CN109078707B - Phosphogypsum stabilizer and stabilizing system - Google Patents
Phosphogypsum stabilizer and stabilizing system Download PDFInfo
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- CN109078707B CN109078707B CN201810673188.4A CN201810673188A CN109078707B CN 109078707 B CN109078707 B CN 109078707B CN 201810673188 A CN201810673188 A CN 201810673188A CN 109078707 B CN109078707 B CN 109078707B
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- China
- Prior art keywords
- phosphogypsum
- stabilizer
- metal salt
- inorganic metal
- dithiocarbamate
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Links
- 239000003381 stabilizer Substances 0.000 title claims abstract description 81
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 title claims abstract description 77
- 230000000087 stabilizing effect Effects 0.000 title claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 47
- 239000002184 metal Substances 0.000 claims abstract description 47
- 150000003839 salts Chemical class 0.000 claims abstract description 47
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 36
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000012990 dithiocarbamate Substances 0.000 claims abstract description 35
- 239000000292 calcium oxide Substances 0.000 claims abstract description 18
- 235000012255 calcium oxide Nutrition 0.000 claims abstract description 18
- 238000003860 storage Methods 0.000 claims abstract description 7
- 239000004571 lime Substances 0.000 claims description 47
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 46
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 46
- 238000002156 mixing Methods 0.000 claims description 46
- 239000000843 powder Substances 0.000 claims description 42
- 238000007664 blowing Methods 0.000 claims description 35
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 30
- 239000000428 dust Substances 0.000 claims description 29
- 229910000831 Steel Inorganic materials 0.000 claims description 18
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 18
- 239000010959 steel Substances 0.000 claims description 18
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 17
- 230000006641 stabilisation Effects 0.000 claims description 17
- 238000011105 stabilization Methods 0.000 claims description 17
- 238000005303 weighing Methods 0.000 claims description 17
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 239000007921 spray Substances 0.000 claims description 13
- 238000001514 detection method Methods 0.000 claims description 11
- 238000005507 spraying Methods 0.000 claims description 11
- 238000007599 discharging Methods 0.000 claims description 10
- 230000001105 regulatory effect Effects 0.000 claims description 5
- 238000010168 coupling process Methods 0.000 claims description 4
- 238000005859 coupling reaction Methods 0.000 claims description 4
- 230000008878 coupling Effects 0.000 claims description 3
- 244000188472 Ilex paraguariensis Species 0.000 claims 1
- 238000009434 installation Methods 0.000 claims 1
- 238000002386 leaching Methods 0.000 abstract description 24
- 238000000034 method Methods 0.000 abstract description 19
- 230000008569 process Effects 0.000 abstract description 16
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 13
- 229910052731 fluorine Inorganic materials 0.000 abstract description 7
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 4
- 230000002378 acidificating effect Effects 0.000 abstract description 4
- 238000003912 environmental pollution Methods 0.000 abstract description 4
- 239000011737 fluorine Substances 0.000 abstract description 4
- 239000011574 phosphorus Substances 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 230000008092 positive effect Effects 0.000 abstract description 3
- 239000002738 chelating agent Substances 0.000 abstract description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000002253 acid Substances 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 150000004659 dithiocarbamates Chemical class 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 239000010440 gypsum Substances 0.000 description 3
- 229910052602 gypsum Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052586 apatite Inorganic materials 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000013468 resource allocation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000009270 solid waste treatment Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 239000000271 synthetic detergent Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C17/00—Disintegrating by tumbling mills, i.e. mills having a container charged with the material to be disintegrated with or without special disintegrating members such as pebbles or balls
- B02C17/10—Disintegrating by tumbling mills, i.e. mills having a container charged with the material to be disintegrated with or without special disintegrating members such as pebbles or balls with one or a few disintegrating members arranged in the container
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C17/00—Disintegrating by tumbling mills, i.e. mills having a container charged with the material to be disintegrated with or without special disintegrating members such as pebbles or balls
- B02C17/18—Details
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B15/00—Preventing escape of dirt or fumes from the area where they are produced; Collecting or removing dirt or fumes from that area
- B08B15/04—Preventing escape of dirt or fumes from the area where they are produced; Collecting or removing dirt or fumes from that area from a small area, e.g. a tool
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/18—Phosphoric acid
- C01B25/22—Preparation by reacting phosphate-containing material with an acid, e.g. wet process
- C01B25/222—Preparation by reacting phosphate-containing material with an acid, e.g. wet process with sulfuric acid, a mixture of acids mainly consisting of sulfuric acid or a mixture of compounds forming it in situ, e.g. a mixture of sulfur dioxide, water and oxygen
Abstract
The invention discloses an phosphogypsum stabilizer and a stabilizing system, wherein the phosphogypsum stabilizer is prepared from the following components in parts by weight: 90-95 parts of quicklime, 2-5 parts of dithiocarbamate and 1-4 parts of inorganic metal salt. The dithiocarbamic acid salt used as an alkaline chelating agent can stabilize F, P, heavy metals and other harmful elements in phosphogypsum, and the quicklime can also replace and reduce soluble P in phosphogypsum 2 O 5 And Fe (Fe) 2+ The phosphogypsum modified by the stabilizer has low leaching concentration of soluble phosphorus, fluorine, harmful heavy metals and the like in the phosphogypsum in an acidic environment or an alkaline environment, has obvious stabilizing effect, avoids the environmental pollution problem caused by the phosphogypsum in the storage process, has very positive effect on environmental protection, has simple operation and low cost, is suitable for popularization and application, and provides scientific basis for pollution-free treatment of phosphogypsum in China.
