CN110065930A - The recycling and reusing method and recycling and reusing device of acid washing rolled steel waste liquid - Google Patents
The recycling and reusing method and recycling and reusing device of acid washing rolled steel waste liquid Download PDFInfo
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- CN110065930A CN110065930A CN201910464581.7A CN201910464581A CN110065930A CN 110065930 A CN110065930 A CN 110065930A CN 201910464581 A CN201910464581 A CN 201910464581A CN 110065930 A CN110065930 A CN 110065930A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/01—Chlorine; Hydrogen chloride
- C01B7/07—Purification ; Separation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/10—Halides
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- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Abstract
The invention discloses a kind of recycling and reusing methods of acid washing rolled steel waste liquid, concentrated hydrochloric acid is reacted the HCl gas generated with anhydrous calcium chloride and is passed through pickle liquor by this method, the hydrochloric acid solution that the mass concentration that solution after concentrated hydrochloric acid is reacted with anhydrous calcium chloride is obtained through distillation, reverse osmosis concentration is about 7% is also added in pickle liquor, after acid waste liquid is reacted with the hydrochloric acid solution of HCl gas, 7% or so, Iron dichloride tetrahydrate crystallization is precipitated, supernatant fluid reuse flow back in the cleaning of steel, completes the recycling and reusing to pickle liquor.The recovery method of the acid washing rolled steel waste liquid of acquisition conveniently and efficiently realizes zero-emission and recycling and reusing to acid washing rolled steel waste liquid, not only significantly reduces enterprise and obtains environmental protection pressure and operating cost, will not also generate secondary pollution.
Description
Technical field
The present invention relates to recovery processing pickle liquor technical field more particularly to a kind of recycling of acid washing rolled steel waste liquid are sharp again
With method, meanwhile, further relate to the recycling and reusing device for the recycling and reusing method
Background technique
The pickling processes of steel are for removing the cold rolled sheet blank i.e. iron scale on hot rolled plate surface.In production hot dip
When zinc steel pipe, zinc plating steel pipe, coated steel pipe or plastic coatings steel pipe, this layer of iron scale must be removed, and otherwise can
Product quality is caused to seriously affect, or even qualified product cannot be produced.Even if zinc-plated preceding in the presence of very thin iron oxide
Skin, it is also not possible to plate complete, continuous zinc layers.When carrying out coating or cladding is handled, if oxide on surface not removed,
It can cause the corrosion resistance for being bubbled and reducing coating.Pickling processes can not when being current steel production and steel surface processing
Or scarce technical process can cause environment seriously to pollute if a large amount of acid pickles of generation do not handle direct emission, it is greatly dirty
Contaminate water and soil.
What the existing processing to spent acid generallyd use is distillation treatment process or neutralizes technique, and distillation treatment process is mainly
Spent acid is heated using distillation equipment, evaporates dilute hydrochloric acid, so that frerrous chloride crystallization is precipitated, although distillation treatment process technique
Simply, the problems such as but to be faced with cost investment big, complicated for operation, and the dilute hydrochloric acid evaporated can not be handled；Neutralize technique master
If it is simple for process using alkali neutralization spent acid, but management is cumbersome, is difficult to control, and processing cost is high, can also generate a large amount of difficulties
With the sludge of disposition, secondary pollution is easily caused；In addition, further including Pintsch process, UF membrane, ion friendship to the treatment process of spent acid
It the technologies such as changes, but haves the defects that very big and deficiency, energy consumption is high, equipment investment is big, byproduct can not be handled.
Summary of the invention
To solve the shortcomings of the prior art, the present invention provides a kind of recycling and reusing sides of acid washing rolled steel waste liquid
Method, this method conveniently, efficiently realize the recycling and reusing to acid washing rolled steel waste liquid, not only reduce the wind of enterprise in environmental protection
The operating cost of danger and enterprise, will not also generate secondary pollution.
