CN112225184A - Method for recycling acid sludge in flue gas purification of pyrite acid making device - Google Patents
Method for recycling acid sludge in flue gas purification of pyrite acid making device Download PDFInfo
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- CN112225184A CN112225184A CN202011263949.2A CN202011263949A CN112225184A CN 112225184 A CN112225184 A CN 112225184A CN 202011263949 A CN202011263949 A CN 202011263949A CN 112225184 A CN112225184 A CN 112225184A
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- Prior art keywords
- acid
- pyrite
- acid sludge
- flue gas
- making device
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- 239000002253 acid Substances 0.000 title claims abstract description 78
- 239000010802 sludge Substances 0.000 title claims abstract description 48
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910052683 pyrite Inorganic materials 0.000 title claims abstract description 34
- 239000011028 pyrite Substances 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 27
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 239000003546 flue gas Substances 0.000 title claims abstract description 22
- 238000000746 purification Methods 0.000 title claims abstract description 21
- 238000004064 recycling Methods 0.000 title claims abstract description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000012065 filter cake Substances 0.000 claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 claims abstract description 15
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 13
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims abstract description 12
- 235000011941 Tilia x europaea Nutrition 0.000 claims abstract description 12
- 239000004571 lime Substances 0.000 claims abstract description 12
- 238000003825 pressing Methods 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 238000011084 recovery Methods 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 239000008267 milk Substances 0.000 claims abstract description 6
- 210000004080 milk Anatomy 0.000 claims abstract description 6
- 235000013336 milk Nutrition 0.000 claims abstract description 6
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 5
- 239000002002 slurry Substances 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 4
- 239000000706 filtrate Substances 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000000926 separation method Methods 0.000 claims abstract description 4
- 239000007787 solid Substances 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- 239000011575 calcium Substances 0.000 claims description 18
- GOLCXWYRSKYTSP-UHFFFAOYSA-N arsenic trioxide Inorganic materials O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 claims description 17
- COHDHYZHOPQOFD-UHFFFAOYSA-N arsenic pentoxide Inorganic materials O=[As](=O)O[As](=O)=O COHDHYZHOPQOFD-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 229910052785 arsenic Inorganic materials 0.000 claims description 7
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 6
- 150000001447 alkali salts Chemical class 0.000 claims description 3
- 229910052925 anhydrite Inorganic materials 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 3
- LGBCMHYFFJVCFY-UHFFFAOYSA-N calcium;hydrogen arsorite Chemical compound [Ca+2].O[As]([O-])[O-] LGBCMHYFFJVCFY-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 2
- 239000001117 sulphuric acid Substances 0.000 claims description 2
- 235000011149 sulphuric acid Nutrition 0.000 claims description 2
- HJTAZXHBEBIQQX-UHFFFAOYSA-N 1,5-bis(chloromethyl)naphthalene Chemical compound C1=CC=C2C(CCl)=CC=CC2=C1CCl HJTAZXHBEBIQQX-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 2
- 239000002920 hazardous waste Substances 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/74—Preparation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/48—Sulfur dioxide; Sulfurous acid
- C01B17/50—Preparation of sulfur dioxide
- C01B17/501—Preparation of sulfur dioxide by reduction of sulfur compounds
- C01B17/506—Preparation of sulfur dioxide by reduction of sulfur compounds of calcium sulfates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/48—Sulfur dioxide; Sulfurous acid
- C01B17/50—Preparation of sulfur dioxide
- C01B17/52—Preparation of sulfur dioxide by roasting sulfides
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Treatment Of Sludge (AREA)
Abstract
The invention discloses a method for recycling acid sludge in a flue gas purification device for producing acid from pyrite, which comprises six processing steps: (1) and (3) settling: the dilute sulfuric acid containing acid sludge is subjected to primary liquid-solid separation in a settling device, clear liquid is returned to the device to be used as washing liquid, and the acid sludge is sent to a neutralization reaction tank; (2) neutralizing: continuously adding lime milk into the acid sludge in the neutralization reaction tank under the stirring state, and sending the slurry completely reacted to a plate-and-frame filter press; (3) and (3) filter pressing: filter-pressing the slurry in a plate-and-frame filter press, returning the filtrate to the neutralization reaction tank, and conveying the filter cake to a hot-blast stove; (4) drying: baking the filter cake in a hot air furnace to reduce moisture; (5) crushing: sending the dried filter cake to a crusher for crushing; (6) blending and roasting: the crushed acid mud and the pyrite are blended in proportion and are used as production raw materials of a roasting furnace of a pyrite acid making device, and the production raw materials are sent to the roasting furnace to be roasted. The method is suitable for resource recovery of acid sludge generated by flue gas purification of the pyrite acid making device.