Description
Technical Field
The invention relates to the field of chemical industrial waste treatment, in particular to an phosphogypsum stabilizer and a stabilization system.
Background
Phosphogypsum is phosphoric acid or phosphorusIndustrial waste residue discharged from fertilizer industry and some synthetic detergent industry contains calcium sulfate as main component. In the usual case, a wet process for producing 1 ton of phosphoric acid will produce about 4.5 to 5.5 tons of phosphogypsum, the main component of which is calcium sulfate (CaSO 4 ·2H 2 O) while also containing various impurities, which are largely classified into insoluble impurities and soluble impurities. The insoluble impurities are mainly: quartz, undegraded apatite, insoluble P 2 O 5 Eutectic P 2 O 5 Fluoride, etc.; the soluble impurities are mainly: water-soluble P 2 O 5 Fluoride and sulfate having low solubility; in addition, phosphogypsum also contains trace harmful heavy metal elements. The fluoride, P, harmful heavy metal and other impurities contained in phosphogypsum are main factors causing environmental pollution in the stacking and disposing process of phosphogypsum. The stacking of a large amount of phosphogypsum not only occupies a large amount of land resources, but also causes pollution to the atmosphere, water system and soil due to wind erosion and rain erosion, and the phosphogypsum has leaching toxicity due to the fact that harmful substances appear in leaching liquid of the phosphogypsum are out of standard, and meanwhile, the yard construction cost and the maintenance cost of the phosphogypsum are quite expensive, so that the harmless treatment of the phosphogypsum becomes a research hotspot in the fields of solid waste treatment and reasonable resource allocation.
At present, more phosphogypsum stabilizers are available on the market, but in the process of adding the stabilizers, manual proportioning and mixing of the components of the stabilizers are very troublesome, in the process of producing phosphoric acid by a wet method, liquid-phase phosphoric acid products are obtained after solid-liquid separation of slurry formed by phosphoric acid and gypsum after the reaction is completed, and a set of equipment for adding the stabilizers into gypsum filter cakes on a filter disc is developed, so that the production efficiency of phosphogypsum stabilization can be greatly improved.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides the phosphogypsum stabilizer which stabilizes F, P and harmful heavy metals in phosphogypsum, so that the leaching concentration of soluble phosphorus, fluorine, harmful heavy metals and other pollutants in phosphogypsum is greatly reduced in an acidic environment or an alkaline environment. On the other hand, the equipment for proportioning and mixing phosphogypsum stabilizer according to the amount is provided, and the stabilizer with the required dosage is automatically generated and added in a filtering link in the production process of producing phosphoric acid by a wet method.
The aim of the invention is realized by the following technical scheme:
the phosphogypsum stabilizer is prepared from the following components in parts by weight:
90 to 95 parts of quicklime,
2 to 5 parts of dithiocarbamate,
1-4 parts of inorganic metal salt.
Phosphogypsum stabilizer is prepared from the following components in parts by weight:
90 parts of quicklime, namely, the mixture of the quicklime and the water,
2 parts of dithiocarbamate salt,
1 part of inorganic metal salt.
Phosphogypsum stabilizer is prepared from the following components in parts by weight:
95 parts of quicklime and the like,
5 parts of dithiocarbamate salt,
4 parts of inorganic metal salt.
Phosphogypsum stabilizer is prepared from the following components in parts by weight:
92.5 parts of quicklime,
3.5 parts of dithiocarbamate,
2.5 parts of inorganic metal salt.
