CN101870456A - Industrial symbiosis processing method for recycling cold rolled waste acid - Google Patents
Industrial symbiosis processing method for recycling cold rolled waste acid Download PDFInfo
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- CN101870456A CN101870456A CN 201010201154 CN201010201154A CN101870456A CN 101870456 A CN101870456 A CN 101870456A CN 201010201154 CN201010201154 CN 201010201154 CN 201010201154 A CN201010201154 A CN 201010201154A CN 101870456 A CN101870456 A CN 101870456A
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Abstract
The invention relates to an industrial symbiosis processing method for recycling cold rolled waste acid, which comprises the following steps of: recycling the cold rolled waste acid, recycling the iron oxide red which is the byproduct produced during regenerating the cold rolled waste acid, recycling the cadmia which is provided by smelting the steel, comprehensively recycling the waste gas resource and the production waste water, and recycling the nitrogen which is the byproduct produced by the metallurgy oxygen generating factory. The method comprehensively recycles the other wastes when smelting the steel and sufficiently recycles various wastes, for example, recycles the zinc oxide which is regenerated by the waste cadmia as the raw material for producing soft magnetic ferrite powder, recycles the nitrogen which is the byproduct produced the oxygen generating factory to sinter the nitrogen in a protecting way when producing a magnetic core of the soft magnetic ferrite, recycles the waste gas to offer energy to the system, and recycles the production waste water, etc. By implementing the scheme, the method can bring better economic benefit and environmental benefit to enterprises.
Description
Technical field
The present invention relates to a kind of industrial symbiosis processing method for recycling cold rolled waste acid.
Background technology
Along with the sustainable and healthy development of Chinese national economy, China's Iron And Steel Industry also will keep high speed development.2009, China's iron and steel output and consumption occupied half of global total amount approximately.In the case, inevitably to produce a large amount of smelting iron and steel wastes.Usually the smelting iron and steel waste all has very high recycle value, and the changing rejected material to useful resource method of research steel smelting procedure has become the important topic in current environmental protection field.Strip pickling is absolutely necessary in the cold-rolling process of smelting iron and steel, so the processing of spent acid is to become an energy collecting source recycle and environmental protection research topic after the pickling.Contain the hydrochloric acid of reproducible utilization in the cold rolled waste acid,, will do great damage environment if do not handled.The high-purity mangesium oxide iron oxide red of cold rolled waste acid regenerative process by-product is the raw materials for production of high-quality soft magnetic ferrite simultaneously, utilize red iron oxide to produce high-grade soft magnetic ferrite, both increase economic benefit of enterprises, and can alleviate environmental pollution again, had very important realistic meaning.
Current, the resource utilization approach of cold rolled waste acid is more single, and main path is that acid regeneration hydrochloric acid is returned the cold rolling process recycle.Do like this, the subject matter of existence has: high value added product is produced in the deep processing that does not have to pay attention to acid regeneration by product red iron oxide; The red iron oxide bulk deposition not only takies valuable land resources, also can cause certain harm to environment; Production process waste water is not handled recycling, caused water resource waste; Cold rolling acid regeneration by product red iron oxide system soft magnetic materials does not have to pay attention to coke-oven gas, the blast furnace gas to the steel smelting procedure by-product, the utilization of coal gas of converter, has caused the serious waste of resource.
Summary of the invention
The objective of the invention is to defective, a kind of industrial symbiosis processing method for recycling cold rolled waste acid is provided at current recycling cold rolled waste acid approach.
For achieving the above object, the present invention adopts following technical proposals:
A kind of industrial symbiosis processing method for recycling cold rolled waste acid, comprise the comprehensive utilization, the utilization of metallurgical oxyen manutactory by product nitrogen of utilization, waste coal gas resource and factory effluent of utilization, smelting iron and steel cadmia of by product red iron oxide of recycling utilization, the cold rolled waste acid regenerative process of cold rolled waste acid, it is characterized in that this method is specific as follows:
A. the recycling utilization of cold rolled waste acid: the main component of cold rolled waste acid is an iron protochloride, generates hydrogen chloride gas by thermal degradation, and the hydrochloric acid recycling is produced in water-soluble regeneration, obtains the byproduct red iron oxide simultaneously;
B. cold rolled waste acid regeneration by product red iron oxide is utilized: the red iron oxide that obtains among the step a is used for magneticsubstance industrial production soft ferromagnetic powder;
C. the smelting iron and steel cadmia utilizes: Steel Plant will have zinc oxide and the step b gained soft ferromagnetic powder that cadmia processes by oneself, be used to produce magnetic ferrite magnetic core;
D. the comprehensive utilization of waste coal gas resource and factory effluent: utilize the energy of the surplus gas of steel manufacture process generation, and the waste water that production process produces is returned recycle in the soft magnetic ferrite production after treatment as production;
E. metallurgical oxyen manutactory by product nitrogen utilizes: utilize the nitrogen of by-product that the magnetic ferrite magnetic core production process is carried out nitrogen protective sintering.
