CN106586976A - Method for concentrating waste acid through hot copper slag air-quenching hot air - Google Patents
Method for concentrating waste acid through hot copper slag air-quenching hot air Download PDFInfo
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- CN106586976A CN106586976A CN201611079658.1A CN201611079658A CN106586976A CN 106586976 A CN106586976 A CN 106586976A CN 201611079658 A CN201611079658 A CN 201611079658A CN 106586976 A CN106586976 A CN 106586976A
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- waste acid
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- acid
- arsenic
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- 239000002699 waste material Substances 0.000 title claims abstract description 88
- 239000002253 acid Substances 0.000 title claims abstract description 86
- 238000000034 method Methods 0.000 title claims abstract description 38
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 25
- 239000010949 copper Substances 0.000 title claims abstract description 25
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000010791 quenching Methods 0.000 title claims abstract description 23
- 239000002893 slag Substances 0.000 title claims abstract description 17
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 24
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims abstract description 24
- 230000000171 quenching effect Effects 0.000 claims abstract description 21
- 239000003513 alkali Substances 0.000 claims abstract description 6
- 238000000926 separation method Methods 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 23
- 235000002918 Fraxinus excelsior Nutrition 0.000 claims description 17
- 239000002956 ash Substances 0.000 claims description 17
- 239000012141 concentrate Substances 0.000 claims description 13
- 238000002347 injection Methods 0.000 claims description 5
- 239000007924 injection Substances 0.000 claims description 5
- 230000000630 rising effect Effects 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- 239000007921 spray Substances 0.000 claims description 5
- 239000002585 base Substances 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- 239000002918 waste heat Substances 0.000 abstract description 9
- 239000007789 gas Substances 0.000 abstract description 7
- GOLCXWYRSKYTSP-UHFFFAOYSA-N Arsenious Acid Chemical group O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 239000002244 precipitate Substances 0.000 abstract 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 abstract 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 abstract 1
- 235000011116 calcium hydroxide Nutrition 0.000 abstract 1
- 239000000920 calcium hydroxide Substances 0.000 abstract 1
- 238000005272 metallurgy Methods 0.000 abstract 1
- 239000002245 particle Substances 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 abstract 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 229910052793 cadmium Inorganic materials 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 229910052745 lead Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 230000007812 deficiency Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000010813 municipal solid waste Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000002354 radioactive wastewater Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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
- C01B17/88—Concentration of sulfuric acid
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B30/00—Obtaining antimony, arsenic or bismuth
- C22B30/04—Obtaining arsenic
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/04—Working-up slag
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Processing Of Solid Wastes (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
Abstract
The invention relates to a method for concentrating waste acid through hot copper slag air-quenching hot air and belongs to the technical field of metallurgy and chemical industry environmental protection. The method includes the steps that high-velocity air is sprayed and blown to high-temperature molten slag with the temperature of 1200-1350 DEG C for air quenching, the high-temperature molten slag is cooled into a particle shape, the temperature of the air obtained after air quenching is increased to obtain high-temperature air, the obtained high-temperature air is sprayed from the bottom of a sealed waste acid pool filled with waste acid to the sealed waste acid pool, gas generated by waste acid and the introduced air are introduced into a Ca(OH)2 solution pool, in the process, solid-liquid separation is conducted to obtain a crystallized precipitate (the temperature of the waste acid is increased, moisture in the waste acid and volatile acid are evaporated, and As3+ and As5+ reach supersaturation and are crystallized and separated out in the As2O3 form) and concentrated waste acid, then the obtained crystallized precipitate is treated with an alkali liquor to obtain an arsenic-containing solution, and the arsenic-containing solution is used for arsenic preparation industry. The waste heat of the high-temperature copper slag is used for heating the concentrated waste acid by using the air as a carrier, the heat can be effectively utilized, and the waste acid is concentrated.
Description
Technical field
The present invention relates to a kind of hot copper ashes wind quenching hot blast concentrates waste acid method, belong to metallurgical and chemical industry environmental protection technology neck
Domain.