Phosphogypsum stabilizer, wherein the inorganic metal salt comprises sulfate and sulfide, and the weight ratio of the sulfate to the sulfide is 1-1.5:1-1.2.
A phosphogypsum stabilization system is used for spraying the stabilizer on a filter disc at the tail end of a filter in a wet phosphoric acid production process and comprises a lime powder supply assembly, a dithiocarbamate supply assembly, an inorganic metal salt supply assembly, a mixing device and a stabilizer spraying device;
the lime powder supply assembly comprises a block lime powder making device and a lime powder metering hopper, wherein a discharge port of the block lime powder making device is connected with a feed port of the lime powder metering hopper, and a discharge port of the lime powder metering hopper is connected with a lime powder feed port of the mixing device through a conveying belt;
the dithiocarbamate supply assembly comprises a dithiocarbamate metering hopper, and a discharge hole of the dithiocarbamate metering hopper is connected with a dithiocarbamate feed inlet of the mixing device through a conveyor belt;
the inorganic metal salt supply assembly comprises an inorganic metal salt metering hopper, and a discharge port of the inorganic metal salt metering hopper is connected with an inorganic metal salt feed inlet of the mixing device through a conveying belt;
the stabilizer discharge port of the mixing device is connected with the inlet of the stabilizer spraying device, and the spray head of the stabilizer spraying device is arranged above the filter disc at the tail end of the filter.
The device is characterized in that the blocky lime powder making device is a ball mill, a feed inlet is formed in the upper portion of the ball mill, a discharge outlet is formed in the lower portion of the ball mill, steel balls are arranged in the ball mill, couplings used for connecting a driving device are arranged at two ends of the ball mill, the driving device is arranged on a frame used for fixing the ball mill, a pressure control device and a pressure detection device are further arranged on the ball mill, one end of the pressure control device extends into the ball mill, and the other end of the pressure control device is connected with the pressure detection device.
The upper part of the ball mill is also provided with a dust removing device, the dust removing device comprises a dust removing port, a bag type dust remover communicated with the dust removing port and an induced draft fan, and the outlet end of the bag type dust remover is connected with the induced draft fan.
The driving device is a motor, the pressure control device is a vacuum pump, and the pressure detection device is a vacuum pressure gauge.
The utility model discloses a novel lime powder weighing hopper, including lime powder weighing hopper, dithiocarbamic acid salt weighing hopper and inorganic metal salt weighing hopper, lime powder weighing hopper, there are dithiocarbamic acid salt weighing hopper and inorganic metal salt weighing hopper are the hopper body that the top is equipped with opening, bottom movable, and hopper body bottom exit is equipped with the apron, the upper surface in the apron is equipped with weighing sensor, the apron is installed in the slot of hopper body bottom inner wall, set up miniature step motor on the outer wall of hopper body, set up the rack on the outer wall of apron, miniature step motor's output connect one with the gear that the rack matches, gear and rack intermeshing install.
The mixing device comprises a high-speed mixer, a jacket, a blowing cylinder and a conical mixer, wherein the high-speed mixer is provided with a lime powder feed inlet, a dithiocarbamate feed inlet and an inorganic metal salt feed inlet, a discharge outlet of the high-speed mixer is connected with the feed inlet of the conical mixer, the discharge outlet of the conical mixer is connected with the feed inlet of the blowing cylinder, the bottom of the blowing cylinder is provided with a stabilizer discharge outlet, the conical mixer is provided with a jacket, and an ultrasonic generator or a microwave generator is arranged in the jacket.
The side wall of the blowing cylinder is obliquely provided with a blowing steel pipe, one end of the blowing steel pipe extends into the inner cavity of the blowing cylinder, and the other end of the blowing steel pipe is connected with a booster pump.
The stabilizer spray device comprises a stabilizer storage tank and a discharging pipeline, wherein the discharging pipeline is provided with a regulating valve, and the tail end of the discharging pipeline is provided with a spray head.
The beneficial effects of the invention are as follows:
through a great deal of experimental researches, the dithiocarbamate serving as an alkaline chelating agent can stabilize F, P, heavy metals and other harmful elements in phosphogypsum.
Dithiocarbamates and inorganic metal salts are mainly stabilization for heavy metals and the principle is to react with heavy metal ions to form precipitates and chelates.