The present invention and existing recycling cold rolled waste acid compare, and have following conspicuous substantive distinguishing features and advantage: the resource utilization of cold rolled waste acid no longer is single acid regeneration, considers the deep processing of acid regeneration by product red iron oxide simultaneously; The present invention fully utilizes other wastes of steel smelting procedure; make full use of various wastes, as utilize discarded cadmia regenerated zinc oxide as the raw material of producing soft ferromagnetic powder, utilize the nitrogen of oxyen manutactory's by-product that the magnetic ferrite magnetic core production process is carried out nitrogen protective sintering, utilized waste coal gas to provide the energy, recycle factory effluent etc. for system.By the enforcement of this programme, can bring favorable economic benefit and environmental benefit for enterprise.
Description of drawings
Fig. 1 is the industrial symbiosis pattern of recycling cold rolled waste acid.
Fig. 2 is the materials flow chart of this industrial symbiosis pattern.
Concrete implementing method
The present invention is an example to produce 1000 ten thousand tons of steel production enterprise per year, about 3.3 ten thousand tons of the annual generation of cold rolled waste acid regenerating oxidation iron oxide red.To produce soft magnetic ferrite material powder 4.5 ten thousand t/a (high magnetic permeability powder 9000t/a, power-type magnet ferromagnetic powder 3.6 ten thousand t/a), magnetic ferrite magnetic core 10,000 t/a (high magnetic conductivity ferrite magnetic core 3000t/a, power-type FERRITE CORE 7000t/a) is example.
The raw material of soft ferromagnetic powder is respectively red iron oxide (accounting for raw material 70%), trimanganese tetroxide (account for raw material composition 22%), zinc oxide (account for raw material composition 8%) and subsidiary material.Red iron oxide is from the cold rolled waste acid by product of regenerating, and trimanganese tetroxide is outsourcing, and zinc oxide is that Steel Plant will have the zinc oxide that cadmia processes by oneself, and subsidiary material such as PVA are outsourcing.
Soft ferromagnetic powder is directly as the raw material of producing magnetic ferrite magnetic core, and the high magnetic permeability powder of producing 4000t per year is as producing high magnetic conductivity ferrite magnetic core, all the other 5000t export trades; The power-type magnet ferromagnetic powder of producing 8000t per year is as producing power-type FERRITE CORE, all the other 2.8 ten thousand t export trades.
Implementing method is referring to Fig. 1 and Fig. 2.
The first step: the spent acid configuration acid recovery plant in that the cold-rolling pickling operation produces, adopt roasting method regenerant salt acid waste liquid, the product regenerating acid returns pickling process and utilizes.Concrete grammar is with reference to " Baosteel Cold Rolling acid regeneration technology profile and the equipment characteristic " of Zhang Chunqing and " recycling treatment process of industrial acid-washed waste hydrochloric acid containing iron " of Zhang Mengmin;
Second step: many (419 ℃ of zinc fusing points, 1535 ℃ of the iron fusing points) that the fusing point of zinc is lower than iron, utilize the difference of boiling point between them under vacuum state, to heat with Graphite Electrodes, make zinc become the zinc fume volatile matter from, after condensation, become liquid zinc to reach to separate and reclaim zinc.Concrete grammar beautiful gloomy with reference to appointing " pot galvanize zinc slag two-step approach reclaims technical study ";
The 3rd step: high-purity iron oxide red, second zinc oxide that obtains of step that the first step is obtained and other auxiliary materials of outsourcing carry out automatic blending, carry out spraying drying again to form particulate state after adopting wet-mixed, and deliver to rotary kiln and carry out pre-burning, the material that comes out behind the rotary kiln baking is delivered to spray-drier again after by the pulverizer grinding and is carried out granulation.Through particle adjustment, packing warehouse-in after the assay was approved.The product that this step obtains is a soft ferromagnetic powder;
The 4th step: adopt the 3rd soft ferromagnetic powder that obtain of step as raw material, can produce magnetic core with definite shape, size, inductance by operations such as moulding, sintering, mill processing, go-on-gos.Magnetic is processed into and has definite shape, behind the blank of size and weight, carries out roasting by nitrogen protection again through delivering to forming room after the assay was approved, and finished product is delivered to pulverizer and carried out abrasive dust processing after the roasting, puts in storage through ultrasonic cleaning, finished product classification back packing;
The 5th step: collect the nitrogen of oxyen manutactory's by-product, utilize nitrogen that the magnetic ferrite magnetic core production process is carried out nitrogen protective sintering;
The 6th step: collect waste coal gas (coke-oven gas, blast furnace gas, coal gas of converter) and provide fuel for operations such as the pre-burning of cold rolling acid regeneration by product red iron oxide system soft magnetic materials, drying, sintering.Part more than needed provides electric power by the mixed gas combined cycle generation for system.Concrete grammar is with reference to heat ice sister-in-law's " renewable resources of Iron And Steel Industry coal gas " and Gao Yongfen " utilizing the Study on Engineering Design of waste coal gas generating ";
The 7th step: collect factory effluent and return the production cycle utilization after treatment.