Background technology
The annual blister copper yield of China at 520,000 tons or so, up to 1,500,000 tons of output slag, along with other by-product waste copper slags
Deng generation, the quantity of copper ashes is quite huge.The temperature of these copper ashes can reach 1200 DEG C -1350 DEG C, containing a large amount of waste heats,
Calorific value is high, belongs to excellent thermal source, very big hence with copper ashes waste heat potentiality.And the energy huge to these parts, do not have now
There is utilization well, mostly processed using the method for bath cooling, waste huge heat, and consume substantial amounts of water money
Source.And field is concentrated in waste acid, suffer from stagnated without cheap calorific value supply always.
For the processing method of waste acid, widely used at present is, using sulfide precipitation-neutralization molysite technique, should to answer
There is many deficiencies in actual application, such as contained valuable element and material do not obtain resource recovery, with
The form for forming solid waste is removed, and causes the waste of resource；Practical operation is complicated, and equipment is had high demands；Generation is difficult to locate in a large number
Reason is utilized and processes the water treatment residues of disposal, and processing cost is high；Water after process is due to originals such as fluorine, cl concn height or hardness height
Cause, seriously governs the reuse of water；Waste acid processes integrated cost height etc..Concentration waste acid is at home and abroad also without extensive pass
Note, and distillation and concentration method is widely used to process high concentrated organic wastewater, radioactive wastewater and percolate from garbage filling field
Process, compare with traditional method, dangerous solid waste is few, processing cost is low, recyclable utility with producing for concentration method
Deng clear superiority.And use air as carrier by Copper making waste residue waste heat for concentrate waste acid this for the first time, be both effectively utilized
Copper ashes waste heat, and concentration waste acid, meet the national policy of the treatment of wastes with processes of wastes against one another, with very big development prospect.
The content of the invention
The problem existed for above-mentioned prior art and deficiency, it is dirty that the present invention provides a kind of hot copper ashes wind quenching hot blast concentration
Sour method.With air as carrier heating concentration waste acid, calorific value can be effectively utilized high temperature copper ashes waste heat of the present invention, and
Concentration waste acid, reaches the purpose of the treatment of wastes with processes of wastes against one another, and economic and environment-friendly, the present invention is achieved through the following technical solutions.
A kind of hot copper ashes wind quenching hot blast concentrates waste acid method, and it is comprised the following steps that：
Step 1, by temperature be 1200～1350 DEG C of high-temperature slags by high-speed air injection carry out wind quenching, high-temperature slag is cooled to
It is granular, the atmosphere temperature rising Jing after wind quenching is obtained into 600～1000 DEG C of high temperature air；
Step 2, the high temperature air for obtaining step 1 are with the pressure of 0.2～0.3MPa units from the sealing waste acid pond equipped with waste acid
Bottom sprays into, and the gas that waste acid is produced and the air being passed through are incorporated into Ca (OH)2Solution pool, is divided in the process admittedly by liquid
From obtaining crystalline deposit（Waste acid temperature is raised, and the moisture and volatile acid in waste acid is evaporated, As3+And As5+Reached
Saturation, with As2O3The form crystallization of precipitation is separated out）With concentration waste acid；
Step 3, the crystalline deposit base extraction for obtaining step 2 obtain arsenic containing solution, and arsenic containing solution is used for arsenic processed industry.
The alkali lye of the step 3 adopts NaOH solution.
The invention has the beneficial effects as follows：
（1）The treatment of wastes with processes of wastes against one another, it is economic and environment-friendly.It is conventional at present for the huge good Application way of copper ashes waste heat neither one
Water-cooled needs to expend huge water resource, and copper ashes waste heat is used to concentrate waste acid, is effectively utilized by the present invention with air as carrier
Copper ashes waste heat, has saved water resource, and with discarded waste heat concentration waste acid, saves the expense for processing waste acid, reach with
It is useless to control useless purpose, it is cost-effective.
（2）The gas of evaporation is passed through into Ca (OH)2Solution pool process, effectively solves the spent acid produced when waste acid is processed
The problem of exhaust emission environment, and with Ca (OH)2The gas of solution process evaporation, economic and environment-friendly, the effect of process is good.
（3）The arsenic of dissolving can be used for the production of arsenic industry, be the very high arsenic raw material of purity.
Description of the drawings
Fig. 1 is present invention process flow chart.
Specific embodiment
With reference to the accompanying drawings and detailed description, the invention will be further described.