Quicklime can also replace and reduce soluble P in phosphogypsum 2 O 5 And Fe (Fe) 2+ Stabilization is carried out:
CaO+H 2 O＝Ca(OH) 2
P 2 O 5 +3Ca(OH) 2 ＝Ca 3 (PO4) 2 +3H 2 O
Fe 2+ +2OH - ＝Fe(OH) 2
thus, after mixing phosphogypsum stabilizer and phosphogypsum in a certain proportion, phosphogypsum is modified, and heavy metal, water-soluble phosphorus and water-soluble fluorine react with the stabilizer to generate indissolvable stabilizing substances which are adhered in the consolidated body.
1) The phosphogypsum modified by the fixing agent has low leaching concentration of soluble phosphorus, fluorine, harmful heavy metals and the like in the phosphogypsum in an acidic environment or an alkaline environment, has obvious stabilizing effect, avoids the problem of environmental pollution caused by the phosphogypsum in the storage process, has very positive effect on environmental protection, and provides scientific basis for pollution-free treatment of phosphogypsum in China.
2) The stabilizer has low cost, simple manufacture, simple operation procedure, outstanding effect and is very suitable for popularization and application.
3) The stabilizer of the invention can effectively reduce the toxicity of phosphogypsum, and the whole stabilizing process is pollution-free.
4) The ball mill in the stabilizing system can fully grind the blocky lime into powder, and the pressure control device and the pressure detection device are arranged, so that the blocky lime can be vacuumized while ball milling of the mixed steel balls is performed, and the working efficiency is improved; the dust removing device is further arranged, dust cannot be generated on the operation site, and therefore the harm to the health of operators is avoided, and meanwhile, the labor intensity of the operators is reduced.
5) The metering hopper can make each component of the stabilizer mix according to the amount, and the mixing device can shorten the material stirring time of each component of the stabilizer, improve the mixing uniformity, improve the material dispersibility and reduce the agglomeration phenomenon by arranging an ultrasonic generator or a microwave generator.
6) The application of the stabilizing system spray stabilizer in the filtering link in the phosphoric acid production process has the following advantages: the stabilizing system is arranged at the tail end of the phosphoric acid production process, and only one stabilizer adding device is arranged on the filtering device, so that the original phosphoric acid production process link is not influenced, the process is simple and convenient to reform and easy to implement; secondly, because the filter device is in a moving state, the complete mixing of the fresh phosphogypsum and the stabilizing agent can be realized only by arranging an adding device at one position of the filter device, the place of a special design of the mixing device is not needed, the phosphogypsum stabilizing treatment process can be finished on the filter device, the equipment composition is greatly simplified, and the investment is saved.
Drawings
FIG. 1 is a flow chart of a stabilization system;
FIG. 2 is a schematic diagram of the structure of a stabilization system;
FIG. 3 is a schematic diagram of the structure of a box of a weighing device of the stabilizing system;
in the figure, 1-lime powder supply assembly, 101-feed inlet, 102-discharge outlet, 103-driving device, 104-coupling, 105-pressure control device, 106-pressure detection device, 107-steel ball, 108-rack, 109-dust removal port, 110-dust remover, 111-induced draft fan, 2-dithiocarbamate supply assembly, 201-cover plate, 202-slot, 203-micro stepping motor, 204-rack, 205-gear, 206-weighing sensor, 3-inorganic metal salt supply assembly, 4-mixing device, 401-high-speed mixer, 402-jacket, 403-blowing cylinder, 404-conical mixer, 405-blowing steel pipe, 406-booster pump, 407-stabilizer discharge port, 5-stabilizer spray device, 501-stabilizer storage tank, 502-blanking pipeline, 503-regulating valve, 504-shower nozzle, 6-filter.
Detailed Description
The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by a person skilled in the art without any inventive effort, are intended to be within the scope of the present invention, based on the embodiments of the present invention.
The invention provides a technical scheme that:
an phosphogypsum stabilizer, which is prepared from the following components in parts by weight:
90 parts of quicklime, namely, the mixture of the quicklime and the water,
2 parts of dithiocarbamate salt,
1 part of inorganic metal salt.
The inorganic metal salt comprises sulfate and sulfide, and the weight ratio of the sulfate to the sulfide is 1.5:1.2.
An phosphogypsum stabilizer, which is prepared from the following components in parts by weight:
95 parts of quicklime and the like,
5 parts of dithiocarbamate salt,
4 parts of inorganic metal salt.
The inorganic metal salt comprises sulfate and sulfide, and the weight ratio of the sulfate to the sulfide is 1.3:1.15.
An phosphogypsum stabilizer, which is prepared from the following components in parts by weight:
92.5 parts of quicklime,
3.5 parts of dithiocarbamate,
2.5 parts of inorganic metal salt.