To achieve the above object, the recycling and reusing method of acid washing rolled steel waste liquid provided by the invention, comprising the following steps:
A, the pickle liquor obtained by hydrochloric acid cleaning steel is collected；
B, reacting for concentrated hydrochloric acid and anhydrous calcium chloride is carried out, HCl gas obtained is passed directly into pickle liquor, will be reacted
Solution handles to obtain dilute hydrochloric acid solution through distillation afterwards；
C, the dilute hydrochloric acid solution that step b is obtained through reverse osmosis concentration obtain mass concentration be 6.5~7.5% hydrochloric acid it is molten
6.5~7.5% hydrochloric acid solution is added in pickle liquor by liquid；
D, acid waste liquid is reacted with HCl gas, hydrochloric acid solution, and Iron dichloride tetrahydrate crystallization, abundant analysis to be crystallized is precipitated
After out, reflux supernatant fluid reuse completes the recycling and reusing to pickle liquor in the cleaning of steel.
Recycling and reusing method of the invention is reacted with anhydrous calcium chloride first with concentrated hydrochloric acid, makes anhydrous chlorination
Calcium uptake moisture is to generate HCl gas, and solution handles to obtain certain density hydrochloric acid molten through distillation, reverse osmosis concentration after reaction
Then the HCL gas of generation is all passed into pickle liquor with certain density hydrochloric acid solution in concentration and reacts, promotees by liquid
The form Precipitation for crystallizing the impurity in acid washing rolled steel waste liquid with four water frerrous chlorides, to obtain in concentration of hydrochloric acid, miscellaneous
Matter content etc. is all satisfied the index request of cleaning steel hydrochloric acid, and realization reaches on a low-cost basis to acid washing rolled steel
It is comprehensive in environmental protection, economy, investment, operability etc. in the process successfully to break through steel waste acid treatment for comprehensive recycling and reusing of waste liquid
The technological deficiency of aspect；In addition, the four water frerrous chloride crystalline solid that the present invention obtains are safe and non-toxic, wastewater treatment is applied also for
In, secondary pollution will not be generated.Concentrated hydrochloric acid need to be only added in recycling and reusing method of the invention during waste acid treatment
It obtains being back to the hydrochloric acid solution of steel cleaning, not only has that low energy consumption, easy to operate, operating cost is low, recycling and reusing
The advantages such as effect is good, will not also generate the byproduct product in addition to four water frerrous chlorides, with positive dissemination and significant
Environment protection significance.
As the restriction to above-mentioned technical proposal, the consumption proportion of the pickle liquor and HCl gas is (0.9~1.1)
T:(190~210) kg.
As the restriction to above-mentioned technical proposal, the consumption proportion of concentrated hydrochloric acid and anhydrous calcium chloride is 1:(1.8 in step b
~2.0)；After first 1~2h of reaction is added into 1t anhydrous calcium chloride solid with the flow velocity of 200~350kg/h in the concentrated hydrochloric acid, then
With the flow velocity of 80~200kg/h, the 0.5~1.5h that is added into anhydrous calcium chloride solid that the reaction was continued.
It controls the additional amount of concentrated hydrochloric acid solution, flow velocity is added, and then control the production quantity of HCl gas and be passed through pickle liquor
Gas flow rate, the gas flow rate requirement needed is reacted to match pickle liquor with HCl, reaches effective and efficient place of spent acid
Reason.
As the restriction to above-mentioned technical proposal, the mass concentration of dilute hydrochloric acid described in step b is 0.8~1.2%.
As the restriction to above-mentioned technical proposal, 6.5~7.5% hydrochloric acid solutions that step c is obtained are before being passed through HCl gas
It is added at one time into pickle liquor.
As the restriction to above-mentioned technical proposal, the acid waste liquid reacts 4.5~5.5h with HCl gas, hydrochloric acid solution
Afterwards, it obtains that the hydrochloric acid solution that the mass concentration of steel cleaning is 25~32% can be back to.
It further limits, the additional amount and addition flow velocity of concentrated hydrochloric acid solution, the hydrochloric acid solution being added into pickle liquor
The standard that concentration and pickling reaction terminate, while improving processing method, it is ensured that the processing of recycling and reusing method is imitated
Fruit.
