out and stir slurries gently, then leaving standstill and separate into after solid (lower floor) and suspension liquid two-phase until slurries, suspension liquid is poured out; The suspended substance (impurity) filtered out in suspension liquid obtains solution, and solution forms slurries with solid phase mixing again.
D. repetition c operates 6 times and washes away impurity, obtains solid matter and the mother liquor of white.And collect mother liquor (mother liquor composition is in table 1).
(3) product washing: the normal-temperature distilled water of the product that (2) step obtains washs rapidly 4 times (using water 75ml) at every turn, filters, obtains filter cake.
(4) dry: by (3) step to filter cake at 45 DEG C ± 1 DEG C, dry 8h namely obtain the finished product.Quality product is 7.68g, and the R457 whiteness value (Wr) recording product with reference to method in GB/T5950-2008 is 91.25%.
Embodiment 5:
(1) raw material washing: working method is with step (1) in example 1.
(2) crystal transition:
A. according to water: concentrated hydrochloric acid (12mol/L): CaCl
2: the proportioning preparation reacting slurry of middle level gypsum (in butt, namely removing the quality after free water)=100.0ml:8.0ml:3.0g:10.0g, then moves into slurries in round-bottomed flask, slurries is heated to 100 DEG C of reaction 170min.
B. a gained slurries to be moved in beaker and at beaker is placed in 25 DEG C, constant temperature leaves standstill 8h.
C. beaker in b and slurries taken out and stir slurries gently, then leaving standstill and separate into after solid (lower floor) and suspension liquid two-phase until slurries, suspension liquid is poured out; The suspended substance (impurity) filtered out in suspension liquid obtains solution, and solution forms slurries with solid phase mixing again.
D. repetition c operates 6 times and washes away impurity, obtains solid matter and the mother liquor of white.And collect mother liquor (mother liquor composition is in table 1).
(3) product washing: the normal-temperature distilled water of the product that (2) step obtains washs rapidly 4 times (using water 75ml) at every turn, filters, obtains filter cake.
(4) dry: by (3) step to filter cake at 45 DEG C ± 1 DEG C, dry 8h namely obtain the finished product.Quality product is 7.63g, and the R457 whiteness value (Wr) recording product with reference to method in GB/T5950-2008 is 90.86%.
Embodiment 6:
(1) raw material washing: working method is with step (1) in example 1.
(2) crystal transition:
A. according to water: concentrated hydrochloric acid (12mol/L): CaCl
2: the proportioning preparation reacting slurry of middle level gypsum (in butt, namely removing the quality after free water)=100.0ml:10.0ml:2.0g:10.0g, then moves into slurries in round-bottomed flask, slurries is heated to 100 DEG C of reaction 240min.
B. a gained slurries to be moved in beaker and at beaker is placed in 25 DEG C, constant temperature leaves standstill 8h.
C. beaker in b and slurries taken out and stir slurries gently, then leaving standstill and separate into after solid (lower floor) and suspension liquid two-phase until slurries, suspension liquid is poured out; The suspended substance (impurity) filtered out in suspension liquid obtains solution, and solution forms slurries with solid phase mixing again.
D. repetition c operates 6 times and washes away impurity, obtains solid matter and the mother liquor of white.And collect mother liquor (mother liquor composition is in table 1).
(3) product washing: the normal-temperature distilled water of the product that (2) step obtains washs rapidly 4 times (using water 75ml) at every turn, filters, obtains filter cake.
(4) dry: by (3) step to filter cake at 45 DEG C ± 1 DEG C, dry 8h namely obtain the finished product.Quality product is 7.58g, and the R457 whiteness value (Wr) recording product with reference to method in GB/T5950-2008 is 91.03%.
Embodiment 7:
(1) raw material washing: working method is with step (1) in example 1.
(2) crystal transition:
A. according to water: concentrated hydrochloric acid (12mol/L): CaCl
2: the proportioning preparation reacting slurry of middle level gypsum (in butt, namely removing the quality after free water)=100.0ml:12.0ml:3.0g:10.0g, then moves into slurries in round-bottomed flask, slurries is heated to 100 DEG C of reaction 120min.
B. a gained slurries to be moved in beaker and at beaker is placed in 25 DEG C, constant temperature leaves standstill 8h.