The inorganic metal salt comprises sulfate and sulfide, and the weight ratio of the sulfate to the sulfide is 1:1.
An phosphogypsum stabilizer, which is prepared from the following components in parts by weight:
92.5 parts of quicklime,
3.5 parts of dithiocarbamate,
2.5 parts of inorganic metal salt.
The inorganic metal salt comprises sulfate and sulfide, and the weight ratio of the sulfate to the sulfide is 1:1.
An phosphogypsum stabilizer, which is prepared from the following components in parts by weight:
91 parts of quicklime and the balance of the lime,
3 parts of dithiocarbamate, wherein the total amount of the dithiocarbamate is,
and 2 parts of inorganic metal salt.
The inorganic metal salt comprises sulfate and sulfide, and the weight ratio of the sulfate to the sulfide is 1.4:1.2.
An phosphogypsum stabilizer, which is prepared from the following components in parts by weight:
93 parts of quicklime and the like,
4 parts of dithiocarbamate, wherein the total amount of the dithiocarbamate is,
3 parts of inorganic metal salt.
The inorganic metal salt comprises sulfate and sulfide, and the weight ratio of the sulfate to the sulfide is 1.5:1.
An phosphogypsum stabilizer, which is prepared from the following components in parts by weight:
94.5 parts of quicklime and the like,
4.5 parts of dithiocarbamate,
3.5 parts of inorganic metal salt.
The inorganic metal salt comprises sulfate and sulfide, and the weight ratio of the sulfate to the sulfide is 1:1.2.
To investigate the stabilization effect, the concentrations of harmful substances in the fresh phosphogypsum and in the acid-leached and water-leached liquid of the stabilized phosphogypsum were determined, and the experiments were arranged in five groups according to the weight ratios of the stabilizer to phosphogypsum of 1:50, 1:100, 1:200, 1:300 and 1:500. The water leaching is a process of taking pure water as a leaching agent and simulating leaching of solid waste by surface water or underground water in a specific occasion, wherein harmful components in the solid waste are leached out and enter the environment; acid leaching is a process of taking a nitric acid/sulfuric acid mixed solution as a leaching agent and simulating that harmful components in waste are leached from the waste to enter the environment under the influence of acid precipitation when the waste is piled up in irregular landfill disposal. Therefore, the concentration of the pollutant in the water leaching solution or the acid leaching solution can represent the release level of the pollutant in phosphogypsum under the influence of external environment (acid and alkali).
Through a large number of experiments, repeated experiments are carried out by using the stabilizing agent with the proportion of the example 3, and we obtain a table of concentration control substances in the leaching solution of P in phosphogypsum and harmful heavy metals under the conditions of acid leaching and water leaching:
table 1.1 stabilization experimental effect (P) units: mg/L
| Water leaching | Acid leaching | |
| Fresh phosphogypsum | 47.33 | 87.45 |
| Mixing ratio of 1:50 | 0.11 | 0.23 |
| Mixing ratio of 1:100 | 0.09 | 0.31 |
| Mixing ratio of 1:200 | 0.30 | 0.44 |
| Mixing ratio of 1:300 | 0.18 | 0.55 |
| Mixing ratio of 1:500 | 0.38 | 3.33 |
Table 1.2 stabilization experimental effect (Pb) units: mg/L
| Water leaching | Acid leaching | |
| Fresh phosphogypsum | 0.012 | 0.037 |
| Mixing ratio of 1:50 | (0.004) | 0.023 |
| Mixing ratio of 1:100 | 0.031 | 0.025 |
| Mixing ratio of 1:200 | 0.002 | 0.025 |
| Mixing ratio of 1:300 | 0.026 | 0.026 |
| Mixing ratio of 1:500 | 0.039 | 0.043 |
Table 1.3 stabilization experimental effect (Cd) units: mg/L
| Water leaching | Acid leaching | |
| Fresh phosphogypsum | 0.015 | 0.008 |
| Mixing ratio of 1:50 | 0.006 | 0.007 |
| Mixing ratio of 1:100 | 0.005 | 0.006 |
| Mixing ratio of 1:200 | 0.005 | 0.006 |
| Mixing ratio of 1:300 | 0.006 | 0.005 |
| Mixing ratio of 1:500 | 0.005 | 0.005 |
As shown in the experimental data in tables 1.1-1.3, phosphogypsum stabilized by the total stabilizer has low leaching concentration of harmful substances P and heavy metals Pb and Cd in phosphogypsum under acidic or alkaline environments, and has remarkable stabilizing effect. The experimental result shows that the phosphogypsum stabilized by the stabilizer effectively reduces the toxicity of the phosphogypsum, the whole stabilizing process is nuisanceless, the problem of environmental pollution caused by the phosphogypsum in the storage process is avoided, the phosphogypsum has very positive effect on environmental protection, and scientific basis is provided for nuisanceless treatment of phosphogypsum in China. In addition, the fixing agents of 6 examples except for example 3 were mixed with gypsum, and the weight ratios of the fixing agents were 1:50, 1:100, 1:200, 1:300 and 1:500, and five groups of the fixing agents were subjected to acid leaching and water leaching experiments, so that the obtained experimental data were very slightly different from those in tables 1.1 to 1.3.