Meanwhile the present invention also provides a kind of recycling and reusing devices of acid washing rolled steel waste liquid, including pickle liquor to collect
Pond collects bottom of pond portion in pickle liquor and is equipped with liquid outlet, and the liquid outlet passes through the lift line equipped with elevator pump and is connected to pickling
Waste disposal unit；
The pickle liquor processing unit includes the two-stage reaction kettle being connected in parallel, and the reaction kettle includes sealable kettle
Air inlet pipeline is arranged at the top of autoclave body in body, and the outlet of the air inlet pipeline extends under the reaction solution liquid level contained in autoclave body,
The entrance of the air inlet pipeline is connected with HCl gas generating device；Gas overflowing pipeline is also set up at the top of autoclave body, it is described
The outlet of gas overflowing pipeline is connected to the air inlet pipeline of another order reaction kettle；The downstream of the HCl gas generating device also according to
It is secondary to be connected with distilling apparatus, reverse osmosis unit, the concentrated solution outlet of the reverse osmosis unit return be connected to be arranged on reaction kettle into
Expects pipe road；Supernatant discharge outlet and solid waste discharge port are additionally provided on the autoclave body.
As the restriction to above scheme, blender is additionally provided on the autoclave body.
As the restriction to above scheme, the first triple valve and electromagnetic flowmeter be set on the lift line, it is described into
Regulating valve and electromagnetic flowmeter are set on air pipe and feeding pipe.
As the restriction to above scheme, the supernatant discharge outlet through the second triple valve, one by circulating pump with into
Air pipe is connected, another to be connected with reuse pipeline.
Recycling and reusing device provided by the invention, is more advantageous to the application of above-mentioned recycling and reusing method, and effectively protects
Hinder the concentration and content of recoverable spent acid, to realize to the zero-emission of spent acid and the recycling of by-product.
In conclusion using technical solution of the present invention, the recycling and reusing method of the acid washing rolled steel waste liquid of acquisition, right
In the treatment process of spent acid, using the HCl gas for reacting preparation with anhydrous calcium chloride by concentrated hydrochloric acid, mentioned into acid washing rolled steel waste liquid
Solution for suitable concentration, the HCl gas of suitable flow rate, and after concentrated hydrochloric acid is reacted with anhydrous calcium chloride is through distillation, reverse osmosis
The certain concentration hydrochloric acid solution that concentration obtains is added to pickle liquor, and the waste acidity recovery of Lai Shixian acid washing rolled steel waste liquid is sharp again
With reaching the zero-emission of spent acid and the recycling of by-product, and four water frerrous chloride of by-product can be used as Waste water treatment medicament, simultaneously
The spent acid for preparing HCl gas reaction generation also obtains reuse, avoids generating secondary pollution comprehensively, and it is useless to solve processing acid washing rolled steel
The technical problem of liquid has significant market value and application value.Recycling and reusing method of the invention, not only reduces enterprise
The pressure of the dual aspect of environmental protection and economy, also has that low energy consumption, easy to operate, the advantages such as operating cost is low.It is provided by the invention
Recyclable device, is more advantageous to the application of above-mentioned recycling and reusing method, and the concentration of effective guarantee recoverable spent acid with contain
Amount.
Detailed description of the invention
With reference to the accompanying drawing and specific embodiment mode does more detailed description to the present invention:
Fig. 1 is the structural schematic diagram of the recycling and reusing device of the embodiment of the present invention；
Fig. 2 is the structural schematic diagram of gas overflowing pipeline in reaction kettle in the embodiment of the present invention；
Fig. 3 is the schematic diagram that concentrated hydrochloric acid solution quality and time are added in the present invention；
Fig. 4 is the quality and the schematic diagram of time that HCL gas is generated in the present invention.
In figure: 1- pickle liquor collecting pit；2- liquid outlet；3- elevator pump；4- lift line；5- reaction kettle；6- gas overflows
Pipeline out；7- air inlet pipeline；8-HCl gas generating device；9- distilling apparatus；10- reverse osmosis unit；11- concentrated solution outlet；
12- feeding pipe；13- supernatant discharge outlet；14- solid waste discharge port；15- blender；The first triple valve of 16-；The second threeway of 17-
Valve；18- electromagnetic flowmeter；19- regulating valve；20- circulating pump；21- reuse pipeline.
Specific embodiment
Below in conjunction with embodiment, technical solution of the present invention is clearly and completely described, it is clear that described
Embodiment is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field
Those of ordinary skill's every other embodiment obtained without making creative work, belongs to protection of the present invention
Range.
Embodiment one
The present embodiment is related to the recycling and reusing method of acid washing rolled steel waste liquid.