C. beaker in b and slurries taken out and stir slurries gently, then leaving standstill and separate into after solid (lower floor) and suspension liquid two-phase until slurries, suspension liquid is poured out; The suspended substance (impurity) filtered out in suspension liquid obtains solution, and solution forms slurries with solid phase mixing again.
D. repetition c operates 6 times and washes away impurity, obtains solid matter and the mother liquor of white.And collect mother liquor (mother liquor composition is in table 1).
(3) product washing: the normal-temperature distilled water of the product that (2) step obtains washs rapidly 4 times (using water 75ml) at every turn, filters, obtains filter cake.
(4) dry: by (3) step to filter cake at 45 DEG C ± 1 DEG C, dry 8h namely obtain the finished product.Quality product is 7.36g, and the R457 whiteness value (Wr) recording product with reference to method in GB/T5950-2008 is 91.32%.
Embodiment 8:
(1) raw material washing: working method is with step (1) in example 1.
(2) crystal transition:
A. according to water: concentrated hydrochloric acid (12mol/L): CaCl
2: the proportioning preparation reacting slurry of middle level gypsum (in butt, namely removing the quality after free water)=100.0ml:10ml:3.0g:7.5g, then moves into slurries in round-bottomed flask, slurries is heated to 100 DEG C of reaction 120min.
B. a gained slurries to be moved in beaker and at beaker is placed in 25 DEG C, constant temperature leaves standstill 8h.
C. beaker in b and slurries taken out and stir slurries gently, then leaving standstill and separate into after solid (lower floor) and suspension liquid two-phase until slurries, suspension liquid is poured out; The suspended substance (impurity) filtered out in suspension liquid obtains solution, and solution forms slurries with solid phase mixing again.
D. repetition c operates 6 times and washes away impurity, obtains solid matter and the mother liquor of white.And collect mother liquor (mother liquor composition is in table 1).
(3) product washing: the normal-temperature distilled water of the product that (2) step obtains washs rapidly 3 times (using water 75ml) at every turn, filters, obtains filter cake.
(4) dry: by (3) step to filter cake at 45 DEG C ± 1 DEG C, dry 8h namely obtain the finished product.Quality product is 5.26g, and the R457 whiteness value (Wr) recording product with reference to method in GB/T5950-2008 is 92.00%.
Embodiment 9:
(1) raw material washing: working method is with step (1) in example 1.
(2) crystal transition:
A. according to water: concentrated hydrochloric acid (12mol/L): CaCl
2: the proportioning preparation reacting slurry of middle level gypsum (in butt, namely removing the quality after free water)=100.0ml:10.0ml:3.0g:15.0g, then moves into slurries in round-bottomed flask, slurries is heated to 100 DEG C of reaction 120min.
B. a gained slurries to be moved in beaker and at beaker is placed in 25 DEG C, constant temperature leaves standstill 8h.
C. beaker in b and slurries taken out and stir slurries gently, then leaving standstill and separate into after solid (lower floor) and suspension liquid two-phase until slurries, suspension liquid is poured out; The suspended substance (impurity) filtered out in suspension liquid obtains solution, and solution forms slurries with solid phase mixing again.
D. repetition c operates 6 times and washes away impurity, obtains solid matter and the mother liquor of white.And collect mother liquor (mother liquor composition is in table 1).
(3) product washing: the normal-temperature distilled water of the product that (2) step obtains washs rapidly 5 times (using water 90ml) at every turn, filters, obtains filter cake.
(4) dry: by (3) step to filter cake at 45 DEG C ± 1 DEG C, dry 8h namely obtain the finished product.Quality product is 12.35g, and the R457 whiteness value (Wr) recording product with reference to method in GB/T5950-2008 is 90.01%.
Embodiment 10:
(1) raw material washing: working method is with step (1) in example 1.
(2) crystal transition:
A. mother liquid obtained according to example 8: concentrated hydrochloric acid (12mol/L): middle level gypsum is (in butt, namely the quality after free water is removed) the proportioning preparation reacting slurry of=100.0ml:2.0ml:7.5g, then slurries are moved in round-bottomed flask, slurries are heated to 100 DEG C of reaction 120min.