As shown in fig. 1-2, an phosphogypsum stabilization system is used for spraying the stabilizer on a filter disc at the tail end of a filter 6 in a wet phosphoric acid production process, and comprises a lime powder supply assembly 1, a dithiocarbamate supply assembly 2, an inorganic metal salt supply assembly 3, a mixing device 4 and a stabilizer spraying device 5;
the lime powder supply assembly 1 comprises a block lime powder making device and a lime powder metering hopper, wherein a discharge port 102 of the block lime powder making device is connected with a feed port of the lime powder metering hopper, and the discharge port of the lime powder metering hopper is connected with a lime powder feed port of the mixing device 4 through a conveying belt;
the dithiocarbamate supply assembly 2 comprises a dithiocarbamate metering hopper, and a discharge hole of the dithiocarbamate metering hopper is connected with a dithiocarbamate feed inlet of the mixing device 4 through a conveyor belt;
the inorganic metal salt supply assembly 3 comprises an inorganic metal salt metering hopper, and a discharge port of the inorganic metal salt metering hopper is connected with an inorganic metal salt feed inlet of the mixing device 4 through a conveying belt;
the stabilizer outlet 407 of the mixing device 4 is connected with the inlet of the stabilizer spraying device 5, and the nozzle 504 of the stabilizer spraying device 5 is arranged above the filter disc at the tail end of the filter 6. The blocky lime is fully ground by a blocky lime powder making device and then is transferred into a lime powder metering hopper for weighing, and the dithiocarbamate and the inorganic metal salt directly enter the metering hopper for weighing.
The blocky lime powder making device is a ball mill, a feed inlet 101 is formed in the upper portion of the ball mill, a discharge outlet 102 is formed in the lower portion of the ball mill, steel balls 107 are arranged in the ball mill, couplings 104 used for connecting a driving device 103 are arranged at two ends of the ball mill, the driving device 103 is mounted on a frame 108 used for fixing the ball mill, a pressure control device 105 and a pressure detection device 106 are further arranged on the ball mill, one end of the pressure control device 105 extends into the ball mill, and the other end of the pressure control device 105 is connected with the pressure detection device 106. The driving device 103 is a motor, the pressure control device 105 is a vacuum pump, and the pressure detection device 106 is a vacuum pressure gauge. The vacuum pump and the vacuum pressure gauge are arranged on the same side of the feed inlet 101, when the block lime of the stabilizer is ground in the ball mill, the pressure in the ball mill can be detected at any time through the vacuum pressure gauge, the pressure in the ball mill is controlled through the vacuum pump, so that the block lime is mixed and ball-milled, and meanwhile, the vacuum is pumped, the working efficiency is improved, and the block lime is fully ground into uniform lime powder. The upper part of the ball mill is also provided with a dust removing device, the dust removing device comprises a dust removing opening 109, a bag type dust remover 110 and an induced draft fan 111, the bag type dust remover 110 is communicated with the dust removing opening 109, and the outlet end of the bag type dust remover 110 is connected with the induced draft fan 111. The dust remover is arranged to ensure that dust is discharged up to standard, and the dust generated in the grinding process is removed through the mutual matching of the induced draft fan 111 and the bag type dust remover 110, so that the dust cannot be generated on the operation site in production, and the health of operators is prevented from being damaged. The fully ground lime powder falls into the feed inlet of the lime powder metering hopper through the discharge outlet 102.