Embodiment 1
As shown in figure 1, the hot copper ashes wind quenching hot blast concentrates waste acid method, it is comprised the following steps that：
Step 1, by temperature be 1300 DEG C of high-temperature slags by high-speed air injection carry out wind quenching, by high-temperature slag cooling granulate,
Atmosphere temperature rising Jing after wind quenching is obtained into 1000 DEG C of high temperature air；
Step 2, the high temperature air for obtaining step 1 are with the pressure of 0.3MPa from equipped with waste acid（The constituent content of the waste acid such as institute of table 1
Show）Sealing waste acid bottom of pond portion spray into, the gas and the air that is passed through that waste acid is produced is incorporated into concentration by flow for 1L/min
For the Ca (OH) of 0.5mol/L2Solution pool, obtains crystalline deposit by solid-liquor separation in the process（Waste acid temperature is raised, dirty
Moisture and volatile acid in acid is evaporated, As3+And As5+Supersaturation is reached, with As2O3The form crystallization of precipitation is separated out）
With concentration waste acid（Cocnentration factor is 7, and cocnentration factor is the ratio that sulfuric acid concentration in the sulfuric acid concentration and waste acid in waste acid is concentrated after concentration
Value, the component for concentrating waste acid is as shown in table 2）；
Step 3, the crystalline deposit for obtaining step 2 are 2 according to liquid-solid ratio：1ml/g alkali lye（NaOH solution, concentration is 1mol/
L）Process obtains arsenic containing solution, and arsenic containing solution is used for arsenic processed industry.
Each component content in the waste acid of table 1（mg）
Table 2 concentrates waste acid each component content（mg）
From shown in Tables 1 and 2, arsenic rate of deposition reaches 68% in waste acid, and removal efficiency of flouride has reached 85%, the change of Cu, Pb, Zn, Cd
It is unobvious.
Embodiment 2
As shown in figure 1, the hot copper ashes wind quenching hot blast concentrates waste acid method, it is comprised the following steps that：
Step 1, by temperature be 1350 DEG C of high-temperature slags by high-speed air injection carry out wind quenching, by high-temperature slag cooling granulate,
Atmosphere temperature rising Jing after wind quenching is obtained into 600 DEG C of high temperature air；
Step 2, the high temperature air for obtaining step 1 are with the pressure of 0.2MPa from equipped with waste acid（The constituent content of the waste acid such as institute of table 3
Show）Sealing waste acid bottom of pond portion spray into, the gas and the air that is passed through that waste acid is produced is incorporated into concentration by flow for 1L/min
For the Ca (OH) of 0.5mol/L2Solution pool, obtains crystalline deposit by solid-liquor separation in the process（Waste acid temperature is raised, dirty
Moisture and volatile acid in acid is evaporated, As3+And As5+Supersaturation is reached, with As2O3The form crystallization of precipitation is separated out）
With concentration waste acid（Cocnentration factor is 7, and cocnentration factor is the ratio that sulfuric acid concentration in the sulfuric acid concentration and waste acid in waste acid is concentrated after concentration
Value, the component for concentrating waste acid is as shown in table 4）；
Step 3, the crystalline deposit for obtaining step 2 are 2 according to liquid-solid ratio：1ml/g alkali lye（NaOH solution, concentration is 1mol/
L）Process obtains arsenic containing solution, and arsenic containing solution is used for arsenic processed industry.
Each component content in the waste acid of table 3（mg）
Table 4 concentrates waste acid each component content（mg）
From shown in table 3 and table 4, arsenic rate of deposition reaches 60% in waste acid, and removal efficiency of flouride has reached 79%, the change of Cu, Pb, Zn, Cd
It is unobvious.