Description
Technical Field
The invention relates to the field of recycling of acid waste residues of chemical devices, in particular to a method for recycling acid sludge from flue gas purification of a pyrite acid making device.
Background
At present, acid sludge generated by flue gas purification of a pyrite acid-making device in a chemical plant generally contains certain sulfuric acid and arsenic, and belongs to hazardous waste. There is no mature and compliant treatment method in China. However, the existing technologies related to acid sludge treatment are few, and domestic patents include CN200910306749.8 "a method for separating and recovering sulfur, iron and selenium from selenium-containing acid sludge", CN201310205229.4 "a smelting method for acid sludge treatment", and CN201710211864.1 "a method for extracting mercury from heavy acid sludge", and the like.
Disclosure of Invention
The invention aims to provide a simple, low-cost and compliant resource recovery method for flue gas purification acid sludge of a pyrite acid making device.
The technical scheme of the invention is as follows: a method for recycling acid sludge from flue gas purification of a pyrite acid making device comprises six treatment steps:
(1) and (3) settling: the dilute sulfuric acid containing acid sludge is subjected to primary liquid-solid separation in a settling device, clear liquid is returned to the device to be used as washing liquid, and the acid sludge is sent to a neutralization reaction tank;
(2) neutralizing: lime milk is continuously added into the acid sludge in the neutralization reaction tank under the stirring state, and the main reaction formula is as follows:
Ca(OH)2+H2SO4=CaSO4+2H2O
the oxide of arsenic in the acid sludge is As2O3，As2O5Arsenic trioxide is also called arsenic trioxide, and is extremely toxic, and arsenic pentoxide is less toxic than arsenic trioxide. Wherein, when trivalent arsenic reacts with lime, insoluble calcium meta-arsenite Ca (AsO) is generated2)2Or the basic salt Ca (OH) AsO of calcium meta-arsenite2When the lime is excessive, calcium pyroarsenite Ca is generated2As2O5
As2O3+2Ca（OH）2＝Ca2As2O5+2H2O
(3) And (3) filter pressing: filter-pressing the slurry in a plate-and-frame filter press, returning the filtrate to a neutralization reaction tank, wherein the water content of a filter cake obtained by filter pressing is 10-12%, and conveying the filter cake to a hot blast stove through a belt conveyor;
(4) drying: baking the filter cake in a hot air furnace to reduce water, wherein the water content is 2-3% after baking;
(5) crushing: sending the baked filter cake to a crusher for crushing;
(6) blending and roasting: the crushed dry acid mud and the pyrite are blended in proportion and used as production raw materials of a roasting furnace of a pyrite acid making device, and the production raw materials are sent to the roasting furnace to be roasted.
Further, the method for recycling the acid sludge through flue gas purification of the pyrite acid making device comprises the step (2) of neutralizing the tank with the pH value of 5-8.
Further, the method for recycling acid sludge through flue gas purification of the pyrite acid making device comprises the following steps of (2): 15 to 65 percent.
Preferably, in the method for recycling the acid sludge through flue gas purification of the pyrite acid making device, the temperature of the hot blast stove in the step (4) is 350-500 ℃.
Preferably, the resource recovery method of the acid sludge from flue gas purification of the pyrite-based sulphuric acid production device comprises the following steps of (5): less than or equal to 10 mm.