As shown in fig. 3, the lime powder metering hopper, the dithiocarbamate metering hopper and the inorganic metal salt metering hopper are hopper bodies with openings at the top and movable bottoms, a cover plate 201 is arranged at the outlet of the bottom of the hopper bodies, a weighing sensor 206 is arranged on the upper surface in the cover plate 201, the cover plate 201 is installed in a slot 202 in the inner wall of the bottom of the hopper bodies, a micro stepping motor 203 is arranged on the outer wall of the hopper bodies, a rack 204 is arranged on the outer wall of the cover plate 201, the output end of the micro stepping motor 203 is connected with a gear 205 matched with the rack 204, the gear 205 is installed in a meshed manner with the rack 204, and data measured by the weighing sensor 206 generate a driving signal of the stepping motor through a microprocessor so as to drive the motor to rotate. Through the preset value of the weighing sensor 206, when the preset value is reached, related data generate a driving signal of the stepping motor through the microprocessor, the micro stepping motor 203 is started, so that the rack 204 moves along the gear 205, the cover plate 201 is driven to move outwards, the stabilizer component in the hopper body falls onto the conveying belt through the bottom outlet, and after conveying is finished, the micro stepping motor 203 reversely rotates to drive the cover plate 201 to be closed. The components in the stabilizer are transported into the corresponding feed inlets of the mixing device 4 through the weighing hopper body by a conveyor belt.
As shown in fig. 1, the mixing device 4 includes a high-speed mixer 401, a jacket 402, a blowing cylinder 403, and a conical mixer 404, where the high-speed mixer 401 is provided with a lime powder inlet, a dithiocarbamate inlet, and an inorganic metal salt inlet, the discharge port of the high-speed mixer 401 is connected with the inlet of the conical mixer 404, the discharge port of the conical mixer 404 is connected with the inlet of the blowing cylinder 403, the bottom of the blowing cylinder 403 is provided with a stabilizer outlet 407, the conical mixer 404 is provided with a jacket 402, and the jacket 402 is provided with an ultrasonic generator or a microwave generator.
The side wall of the blowing cylinder 403 is obliquely provided with a blowing steel pipe 405, one end of the blowing steel pipe 405 extends into the inner cavity of the blowing cylinder 403, and the other end is connected with a booster pump 406. All components of the stabilizer are firstly mixed in a high-speed mixer 401, then enter a conical mixer 404 for secondary mixing, and the components are further mixed uniformly through ultrasonic vibration treatment or microwave conditioning, and the uniformly mixed stabilizer enters a blowing cylinder 403. The side wall of the blowing cylinder 403 is obliquely provided with a blowing steel pipe 405, one end of the blowing steel pipe 405 extends into the inner cavity of the blowing cylinder 403, the other end of the blowing steel pipe is connected with a booster pump 406, an included angle between the blowing steel pipe 405 and the central axis of the blowing cylinder 403 is an acute angle, the blowing cylinder is additionally arranged, the speed of stabilizer blanking and the flow rate of the whole pipeline output are improved, the problem of blockage is avoided, and the blowing cylinder is simple and effective.
After the raw materials are fully mixed by the mixing device 4, a stabilizer is generated, and the raw materials enter the inlet of the stabilizer spraying device 5 through the stabilizer discharge port 407. The stabilizer spraying device 5 stabilizer storage tank 501 and a blanking pipeline 502, a regulating valve 503 is arranged on the blanking pipeline 502, a spray head 504 is arranged at the tail end of the blanking pipeline 502, and the spray head 504 is arranged above a filter disc at the tail end of the filter 6. The regulating valve 503 can be preset to a value such as regulating the amount of stabilizer by the flow rate of stabilizer powder of the discharging pipe 502, and the amount of stabilizer is determined by the actual amount of phosphogypsum produced. The stabilizing system is applied to the filtering link in the phosphoric acid production process to add the stabilizing agent, and has the following advantages: the stabilizing system is arranged at the tail end of the phosphoric acid production process, and only one stabilizer adding device is arranged on the filtering device, so that the original phosphoric acid production process link is not influenced, the process is simple and convenient to reform and easy to implement; secondly, because the filter device is in a moving state, the complete mixing of the fresh phosphogypsum and the stabilizing agent can be realized only by arranging an adding device at one position of the filter device, the place of a special design of the mixing device is not needed, the phosphogypsum stabilizing treatment process can be finished on the filter device, the equipment composition is greatly simplified, and the investment is saved.
The foregoing is merely a preferred embodiment of the invention, and it is to be understood that the invention is not limited to the form disclosed herein but is not to be construed as excluding other embodiments, but is capable of numerous other combinations, modifications and environments and is capable of modifications within the scope of the inventive concept, either as taught or as a matter of routine skill or knowledge in the relevant art. And that modifications and variations which do not depart from the spirit and scope of the invention are intended to be within the scope of the appended claims.
