CN110306057A - A kind of processing method of stainless steel acid cleaning waste water recycling - Google Patents
A kind of processing method of stainless steel acid cleaning waste water recycling Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- 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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/005—Preliminary treatment of scrap
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/32—Obtaining chromium
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- 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
- C22B47/00—Obtaining manganese
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- 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
- C22B7/001—Dry processes
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- 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
- C22B7/006—Wet processes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/70—Treatment of water, waste water, or sewage by reduction
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
- C02F2101/14—Fluorine or fluorine-containing compounds
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
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Abstract
The invention discloses a kind of processing methods of stainless steel acid cleaning waste water recycling, include the following steps: stainless steel acid cleaning waste water after sediment is handled, it adds aluminum salt flocculant and milk of lime carries out flocculation reaction, the first reducing agent is put into its filtrate, point three steps add alkaline matter and are precipitated in reduction reaction completion liquid, after the progress flocculation reaction of the second flocculant is added in obtaining filtrate, its filtrate neutralisation treatment after separation of solid and liquid, oil removal is removed, can be discharged；The filter residue that above-mentioned every step obtains is respectively fed to calcining furnace, the second reducing agent is added, and calcines 2-3h under 1500 DEG C of reducing atmosphere, calcined product is crushed respectively, separation ore-sorting is carried out by flotation or magnetic selection method, obtains the respective metal concentrate slag of siderochrome manganese.The present invention realizes its resource utilization while wastewater treatment, provides a kind of new and innovative ways of resource utilization for the processing of stainless steel acid cleaning waste water.
Description
Technical field
The invention belongs to waste water to reprocess technical field, in particular it relates to a kind of stainless steel acid cleaning waste water resource
The method of change.
Background technique
Stainless steel acid cleaning waste water is in order to remove oxidation on metal surface object, using sulfuric acid, nitric acid, hydrochloric acid, hydrofluoric acid and phosphorus
The waste water generated when the acid such as acid carries out acid wash processing.Waste water mostly from steel plant or electroplate factory, pH value generally 1.5 with
Under (free acid 0.5-2%), be in highly acid；Its direct emission would seriously pollute the environment.Therefore, to the General Office of pickling waste waters
Reason, recycling are to solve the effective way of pickling waste waters pollution environment and Resource recovery.
The more common method of pickling waste waters processing at present is neutralisation, such as is neutralized in water with lime, dolomite and magnesia
Acid；But the method cannot not only recycle utility and can generate a large amount of solid waste, so as to cause secondary pollution.To pickling
Sour utilization approaches have the recovery method of acid to have evaporation, roasting method, crystallisation, ion-exchange etc. in waste water.Each method has
The advantage and disadvantage of itself, although such as evaporation can effectively recycle hydrochloric acid, hydrofluoric acid effumability acid, but still the crystallization in raffinate
The easy occluding device pipeline of body, service condition are high and equipment is perishable；Roasting method HCl recovery rate has reached 99%, but it is high to consume energy；Knot
Crystallization advantage is that treatment process does not need consumption eo-acid, and recovery acid can be directly used for Hao Suan workshop section；The disadvantage is that equipment is more, investment
Greatly, energy consumption is high；Ion-exchange processing industrial wastewater is widely used, the object that cements out good with effluent quality
The advantages that matter is recyclable, and resin can be eluted and be used again, without secondary pollution, and equipment operation is easy, is easy to implement automation, but ion is handed over
It changes method also to have disadvantages that, if ion-exchange can only handle the low waste water of metal ion content, the waste water of high concentration can pollute
Resin reduces adsorption capacity, and resin needs to elute, and cost improves.
The disclosed technical solution of Chinese patent application CN102659274A is proposed the spent acid resin in pickling waste waters
Adsorption, then with two-step method neutralization precipitation separating metal ions and fluorine ion, the resource reclaim of inorganic acid and nickel is realized, but
It is that the metal sediment that its precipitating generates does not make recycling treatment, results in waste of resources.Chinese Patent Application No. is
200710067749.8 disclosed technical solution proposition uses sodium hydroxide to replace lime as neutralizer, to the huge sum of money in waste water
Belong to individually precipitating, then add lime fluorine removal, realize the separation of metal ion and calcirm-fluoride, and heavy metal sewage sludge has and melts down
Condition, but ingredient is unstable, is unfavorable for determining the nickel chromium triangle amount required supplementation with, is unfavorable for the stable operation of stainless steel production.