Embodiment 1.1
A kind of recycling and reusing method of acid washing rolled steel waste liquid, comprising the following steps:
A, the pickle liquor obtained by hydrochloric acid cleaning steel is collected, 1 ton of pickle liquor is contained in 2 tons by elevator pump
In closed reaction kettle；
B, the anhydrous calcium chloride of 1350kg, the concentrated hydrochloric acid of 675kg are weighed, and adds concentrated hydrochloric acid first with the flow velocity of 300kg/h
Enter into anhydrous calcium chloride solid and react 1.5h, then is continued instead with being added after the flow velocity of 150kg/h into anhydrous calcium chloride solid
Answer 1.5h (in concentrated hydrochloric acid solution and anhydrous calcium chloride reaction process, as shown in Figure 3-4, be added concentrated hydrochloric acid solution quality and
The quality for generating HCl gas is inversely proportional with the time, and the frequency of concentrated hydrochloric acid quality is added and generates the frequency of HCl gaseous mass
Match), HCl gas and reaction solution are obtained after reaction, and reaction solution distillation is handled to obtain dilute salt that mass concentration is 1%
Acid solution；
C, it is 7% that the dilute hydrochloric acid solution that the mass concentration that step b is obtained is 1%, which obtains mass concentration through reverse osmosis concentration,
7% hydrochloric acid solution is added in pickle liquor by hydrochloric acid solution；
D, after being added at one time 7% hydrochloric acid solution of 70kg into the acid waste liquid of 1t, then it is passed through HCl made from step a
Gas, reacting after 5h terminates, and obtains the hydrochloric acid solution that can be back to steel cleaning, to complete sharp again to the recycling of pickle liquor
With can concentration of hydrochloric acid be 28% in the supernatant of reuse, impurity F e content is 3.2%.
Embodiment 1.2
A kind of recycling and reusing method of acid washing rolled steel waste liquid, comprising the following steps:
A, the pickle liquor obtained by hydrochloric acid cleaning steel is collected, 1.5 tons of pickle liquors are contained in 2.5 by elevator pump
In the closed reaction kettle of ton；
B, the anhydrous calcium chloride of 1980kg, the concentrated hydrochloric acid of 990kg are weighed, and adds concentrated hydrochloric acid first with the flow velocity of 480kg/h
Enter into anhydrous calcium chloride solid and react 1.5h, then is continued instead with being added after the flow velocity of 225kg/h into anhydrous calcium chloride solid
Answer 1.2h, HCl gas and reaction solution obtained after reaction, by reaction solution distillation handle to obtain mass concentration be 0.95% it is dilute
Hydrochloric acid solution；
C, the dilute hydrochloric acid solution that the mass concentration that step b is obtained is 0.95% obtains mass concentration through reverse osmosis concentration and is
6.8% hydrochloric acid solution is added in pickle liquor by 6.8% hydrochloric acid solution；
D, after being added at one time 6.8% hydrochloric acid solution of 106.5kg into the acid waste liquid of 1.5t, then it is passed through step a system
HCl gas, react after 5.3h terminates, and the hydrochloric acid solution that can be back to steel cleaning is obtained, so that completion is to pickle liquor
Recycling and reusing, can concentration of hydrochloric acid be 31% in the supernatant of reuse, impurity F e content is 3.5%.
Embodiment 1.3
A kind of recycling and reusing method of acid washing rolled steel waste liquid, comprising the following steps:
A, the pickle liquor obtained by hydrochloric acid cleaning steel is collected, 2.5 tons of pickle liquors are contained in 3 tons by elevator pump
Closed reaction kettle in；
B, the anhydrous calcium chloride of 3240kg, the concentrated hydrochloric acid of 1620kg are weighed, and adds concentrated hydrochloric acid first with the flow velocity of 700kg/h
Enter into anhydrous calcium chloride solid and react 1.8h, then is continued instead with being added after the flow velocity of 300kg/h into anhydrous calcium chloride solid
Answer 1.2h, HCl gas and reaction solution obtained after reaction, by reaction solution distillation handle to obtain mass concentration be 1.1% it is dilute
Hydrochloric acid solution；
C, the dilute hydrochloric acid solution that the mass concentration that step b is obtained is 1.1% obtains mass concentration through reverse osmosis concentration and is
7.2% hydrochloric acid solution is added in pickle liquor by 7.2% hydrochloric acid solution；
D, after being added at one time 7.2% hydrochloric acid solution of 187.5kg into the acid waste liquid of 2.5t, then it is passed through step a system
HCl gas, react after 5h terminates, and the hydrochloric acid solution that can be back to steel cleaning is obtained, so that completion is to pickle liquor
Recycling and reusing can concentration of hydrochloric acid be 32% in the supernatant of reuse, and impurity F e content is 4.0%.