Preferably, in the method for recycling the acid sludge from flue gas purification of the pyrite-based acid making device, the dried acid sludge crushed in the step (6) and pyrite are blended according to 1-40% and are used as production raw materials of a roasting furnace of the pyrite-based acid making device, and the production raw materials are sent to the roasting furnace for roasting.
The invention has the beneficial effects that: the method is simple and convenient to operate, simple in equipment and capable of effectively solving the problem that the flue gas purification acid sludge of the pyrite acid making device is difficult to recover; the method can realize the reutilization of resources, reduce the production cost, save the energy and have very important significance in the aspects of resource recovery and environmental protection.
Drawings
FIG. 1 is a schematic flow chart of the present invention.
Detailed Description
A method for recycling acid sludge from flue gas purification of a pyrite acid making device is characterized by comprising six processing steps: (1) and (3) settling: the dilute sulfuric acid containing acid sludge is subjected to primary liquid-solid separation in a settling device, clear liquid is returned to the device to be used as washing liquid, and the acid sludge is sent to a neutralization reaction tank; (2) neutralizing: continuously adding lime milk into the acid sludge in the neutralization reaction tank under the stirring state, wherein the concentration of the added lime milk is as follows: 50 percent.
The main reaction formula is as follows:
Ca(OH)2+H2SO4=CaSO4+2H2O
the oxide of arsenic in the acid sludge is As2O3，As2O5Arsenic trioxide is also called as arsenic trioxide, and has strong toxicity, and the toxicity of arsenic pentoxide is weaker than that of arsenic trioxide; wherein, when trivalent arsenic reacts with lime, insoluble calcium meta-arsenite Ca (AsO) is generated2)2Or the basic salt Ca (OH) AsO of calcium meta-arsenite2When the lime is excessive, calcium pyroarsenite Ca is generated2As2O5；
As2O3+2Ca（OH）2＝Ca2As2O5+2H2O
(2) And (3) filter pressing: filter-pressing the slurry in a plate-and-frame filter press, returning the filtrate to a neutralization reaction tank, wherein the water content of a filter cake obtained by filter pressing is 10-12%, and conveying the filter cake to a hot blast stove through a belt conveyor; (4) drying: baking the filter cake in a hot air furnace, wherein the temperature of the hot air furnace is set to be 350-500 ℃. Reducing water content, and after baking, the water content is 2 to 3 percent; (5) crushing: sending the baked filter cake to a crusher for crushing, wherein the crushing particle size is as follows: less than or equal to 10 mm; (6) blending and roasting: the crushed dry acid mud and the pyrite are blended in proportion and used as production raw materials of a roasting furnace of a pyrite acid making device, and the production raw materials are sent to the roasting furnace to be roasted.
The implementation benefit is as follows: at present, the acid sludge generated by the flue gas purification of the pyrite acid making device does not have a mature treatment method, the acid sludge is sent to a hazardous waste treatment device, the comprehensive cost is higher, and the sulfur element of the acid sludge is not recovered, so that the resources are wasted, and the cost of harmless treatment is increased. After the method is adopted, enterprises can carry out harmless treatment on the acid sludge by fully utilizing the existing production device with less investment, and recover the sulfur element in the acid sludge, thereby realizing resource recovery of the acid sludge. Has good economic and social benefits.