Processing for the sludge of a large amount of pickling waste waters and neutralization precipitation that generate in producing stainless steel process needs to propose
New solution route, while tenor reaches discharge standard in reducing waste water can also metal therein carry out at recycling
Reason is all the direction of research all the time.
Summary of the invention
To solve the above-mentioned problems, the embodiment of the invention provides its technical solution is as follows:
A kind of processing method of stainless steel acid cleaning waste water recycling, including the following steps: S1: stainless steel acid cleaning waste water is passed through
Cross sediment processing after, add the first flocculant and milk of lime, and adjust pH to 4.0-4.5 carry out flocculation reaction, filter first
Filter residue and the first filtrate；
S2: putting into the first reducing agent into the first filtrate of step S1, carries out reduction treatment；
S3: completing to add alkaline matter in liquid to the reduction reaction of step S2, and adjust pH to 5-7, after precipitating, solid-liquid point
From obtaining the second filter residue and the second filtrate；
S4: adding alkaline matter into the second filtrate liquid that step S3 is obtained, and adjust pH to 8-9, after precipitating, solid-liquid point
Third filter residue and third filtrate are obtained from after；
S5: adding alkaline matter into the third filtrate that step S4 is obtained, and adjust pH to 11-11.5, after precipitating, solid-liquid
The 4th filter residue and the 4th filtrate are obtained after separation；
S6: adding the second flocculant into the 4th filtrate that step S4 is obtained, and after carrying out flocculation reaction, separation of solid and liquid is obtained
5th filter residue and the 5th filtrate；5th filtrate is neutralized to pH 6.5-7.2, and is filtered, suspended matter is removed
Discharge；
S7: the first filter residue, the second filter residue, third filter residue, the 4th filter residue and the 5th filter residue are respectively fed in calcining furnace, added
Enter the second reducing agent, and calcine 2-3h under 1500 DEG C of reducing atmosphere, respectively obtains the first calcined product, the second calcining produces
Object, third calcined product, the 4th calcined product and the 5th calcined product；
S8: the first calcined product, the second calcined product, third calcined product, the 4th calcined product that step S6 is obtained
It is crushed respectively with the 5th calcined product, separation ore-sorting is carried out by flotation or magnetic selection method, obtains the respective gold of siderochrome manganese
Belong to concentrate slag.
Technical solution provided in an embodiment of the present invention is include at least the following beneficial effects:
The present invention is by carrying out fluorine removal to stainless steel waste water, then waste water is carried out reduction treatment, then batch precipitation is returned respectively
Iron, chromium, manganese are received, and obtains the calcined product of high-grade iron, chromium, manganese, while it discharges water and meets " steel and iron industry sewage pollution
Object discharge standard " (GB13456-2012) discharge standard.The present invention realizes its resource utilization while wastewater treatment,
A kind of new and innovative ways of resource utilization are provided for the processing of stainless steel acid cleaning waste water.
Further advantage, target and feature of the invention will be partially reflected by the following instructions, and part will also be by this
The research and practice of invention and be understood by the person skilled in the art.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, the present invention will be made below further detailed
Description.Obviously, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based on this hair
Embodiment in bright, every other implementation obtained by those of ordinary skill in the art without making creative efforts
Example, belongs to the scope of protection of the invention.In the description of the present invention, it is to be understood that, term " first ", " second ", "
Three ", " 4th " etc. is only used for distinguishing description, is not understood to indicate or imply relative importance.
For achieving the above object, the present invention provides a kind of processing method of stainless steel acid cleaning waste water recycling, comprising:
S1: stainless steel acid cleaning waste water is flowed into flocculation tank after sediment is handled, adds the first flocculant and lime
Cream, and adjust pH to 4.0-4.5 and carry out flocculation reaction, flocculation water outlet flows into dissolved air flotation pond, floccule body is hauled out the water surface, is passed through
Slag Scraping Device scrapes dross, and enters after mummifying pool up to the first filter residue, it is quiet it is heavy after cleaning solution be the first filtrate；
Specifically, the first flocculant is aluminum salt flocculant, and selected from poly-aluminium, (body structure representative formula is AlO4Al12(OH)24
(H2O)12Cl7), poly aluminium sulfate (PAS), polyaluminium chloride (PAC), Polyaluminium Sulfate Chloride (PACS), poly- phosphorus aluminium chloride (PPAC), ferro-aluminum
The copolymerized flocculant of copolymerized flocculant, magnalium.