According to embodiment 1.1-1.3 it is found that in the reaction system of the recycling and reusing method of the acid washing rolled steel waste liquid, reaction
Raw material only has concentrated hydrochloric acid, anhydrous calcium chloride and pickle liquor, and wherein there is no escape and environmental pollution phenomenon, anhydrous chlorine for concentrated hydrochloric acid
Change calcium need to only be added and can once recycle, and treated, and pickle liquor is back to steel cleaning；The generation of the reaction system
Object is pure water and the four water frerrous chloride of by-product having use value；It can be seen that the recycling and reusing method is at spent acid
Advantage is all had in terms of the synthesis such as environmental protection, economy, investment, operability during reason, achievees the purpose that clean manufacturing.
For convenient for the recycling and reusing to acid washing rolled steel waste liquid, above-mentioned processing method can be in following recycling and reusing device
It carries out:
It is as shown in Figs. 1-2: the recycling and reusing device of the acid washing rolled steel waste liquid, including pickle liquor collecting pit 1, in pickling
1 bottom of waste collection pond is equipped with liquid outlet 2, and the liquid outlet 2 is connected to pickle liquor through being equipped with the lift line 4 of elevator pump 3
Processing unit；
The pickle liquor processing unit includes the two-stage reaction kettle 5 being connected in parallel, and level-one is anti-in the two-stage reaction kettle 5
Answering kettle is main reaction kettle, and another order reaction kettle is secondary reacting kettle, and electromagnetic flowmeter 18 and the one or three can be arranged on lift line 4
Port valve 16 can also pass through observation electromagnetic flowmeter using the progress of the first triple valve 16 not only 5 main side effect of interchangeable reaction kettle
The data of 18 displays control the amount that pickle liquor is contained into 5 autoclave body of reaction kettle；Reaction kettle 5 includes sealable autoclave body, autoclave body
It is interior to be coated with anti-corrosion material, it avoids inside pickle liquor corrosion autoclave body；At the top of autoclave body, air inlet pipeline 7, air inlet pipeline 7 are set
Outlet extend under the reaction solution liquid level contained in autoclave body, convenient for reacting HCl gas sufficiently with pickle liquor, thus favorably
HCl gas generating device 8 is connected in the entrance of the recycling of spent acid, air inlet pipeline 7, while being equipped with electricity on air inlet pipeline 7
Magnetic flowmeter 18 and regulating valve 19, for controlling the flow velocity from gas to autoclave body and dosage that are passed through；
Gas overflowing pipeline 6 is also set up at the top of autoclave body, it is anti-that the outlet of the gas overflowing pipeline 6 is connected to another grade
The air inlet pipeline 7 for answering kettle 5 is designed in this way and HCl gas generation escape in autoclave body is avoided to endanger environment, and makes HCl gas and pickling
Waste liquid sufficiently reacts；The downstream of the HCl gas generating device 8 is also connected with distilling apparatus 9 in turn, will by distilling apparatus 9
Solution handles to obtain dilute hydrochloric acid solution through distillation after HCl gas generating device 8 reacts, then by dilute hydrochloric acid solution through reverse osmosis unit
Certain density hydrochloric acid solution can be obtained after 10 concentrations, the concentrated solution outlet 11 through reverse osmosis unit 10, which returns, is connected to reaction kettle
The feeding pipe 12 being arranged on 5, while electromagnetic flowmeter 18 and regulating valve 19 are set on feeding pipe 12, for controlling to kettle
It is passed through the flow velocity and dosage of hydrochloric acid solution in vivo, HCl gas generating device 8, distilling apparatus 9 and reverse osmosis unit 10 are all made of
It is existing, two-stage reaction kettle 5 connect HCl gas generating device 8, distilling apparatus 9 and reverse osmosis unit 10 can share it is a set of,
Can reaction kettles at different levels be used alone it is a set of；
Supernatant discharge outlet 13 is additionally provided on the autoclave body, the supernatant discharge outlet 13 is through the second triple valve 17, one
It is connected by circulating pump 20 with air inlet pipeline 7, to after pickle liquor and HCl gas reaction, by circulating pump 20 by autoclave body