Embodiment 3
As shown in figure 1, the hot copper ashes wind quenching hot blast concentrates waste acid method, it is comprised the following steps that：
Step 1, by temperature be 1200 DEG C of high-temperature slags by high-speed air injection carry out wind quenching, by high-temperature slag cooling granulate,
Atmosphere temperature rising Jing after wind quenching is obtained into 800 DEG C of high temperature air；
Step 2, the high temperature air for obtaining step 1 are with the pressure of 0.3MPa from equipped with waste acid（The constituent content of the waste acid such as institute of table 5
Show）Sealing waste acid bottom of pond portion spray into, the gas and the air that is passed through that waste acid is produced is incorporated into concentration by flow for 1L/min
For the Ca (OH) of 0.5mol/L2Solution pool, obtains crystalline deposit by solid-liquor separation in the process（Waste acid temperature is raised, dirty
Moisture and volatile acid in acid is evaporated, As3+And As5+Supersaturation is reached, with As2O3The form crystallization of precipitation is separated out）
With concentration waste acid（Cocnentration factor is 7, and cocnentration factor is the ratio that sulfuric acid concentration in the sulfuric acid concentration and waste acid in waste acid is concentrated after concentration
Value, the component for concentrating waste acid is as shown in table 6）；
Step 3, the crystalline deposit for obtaining step 2 are 2 according to liquid-solid ratio：1ml/g alkali lye（NaOH solution, concentration is 1mol/
L）Process obtains arsenic containing solution, and arsenic containing solution is used for arsenic processed industry.
Each component content in the waste acid of table 5（mg）
Table 6 concentrates waste acid each component content（mg）
From shown in table 5 and table 6, arsenic rate of deposition reaches 63% in waste acid, and removal efficiency of flouride has reached 82%, the change of Cu, Pb, Zn, Cd
It is unobvious.
Above in association with accompanying drawing to the present invention specific embodiment be explained in detail, but the present invention be not limited to it is above-mentioned
Embodiment, in the ken that those of ordinary skill in the art possess, can be with before without departing from present inventive concept
Put that various changes can be made.
Claims (2)
1. a kind of hot copper ashes wind quenching hot blast concentrates waste acid method, it is characterised in that comprise the following steps that：
Step 1, by temperature be 1200～1350 DEG C of high-temperature slags by high-speed air injection carry out wind quenching, high-temperature slag is cooled to
It is granular, the atmosphere temperature rising Jing after wind quenching is obtained into 600～1000 DEG C of high temperature air；
Step 2, the high temperature air for obtaining step 1 are with the pressure of 0.2～0.3MPa from the sealing waste acid bottom of pond portion equipped with waste acid
Spray into, the gas that waste acid is produced and the air being passed through are incorporated into Ca (OH)2Solution pool, is obtained in the process by solid-liquor separation
To crystalline deposit and concentration waste acid；
Step 3, the crystalline deposit base extraction for obtaining step 2 obtain arsenic containing solution, and arsenic containing solution is used for arsenic processed industry.
2. hot copper ashes wind quenching hot blast according to claim 1 concentrates waste acid method, it is characterised in that：The step 3
Alkali lye adopts NaOH solution.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611079658.1A CN106586976B (en) | 2016-11-30 | 2016-11-30 | A kind of hot copper ashes wind quenching hot wind concentration waste acid method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611079658.1A CN106586976B (en) | 2016-11-30 | 2016-11-30 | A kind of hot copper ashes wind quenching hot wind concentration waste acid method |
Publications (2)
| Publication Number | Publication Date |
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| CN106586976A true CN106586976A (en) | 2017-04-26 |
| CN106586976B CN106586976B (en) | 2018-12-14 |
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| CN201611079658.1A Active CN106586976B (en) | 2016-11-30 | 2016-11-30 | A kind of hot copper ashes wind quenching hot wind concentration waste acid method |
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| Country | Link |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109534476A (en) * | 2018-11-01 | 2019-03-29 | 昆明理工大学 | A kind of method that copper ashes handles arsenic in nonferrous smelting waste acid |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103351049A (en) * | 2013-06-28 | 2013-10-16 | 中国恩菲工程技术有限公司 | Method of processing waste acid |
| CN105177316A (en) * | 2015-08-28 | 2015-12-23 | 湖南雷恩蒙特冶化环境与资源科技有限公司 | Treatment method for arsenical waste liquid |
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2016
- 2016-11-30 CN CN201611079658.1A patent/CN106586976B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103351049A (en) * | 2013-06-28 | 2013-10-16 | 中国恩菲工程技术有限公司 | Method of processing waste acid |
| CN105177316A (en) * | 2015-08-28 | 2015-12-23 | 湖南雷恩蒙特冶化环境与资源科技有限公司 | Treatment method for arsenical waste liquid |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109534476A (en) * | 2018-11-01 | 2019-03-29 | 昆明理工大学 | A kind of method that copper ashes handles arsenic in nonferrous smelting waste acid |
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