Wherein, inorganic flocculating agent of the Al-fe Co Polymer Inorganic Coagulant based on aluminium salt, supplemented by molysite, generally high-temperature roasting
Heat the preparation of acidolysis copolymerization method；Inorganic flocculating agent of the copolymerized flocculant of magnalium based on aluminium salt, supplemented by magnesium salts, preparation side
Method is similar with Al-fe Co Polymer Inorganic Coagulant.
Specifically, the dosage of aluminium salt is the 2-5%wt of total waste water, removes fluorine in wastewater by S1 step, while also sinking
Form sediment a small amount of metal ion.
S2: the first reducing agent is put into the first filtrate of step S1 and is reacted；First reducing agent is selected from thiosulfuric acid
Sodium, sodium hydrogensulfite, sodium sulfite, sodium pyrosulfite, potassium thiosulfate, potassium bisulfite, potassium sulfite, potassium metabisulfite,
Sodium nitrite, sodium hypophosphite, ortho phosphorous acid hydrogen sodium；It is preferred that sodium thiosulfate, sodium hydrogensulfite, sodium sulfite, thiosulfuric acid
One of potassium, potassium bisulfite, potassium sulfite, sodium hypophosphite, ortho phosphorous acid hydrogen sodium are a variety of.
Specifically, the dosage of reducing agent is the 1-4%wt of the first filtrate, can be by ferric ion also by reducing agent
Originally it is ferrous ion, hexavalent chromium is reduced to trivalent chromic ion, while can also be low price manganese by value Mn ion reduction
Ion.
S3: it completes to add alkaline matter in liquid to the reduction reaction of step S2, and pH to 6.5- is adjusted by sodium hydroxide
7.8, reaction is sufficiently stirred, the second filter residue and the second filtrate are obtained after separation of solid and liquid；The dosage of alkaline matter is that S3 has reacted
At the 6-8%wt of liquid, liquid ferrous ions are precipitated into its hydroxide.
S4: adding alkaline matter into the second filtrate liquid that step S3 is obtained, and adjust pH to 8-9 by sodium hydroxide,
Reaction is sufficiently stirred, third filter residue and third filtrate are obtained after separation of solid and liquid；The dosage of alkaline matter is the 5- of the second filtrate
7%wt.Cr in alkaline matter and the second filtrate3+Reaction generates Cr (OH) completely3。
S5: alkaline matter is added into the third filtrate that step S4 is obtained, and pH to 11- is adjusted by sodium hydroxide
11.5, reaction is sufficiently stirred, the 4th filter residue and the 4th filtrate are obtained after separation of solid and liquid；The dosage of alkaline matter is third filtrate
3-5%wt.Alkaline matter reacts completely with the Mn2+ in third filtrate generates Mn (OH)2。
S6: adding the second flocculant into the 4th filtrate that step S4 is obtained, and carries out flocculation reaction, obtains after separation of solid and liquid
5th filter residue and the 5th filtrate；5th filtrate is neutralized to pH 6.5-7.2, and is filtered, suspended matter is removed
Discharge；Second flocculant is the mixture of Fred salts, high-molecule metal flocculant (MHMF) or both, wherein the second flocculant
Quality is 1:2.5-1:4 when for Fred salts and high-molecule metal flocculant mixture, it is preferable that Fred salts: MHMF mass
Than for 1:3.5, the dosage of second flocculant is the 6-8%wt of the 4th filtrate, to the metal ion in the 4th filtrate into
Row is thoroughly removed, and the standard of discharge is reached.
Heavy metal chelating agent generally uses the salt of soluble active dihydrocarbyl dithiophosphate phosphoric acid, generates with heavy metal ion
It is insoluble in the dialkyl dithiophosphate precipitating of water and removes, removal rate is up to 99% or more, and treatment effect is not by pH
The influence of value, coexistent metallic ion.Heavy metal chelating agent citing: the modified shell of PEI, cross-linked amino-starch, DTC modified starch, DTC
Glycan.
Fred salts are a kind of LDHs mineral, and rhombohedron is symmetrical, and main layer is [Ca2Al(OH)6]+, wherein Al3+Be coordinated for 6,
Ca2+ is special 7 coordination.Middle layer is [the Cl ﹒ 2H of ordered arrangement2O]-.Middle layer is hydrated Cl-Respectively with 3 hydrogen bonds with it is upper
Hexa-coordinate aluminum-oxide polyhedron and seven coordination calcium oxygen polyhedrons in lower main layer are mutually bonded, and Fred salts have superior characteristic, such as
Large specific surface area, anion-exchange capacity are high, thermal stability is good, it can remove remaining in waste water after comprehensive step
Electrodeless metal ion such as siderochrome manganese nickel and other metal ions, and removes remaining nocuousness oxygen anion, such as sulphur in waste water simultaneously
Acid ion, nitrate ion, fluorine ion etc..