Interior liquid is passed into air inlet pipeline 7, avoids the pipeline blockage of air inlet pipeline 7 Yu liquid contact position；The supernatant discharge
Mouthfuls 13 are connected through the second triple valve 17 is another with reuse pipeline 21, after pickle liquor is disposed, pass through the general of reuse pipeline 21
The hydrochloric acid solution that steel cleaning can be back to emits；In addition, the reuse pipeline 21 of two-stage reaction kettle 5 can be pooled to a root canal
Enterprising enforcement is used, can also individually carry out using；Solid waste discharge port 14 is additionally provided on the autoclave body, four water chlorine being precipitated for outlet
Change ferrous crystal, and the blender 15 by being arranged on autoclave body, start blender 15 when discharging four water frerrous chloride crystal,
Make four water frerrous chloride crystal convenient for discharge autoclave body, at the same time, four obtained water frerrous chloride crystalline solid are safe and non-toxic, may be used also
Applied in wastewater treatment, secondary pollution will not be generated.
Comparative example one
This comparative example is related to being passed through influence of the rate to processing result of concentrated hydrochloric acid in recycling and reusing method of the present invention.
Comparative example 1.1
The recycling and reusing method that this comparative example is related to is similar to embodiment 1.1, only difference is that concentrated hydrochloric acid is molten
Liquid is passed through that rate is slow, although the still available hydrochloric acid solution that can be back to steel cleaning, lower to the handling rate of pickle liquor,
And the obtained hydrochloric acid solution for being back to steel cleaning using effect when cleaning steel is poor.
Comparative example 1.2
The recycling and reusing method that this comparative example is related to is similar to embodiment 1.1, only difference is that concentrated hydrochloric acid is molten
Liquid is passed through that rate is fast, although the still available hydrochloric acid solution that can be back to steel cleaning, HCl gas be easy to cause gas to escape
Ease increases processing cost, causes secondary pollution, cannot meet environmental requirements.
Comparative example two
The recycling and reusing method that this comparative example is related to is similar to embodiment 1.1, only difference is that useless to pickling
HCl gas is only passed through in liquid, it is not necessary to be passed through hydrochloric acid solution；Although can be precipitated crystal in processing pickle liquor process, crystal packet
Containing two water frerrous chlorides, four water frerrous chlorides etc., causing by-product is not monolithic entity, and purity is low, and application value is low, and content ratio
More miscellaneous, use value is poor, it is also possible to cause secondary pollution.
In conclusion the recycling and reusing method of acid washing rolled steel waste liquid of the invention, utilizes concentrated hydrochloric acid and anhydrous calcium chloride
The HCl gas of generation and hydrochloric acid solution after processing, and defined reaction parameter enable pickle liquor to recycle comprehensively again sharp
With reaching the zero-emission of spent acid and the recycling of by-product.Recycling and reusing method of the invention, have low energy consumption, it is easy to operate,
The advantages such as operating cost is low, and recycling and reusing effect is good.
Claims (10)
1. a kind of recycling and reusing method of acid washing rolled steel waste liquid, which comprises the following steps:
A, the pickle liquor obtained by hydrochloric acid cleaning steel is collected；
B, reacting for concentrated hydrochloric acid and anhydrous calcium chloride is carried out, HCl gas obtained is passed directly into pickle liquor, it will be molten after reaction
Liquid handles to obtain dilute hydrochloric acid solution through distillation；
C, the dilute hydrochloric acid solution that step b is obtained obtains the hydrochloric acid solution that mass concentration is 6.5~7.5% through reverse osmosis concentration, will
6.5~7.5% hydrochloric acid solution is added in pickle liquor；
D, acid waste liquid is reacted with HCl gas, hydrochloric acid solution, and Iron dichloride tetrahydrate crystallization is precipitated, after abundant precipitation to be crystallized,
Supernatant fluid reuse flow back in the cleaning of steel, completes the recycling and reusing to pickle liquor.
