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 PDF

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Publication number
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
air
temperature
acid
arsenic
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CN106586976B (en
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祝星
李勋
祁先进
王�华
韦龙华
徐媛
李勇
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Kunming University of Science and Technology
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Kunming University of Science and Technology
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00Sulfur; Compounds thereof
    • C01B17/69Sulfur trioxide; Sulfuric acid
    • C01B17/88Concentration of sulfuric acid
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B30/00Obtaining antimony, arsenic or bismuth
    • C22B30/04Obtaining arsenic
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00Working 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
    • C22B7/04Working-up slag
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/10Process efficiency
    • Y02P20/129Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines

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  • 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

A kind of hot copper ashes wind quenching hot blast concentrates waste acid method
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.
CN201611079658.1A 2016-11-30 2016-11-30 A kind of hot copper ashes wind quenching hot wind concentration waste acid method Active CN106586976B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
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

Patent Citations (2)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
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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