Economic benefit
The recycle of cold rolled waste acid regeneration hydrochloric acid, waste coal gas utilization, factory effluent utilize again, have saved the resource consumption cost; To produce 1000 ten thousand tons of steel production enterprise per year is example, about 3.3 ten thousand tons of the annual generation of cold rolled waste acid regenerating oxidation iron oxide red.These red iron oxides are added other raw materials, can produce 4.5 ten thousand tons in soft magnetic ferrite material powder per year, wherein 3.3 ten thousand tons of soft magnetic ferrite material powder export trade remains 1.2 ten thousand tons and is used to produce magnetic ferrite magnetic core, can produce 10000 tons of magnetic ferrite magnetic cores per year.By the enforcement of scheme, not only saved the cost of a part of resource consumption, also the high value added product that can produce can bring favorable economic benefit for enterprise.
Claims (1)
1. industrial symbiosis processing method for recycling cold rolled waste acid, comprise the comprehensive utilization, the utilization of metallurgical oxyen manutactory by product nitrogen of utilization, waste coal gas resource and factory effluent of utilization, smelting iron and steel cadmia of by product red iron oxide of recycling utilization, the cold rolled waste acid regenerative process of cold rolled waste acid, it is characterized in that this method is specific as follows:
B. the recycling utilization of cold rolled waste acid: the main component of cold rolled waste acid is an iron protochloride, generates hydrogen chloride gas by thermal degradation, and the hydrochloric acid recycling is produced in water-soluble regeneration, obtains the byproduct red iron oxide simultaneously;
C. cold rolled waste acid regeneration by product red iron oxide is utilized: the red iron oxide that obtains among the step a is used for magneticsubstance industrial production soft ferromagnetic powder;
D. the smelting iron and steel cadmia utilizes: Steel Plant will have zinc oxide and the step b gained soft ferromagnetic powder that cadmia processes by oneself, be used to produce magnetic ferrite magnetic core;
E. the comprehensive utilization of waste coal gas resource and factory effluent: utilize the energy of the surplus gas of steel manufacture process generation, and the waste water that production process produces is returned recycle in the soft magnetic ferrite production after treatment as production;
F. metallurgical oxyen manutactory by product nitrogen utilizes: utilize the nitrogen of by-product that the magnetic ferrite magnetic core production process is carried out nitrogen protective sintering.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102093042A (en) * | 2010-11-28 | 2011-06-15 | 上海大学 | Resource industrial symbiosis treatment method for hot-rolled iron scale |
| CN102219493A (en) * | 2011-04-29 | 2011-10-19 | 河北钢铁股份有限公司邯郸分公司 | Method for preparing MnZn ferrite material powder from acid washing waste liquid and galvanized zinc slag |
| CN102260070A (en) * | 2011-04-29 | 2011-11-30 | 河北钢铁股份有限公司邯郸分公司 | Preparation method of MnZn ferrite powder with galvanizing zinc slag and pickling waste liquid as raw materials |
| CN102721080A (en) * | 2012-06-13 | 2012-10-10 | 鞍钢股份有限公司 | Method for using coke oven gas on acid regeneration roasting furnace |
-
2010
- 2010-06-12 CN CN 201010201154 patent/CN101870456A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 《现代化工》 20100520 宋金涛等 冷轧废酸再生氧化铁红资源化的工业共生研究 第30卷, 第5期 2 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102093042A (en) * | 2010-11-28 | 2011-06-15 | 上海大学 | Resource industrial symbiosis treatment method for hot-rolled iron scale |
| CN102219493A (en) * | 2011-04-29 | 2011-10-19 | 河北钢铁股份有限公司邯郸分公司 | Method for preparing MnZn ferrite material powder from acid washing waste liquid and galvanized zinc slag |
| CN102260070A (en) * | 2011-04-29 | 2011-11-30 | 河北钢铁股份有限公司邯郸分公司 | Preparation method of MnZn ferrite powder with galvanizing zinc slag and pickling waste liquid as raw materials |
| CN102721080A (en) * | 2012-06-13 | 2012-10-10 | 鞍钢股份有限公司 | Method for using coke oven gas on acid regeneration roasting furnace |
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Open date: 20101027 |