Claims (6)
1. An phosphogypsum stabilizing system for spraying stabilizing agent onto a terminal filter disc of a filter (6) in a wet phosphoric acid production process is characterized in that: comprises a lime powder supply assembly (1), a dithiocarbamate supply assembly (2), an inorganic metal salt supply assembly (3), a mixing device (4) and a stabilizer spray device (5);
the lime powder supply assembly (1) comprises a block lime powder making device and a lime powder metering hopper, a discharge port (102) of the block lime powder making device is connected with a feed port of the lime powder metering hopper, and the discharge port of the lime powder metering hopper is connected with a lime powder feed port of the mixing device (4) through a conveying belt;
the dithiocarbamate supply assembly (2) comprises a dithiocarbamate metering hopper, and a discharge port of the dithiocarbamate metering hopper is connected with a dithiocarbamate feed port of the mixing device (4) through a conveyor belt;
the inorganic metal salt supply assembly (3) comprises an inorganic metal salt metering hopper, and a discharge hole of the inorganic metal salt metering hopper is connected with an inorganic metal salt feed inlet of the mixing device (4) through a conveying belt;
the stabilizer discharge outlet (407) of the mixing device (4) is connected with the inlet of the stabilizer spray device (5), and the spray head (504) of the stabilizer spray device (5) is arranged above the end filter disc of the filter (6);
the device comprises a ball mill, wherein a feed inlet (101) is formed in the upper part of the ball mill, a discharge outlet (102) is formed in the lower part of the ball mill, steel balls (107) are arranged in the ball mill, couplings (104) used for connecting a driving device (103) are arranged at two ends of the ball mill, the driving device (103) is arranged on a frame (108) used for fixing the ball mill, a pressure control device (105) and a pressure detection device (106) are further arranged on the ball mill, one end of the pressure control device (105) stretches into the ball mill, and the other end of the pressure control device is connected with the pressure detection device (106);
the stabilizer is prepared from the following components in parts by weight:
90 to 95 parts of quicklime,
2 to 5 parts of dithiocarbamate,
1-4 parts of inorganic metal salt;
the mixing device (4) comprises a high-speed mixer (401), a jacket (402), a blowing cylinder (403) and a conical mixer (404), wherein a lime powder feeding port, a dithiocarbamate feeding port and an inorganic metal salt feeding port are formed in the high-speed mixer (401), a discharging port of the high-speed mixer (401) is connected with a feeding port of the conical mixer (404), a discharging port of the conical mixer (404) is connected with a feeding port of the blowing cylinder (403), a stabilizer discharging port (407) is formed in the bottom of the blowing cylinder (403), the jacket (402) is arranged on the conical mixer (404), and an ultrasonic generator or a microwave generator is arranged in the jacket (402);
the side wall of the blowing cylinder (403) is obliquely provided with a blowing steel pipe (405), one end of the blowing steel pipe (405) extends into the inner cavity of the blowing cylinder (403), and the other end of the blowing steel pipe is connected with a booster pump (406).
2. The phosphogypsum stabilization system of claim 1, wherein the inorganic metal salt comprises sulfate and sulfide in a weight ratio of 1-1.5:1-1.2.
3. Phosphogypsum stabilization system according to claim 1, characterized in that: the upper part of the ball mill is also provided with a dust removing device, the dust removing device comprises a dust removing opening (109), a bag type dust remover (110) and an induced draft fan (111), wherein the bag type dust remover is communicated with the dust removing opening (109), and the outlet end of the bag type dust remover (110) is connected with the induced draft fan (111).
4. Phosphogypsum stabilization system according to claim 1, characterized in that: the driving device (103) is a motor, the pressure control device (105) is a vacuum pump, and the pressure detection device (106) is a vacuum pressure gauge.
5. The phosphogypsum stabilization system of claim 3, wherein: lime powder measuring hopper, dithiocarbamate measuring hopper and inorganic metal salt measuring hopper are the hopper body that the top is equipped with opening, bottom movable, and hopper body bottom exit is equipped with apron (201), the upper surface in apron (201) is equipped with weighing sensor (206), apron (201) are installed in slot (202) of hopper body bottom inner wall, set up miniature stepper motor (203) on the outer wall of hopper body, set up rack (204) on the outer wall of apron (201), the output of miniature stepper motor (203) connect one with gear (205) that rack (204) matees, gear (205) and rack (204) intermeshing installation.
6. Phosphogypsum stabilization system according to claim 1, characterized in that: the stabilizer spray device (5) comprises a stabilizer storage tank (501) and a discharging pipeline (502), wherein a regulating valve (503) is arranged on the discharging pipeline (502), and a spray head (504) is arranged at the tail end of the discharging pipeline (502).
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