B. a gained slurries to be moved in beaker and at beaker is placed in 25 DEG C, constant temperature leaves standstill 8h.
C. beaker in b and slurries taken out and stir slurries gently, then leaving standstill and separate into after solid (lower floor) and suspension liquid two-phase until slurries, suspension liquid is poured out; The suspended substance (impurity) filtered out in suspension liquid obtains solution, and solution forms slurries with solid phase mixing again.
D. repetition c operates 6 times and washes away impurity, obtains solid matter and the mother liquor of white.And collect mother liquor (mother liquor composition is in table 1).
(3) product washing: the normal-temperature distilled water of the product that (2) step obtains washs rapidly 3 times (using water 75ml) at every turn, filters, obtains filter cake.
(4) dry: by (3) step to filter cake at 45 DEG C ± 1 DEG C, dry 8h namely obtain the finished product.Quality product is 5.41g, and the R457 whiteness value (Wr) recording product with reference to method in GB/T5950-2008 is 91.46%.
Embodiment 11:
Get the mother liquor 150ml obtained by example 8 method and proportioning, make mother liquor and repeatedly circulate.Concrete operation step and method as follows:
(1) raw material washing: working method is with step (1) in example 1.
(2) crystal transition:
A. according to mother liquor: concentrated hydrochloric acid (12mol/L): middle level gypsum (in butt)=Xn:Yn:Zn(X, Y, Z value sees the following form, n is cycle index) proportioning preparation reacting slurry, then slurries are moved in round-bottomed flask, slurries are heated to 100 DEG C of reaction 120min.
B. a gained slurries to be moved in beaker and at beaker is placed in 25 DEG C, constant temperature leaves standstill 8h.
C. beaker in b and slurries taken out and stir slurries gently, then leaving standstill and separate into after solid (lower floor) and suspension liquid two-phase until slurries, suspension liquid is poured out; The suspended substance (impurity) filtered out in suspension liquid obtains solution, and solution forms slurries with solid phase mixing again.
D. repetition c operates 6 times and washes away impurity, obtains solid matter and the mother liquor of white.And collect mother liquor and to get and wherein 5ml is for analyzing (mother liquor composition in table 2), residue mother liquor is used for Recycling Mother Solution next time.
(3) product washing: the normal-temperature distilled water of the product that (2) step obtains washs rapidly 4 times (using water 85ml) at every turn, filters, obtains filter cake.
(4) dry: by (3) step to filter cake at 45 DEG C ± 1 DEG C, dry 8h namely obtain the finished product.The R457 whiteness value (Wr) of product, product chemical constitution is recorded in table 3 with reference to method in GB/T5950-2008
During first time Recycling Mother Solution operation, n=1 in the operation of (1) step, then completes (2), (3) successively, the operation of (4) step obtains 1 Recycling Mother Solution product and mother liquor.
During the operation of second time Recycling Mother Solution, n=2 in the operation of (1) step, then completes (2), (3) successively, the operation of (4) step obtains 2 Recycling Mother Solution products and mother liquor.
For the third time, the 4th time, the 5th time Recycling Mother Solution working method is with reference to first time.
Embodiment 12:
Due to Fe during recycle mother liquor
3+can add up in the solution, too high Fe
3+content can affect product quality.Get example 11 gained 5 mother liquor 50%TBP ~ 50% kerosene extraction liquid extraction Fe wherein
3+, mother liquor adopts three grades of extractions, the mother liquor one-tenth after extraction be extracting mother liquid; Reverse-extraction agent is distilled water, and extraction agent adopts secondary back extraction regeneration.
Then decolour, operation steps is as follows:
(1) raw material washing: working method is with step (1) in example 1.
(2) crystal transition:
A. according to extracting mother liquid: concentrated hydrochloric acid (12mol/L): the proportioning preparation reacting slurry of middle level gypsum (in butt)=100.0ml:1.3ml:7.5g, then moves into slurries in round-bottomed flask, slurries is heated to 100 DEG C of reaction 120min.
B. a gained slurries to be moved in beaker and at beaker is placed in 25 DEG C, constant temperature leaves standstill 8h.