2. the recycling and reusing method of acid washing rolled steel waste liquid according to claim 1, it is characterised in that: the pickle liquor
Consumption proportion with HCl gas is (0.9~1.1) t:(190~210) kg.
3. the recycling and reusing method of acid washing rolled steel waste liquid according to claim 1, it is characterised in that: dense salt in step b
The consumption proportion of acid and anhydrous calcium chloride is 1:(1.8~2.0)；The concentrated hydrochloric acid first with the flow velocity of 200~350kg/h be added to
After reacting 1~2h in 1t anhydrous calcium chloride solid, then it is added with the flow velocity of 80~200kg/h into anhydrous calcium chloride solid and is continued
React 0.5~1.5h.
4. the recycling and reusing method of acid washing rolled steel waste liquid according to claim 1, it is characterised in that: described in step b
The mass concentration of dilute hydrochloric acid is 0.8~1.2%.
5. the recycling and reusing method of acid washing rolled steel waste liquid according to claim 1, it is characterised in that: step c is obtained
6.5~7.5% hydrochloric acid solutions are added at one time before being passed through HCl gas into pickle liquor.
6. the recycling and reusing method of acid washing rolled steel waste liquid according to claim 1, it is characterised in that: the acid waste liquid
After reacting 4.5~5.5h with HCl gas, hydrochloric acid solution, the mass concentration for obtaining that steel cleaning can be back to is 25~32%
Hydrochloric acid solution.
7. a kind of recycling and reusing device of acid washing rolled steel waste liquid, it is characterised in that: useless in pickling including pickle liquor collecting pit
Liquid collection bottom of pond portion is equipped with liquid outlet, and the liquid outlet passes through the lift line equipped with elevator pump and is connected to pickle liquor processing list
Member；
The pickle liquor processing unit includes the two-stage reaction kettle being connected in parallel, and the reaction kettle includes sealable autoclave body,
Air inlet pipeline is set at the top of autoclave body, the outlet of the air inlet pipeline extends under the reaction solution liquid level contained in autoclave body, institute
The entrance for stating air inlet pipeline is connected with HCl gas generating device；Gas overflowing pipeline, the gas are also set up at the top of autoclave body
The outlet that body overflows pipeline is connected to the air inlet pipeline of another order reaction kettle；The downstream of the HCl gas generating device is also successively
It is connected with distilling apparatus, reverse osmosis unit, the concentrated solution outlet of the reverse osmosis unit, which returns, is connected to the charging being arranged on reaction kettle
Pipeline；Supernatant discharge outlet and solid waste discharge port are additionally provided on the autoclave body.
8. a kind of recycling and reusing device of acid washing rolled steel waste liquid according to claim 7, it is characterised in that: the autoclave body
On be additionally provided with blender.
9. a kind of recycling and reusing device of acid washing rolled steel waste liquid according to claim 7, it is characterised in that: the promotion
First triple valve and electromagnetic flowmeter are set on pipeline, are respectively provided with regulating valve and electromagnetic current on the air inlet pipeline and feeding pipe
Meter.
10. a kind of recycling and reusing device of acid washing rolled steel waste liquid according to claim 7, it is characterised in that: on described
Through the second triple valve, one is connected by circulating pump with air inlet pipeline clear liquid discharging mouth, another to be connected with reuse pipeline.
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| US20020005210A1 (en) * | 2000-01-05 | 2002-01-17 | Olsen Douglas R. | Regenerating spent pickling liquor |
| CN101665301A (en) * | 2008-09-05 | 2010-03-10 | 中国科学院生态环境研究中心 | Resource treatment method for hydrochloric acid pickling waste liquor |
| CN101891259A (en) * | 2009-05-20 | 2010-11-24 | 北京紫光英力化工技术有限公司 | New process for recycling pickling waste liquid |
| CN205773357U (en) * | 2016-06-01 | 2016-12-07 | 洛阳双瑞精铸钛业有限公司 | A kind of titanium material pickling zone waste acidity recovery reuse means |
| CN109467239A (en) * | 2017-09-08 | 2019-03-15 | 河北工业大学 | A kind of method of iron and steel pickling waste liquid recovery acid |
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