Claims (6)
1. A method for recycling acid sludge from flue gas purification of a pyrite acid making device is characterized by comprising the following steps: comprises six processing steps:
and (3) settling: the dilute sulfuric acid containing acid sludge is subjected to primary liquid-solid separation in a settling device, clear liquid is returned to the device to be used as washing liquid, and the acid sludge is sent to a neutralization reaction tank;
(2) neutralizing: lime milk is continuously added into the acid sludge in the neutralization reaction tank under the stirring state, and the main reaction formula is as follows:
Ca(OH)2+H2SO4=CaSO4+2H2O
the oxide of arsenic in the acid sludge is As2O3Wherein, when trivalent arsenic is acted with lime, insoluble calcium meta-arsenite Ca (AsO) is generated2)2Or the basic salt Ca (OH) AsO of calcium meta-arsenite2When the lime is excessive, calcium pyroarsenite Ca is generated2As2O5
As2O3+2Ca（OH）2＝Ca2As2O5+2H2O
(3) And (3) filter pressing: filter-pressing the slurry in a plate-and-frame filter press, returning the filtrate to a neutralization reaction tank, wherein the water content of a filter cake obtained by filter pressing is 10-12%, and conveying the filter cake to a hot blast stove through a belt conveyor;
(4) drying: baking the filter cake in a hot air furnace to reduce water, wherein the water content is 2-3% after baking;
(5) crushing: sending the baked filter cake to a crusher for crushing;
(6) blending and roasting: the crushed dry acid mud and the pyrite are blended in proportion and used as production raw materials of a roasting furnace of a pyrite acid making device, and the production raw materials are sent to the roasting furnace to be roasted.
2. The resource recovery method of the acid sludge from flue gas purification of the pyrite acid making device according to claim 1, wherein in the step (2), the pH value of the neutralization tank is 5-8.
3. The resource recovery method of the acid sludge purified by the flue gas of the pyrite acid making device according to claim 1, characterized in that the concentration of lime milk added in the step (2): 15 to 65 percent.
4. The resource recovery method of the acid sludge from flue gas purification of the pyrite acid making device according to claim 1, wherein the temperature of the hot blast stove in the step (4) is 350-500 ℃.
5. The resource recovery method of the acid sludge from flue gas purification of the pyrite-based sulphuric acid production plant according to claim 1, characterized in that the crushing particle size in step (5): less than or equal to 10 mm.
6. The method for recycling the acid sludge from the flue gas purification of the pyrite-based acid making device according to claim 1, wherein the dried crushed acid sludge and the pyrite in the step (6) are blended according to 1-40% and used as production raw materials of a roasting furnace of the pyrite-based acid making device to be sent to the roasting furnace for roasting.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011263949.2A CN112225184A (en) | 2020-11-12 | 2020-11-12 | Method for recycling acid sludge in flue gas purification of pyrite acid making device |
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| CN202011263949.2A CN112225184A (en) | 2020-11-12 | 2020-11-12 | Method for recycling acid sludge in flue gas purification of pyrite acid making device |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115818586A (en) * | 2023-02-24 | 2023-03-21 | 昆明理工大学 | Method for extracting selenium and mercury by cooperatively treating mercury selenate sludge and neutralized slag |
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| CN101245409A (en) * | 2008-03-31 | 2008-08-20 | 昆明理工大学 | Method for producing iron ore concentrate with high arsenic ferro-sulphur ore concentrate |
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| CN103468956A (en) * | 2013-09-11 | 2013-12-25 | 河南中原黄金冶炼厂有限责任公司 | Method for recycling multiple elements in acid mud generated in acid making through gold smelting |
| CN109626339A (en) * | 2018-12-18 | 2019-04-16 | 广州华润热电有限公司 | A kind of method that gypsum prepares sulfuric acid |
-
2020
- 2020-11-12 CN CN202011263949.2A patent/CN112225184A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101245409A (en) * | 2008-03-31 | 2008-08-20 | 昆明理工大学 | Method for producing iron ore concentrate with high arsenic ferro-sulphur ore concentrate |
| CN102849814A (en) * | 2011-06-28 | 2013-01-02 | 湖南合磷化工有限公司 | Treatment method for purifying sewage and tail gas from furnace gas in acid production from gypsum |
| CN103468956A (en) * | 2013-09-11 | 2013-12-25 | 河南中原黄金冶炼厂有限责任公司 | Method for recycling multiple elements in acid mud generated in acid making through gold smelting |
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| CN115818586A (en) * | 2023-02-24 | 2023-03-21 | 昆明理工大学 | Method for extracting selenium and mercury by cooperatively treating mercury selenate sludge and neutralized slag |
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