C. beaker in b and slurries taken out and stir slurries gently, then leaving standstill and separate into after solid (lower floor) and suspension liquid two-phase until slurries, suspension liquid is poured out; The suspended substance (impurity) filtered out in suspension liquid obtains solution, and solution forms slurries with solid phase mixing again.
D. repetition c operates 6 times and washes away impurity, obtains solid matter and the mother liquor of white.And collect mother liquor (mother liquor composition is in table 1).
(3) product washing: the normal-temperature distilled water of the product that (2) step obtains washs rapidly 3 times (using water 75ml) at every turn, filters, obtains filter cake.
(4) dry: by (3) step to filter cake at 45 DEG C ± 1 DEG C, dry 8h namely obtain the finished product.Quality product is 6.4787g, and the R457 whiteness value (Wr) recording product with reference to method in GB/T5950-2008 is 89.27%.
Each leading ion content in table 1. mother liquor
Each leading ion content in table 2. circulating mother liquor
Dihydrate gypsum chemical constitution (wt/%) prepared by table 3. Recycling Mother Solution process
Claims (3)
1. a method for desulfurated plaster decolorization and purification, is characterized by and comprise the following steps:
(1) raw material washing:
A. according to quality than desulfurated plaster: water=1 ~ 3:10, is positioned in container together, stir 30 ~ 90min, then leave standstill 1 ~ 3min, make its layering;
B. the suspension liquid on the top after layering in a being poured into the degree of depth is in the disk container of 25 ~ 50mm, leaves standstill 1 ~ 3min, makes its layering; Lower floor in a after layering abandons;
C. the upper suspension after layering in b slowly poured out, in disk container, remaining lower floor is exactly comparatively pure middle level gypsum;
D. c is walked the suspension liquid poured out and carry out solid-liquid separation, removing suspended substance, the water obtained continues to use as a step in next circulation;
(2) crystal transition:
A. be: concentrated hydrochloric acid: solvent=1: 7.5 ~ 12.5 that mass ratio is CaCl according to volume ratio
2: gypsum=1, middle level: 1.75 ~ 15, every 7 ~ 15g middle level gypsum adds concentrated hydrochloric acid 8 ~ 12mL, preparation reacting slurry, and slurries is heated to 90 ~ 100 DEG C of reaction 1 ~ 5h; Wherein, the quality of middle level gypsum, in butt, namely removes the quality after free water;
B. a gained slurries constant temperature at 10 DEG C ~ 40 DEG C is left standstill 8h;
C. gained slurries in b taken out and stir, then leaving standstill and separate into after solid and suspension liquid two-phase until slurries, suspension liquid is poured out; The suspended impurity filtered out in suspension liquid obtains solution, and solution forms slurries with solids mixing again;
D. repeat c operation 5 ~ 7 times, finally obtain solid matter and the mother liquor of white;
(3) product washing: the product distilled water wash that (2) step is obtained 3 ~ 5 times;
(4) dry: by (3) step to product at 45 DEG C ± 1 DEG C, dry 8 ~ 10h can obtain the finished product.
2. the method for desulfurated plaster decolorization and purification as claimed in claim 1, is characterized by the mother liquor that in described step (2), in crystal transition process, the solvent described in a is water or obtains in previously producing, or the mixture of the two.
3. the method for desulfurated plaster decolorization and purification as claimed in claim 1, is characterized by the method for described desulfurated plaster decolorization and purification, further comprising the steps of: in step (2) crystal transition, d walks the mother liquor obtained, as wherein H
+concentration is lower than adding concentrated hydrochloric acid during 1.44mol/L again by H
+reuse after being supplemented to 1.44mol/L; Extracted Fe by TBP-kerosene three grades after the iron in solution runs up to 20mmol/L
3+concentration controls at below 0.6mmol/L; The TBP-kerosene water extracting iron later reclaims through secondary back extraction; The concentration of concentrated hydrochloric acid is 12mol/L.
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| CN110304852B (en) * | 2019-08-14 | 2020-10-09 | 江苏一夫科技股份有限公司 | Method for whitening desulfurized gypsum, gypsum obtained by method and application of gypsum |
| CN113149037A (en) * | 2021-05-25 | 2021-07-23 | 天津渤化永利化工股份有限公司 | Method for preparing potassium sulfate by utilizing desulfurized gypsum |
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