S7: the first filter residue, the second filter residue, third filter residue, the 4th filter residue and the 5th filter residue are respectively fed in calcining furnace, added
Enter the second reducing agent, and calcined under 1500 DEG C of reducing atmosphere, respectively obtains the first calcined product, the second calcined product,
Three calcined products, the 4th calcined product and the 5th calcined product；Second reducing agent is solid carbon, straw or stalk, and also Primordial Qi is
CO or hydrogen or coal gas.By in high temperature respectively to the first filter residue, the second filter residue, third filter residue, the 4th filter residue and the 5th filter residue
It is calcined and is restored, obtaining the first calcined product is mainly CaF2With ferro-aluminum chromium manganese-nickel mine, the second calcined product is main
For iron ore, third calcined product is mainly chrome ore, and the 4th calcined product is mainly manganese ore, and the 5th calcining is siderochrome manganese-nickel
Mine.
S8: the first calcined product, the second calcined product, third calcined product, the 4th calcined product that step S6 is obtained
It is crushed respectively with the 5th calcined product, separation ore-sorting is carried out by flotation or magnetic selection method, it is respective to obtain siderochrome manganese nickel
Metal concentrate slag.First calcined product first passes through 400mT magnetic separation, removes silicon carrying out flotation, floating agent is lauryl amine, is floated
Calcirm-fluoride is selected to can be used as cement mineralizing agent, glass cosolvent；Second and third and four calcined products first carry out broken rod milling respectively,
Then 400mT magnetic separation is carried out to get to the concentrate for respectively obtaining iron, chromium, manganese.
It is illustrated below with reference to embodiment.
The cold-rolling pickling wastewater day discharge amount of certain Stainless Steel Plant is 1 ton, water quality situation such as table 1.
Table 1
| Index | Total iron | Total chromium | Containing manganese | It is nickeliferous | Total fluorine | pH | COD | Other metals |
| Pickling waste waters | 15.55g/L | 2.03g/L | 1.53g/L | 0.85g/L | 6.2g/L | 2.5 | 80 | 22mg/L |
Table 2 be embodiment 1-5, respective first flocculant, the first reducing agent, the substance of the second flocculant and quality,
The basic species quality that each step adds.
Table 2
Table 3 is the discharge water index in the step S6 of embodiment 1-5, meets " steel and iron industry wastewater pollutants discharge mark
It is quasi- " requirement of (GB13456-2012) direct emission.From table 3 it is observed that embodiment 5 is discharged in water in addition to iron content,
The content of his metal, fluoride and C0D is minimum in 5 embodiments, also below discharge standard.
Table 3
| Embodiment | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Total iron mg/L | 8.53 | 6.35 | 4.38 | 3.68 | 6.87 |
| Total chromium mg/L | 1.04 | 0.87 | 0.69 | 0.48 | 0.37 |
| Total manganese mg/L | 0.72 | 0.57 | 0.38 | 0.16 | 0.65 |
| Total nickel mg/L | 0.85 | 0.67 | 0.42 | 0.27 | 0.057 |
| Other metals mg/L | 15.23 | 14.86 | 14.35 | 14.27 | 8.36 |
| Fluoride mg/L | 2.35 | 3.17 | 1.77 | 2.94 | 0.41 |
| COD | 25.13 | 16.92 | 18.53 | 17.62 | 12.36 |
| pH | 6.82 | 6.78 | 6.93 | 7.02 | 6.86 |
And finally obtain the first calcined product, the second calcined product, third calcined product, the 4th calcined product and the 5th
The quality of calcined product is listed in table 4.From table 4, it can be seen that the second calcined product contains high-grade iron (79.42%-
82.87%), third calcined product (90.25%-95.15%) containing high-grade chromium, the 4th calcined product contain high-grade manganese
(87.3%-89.23%), these three calcined products can be used as the raw mineral materials of further metal smelt, realize stainless steel
Metal resourceization in pickling waste waters utilizes, while also causing the discharge underwater gold category content of embodiment 1-5 up to standard.
Table 4
It should be noted that the above various embodiments belongs to same inventive concept, the description of each embodiment emphasizes particularly on different fields,
Not detailed place is described in separate embodiment, can refer to the description in other embodiments.
Embodiments of the present invention above described embodiment only expresses, the description thereof is more specific and detailed, but can not
Therefore it is construed as limiting the scope of the patent.It should be pointed out that for those of ordinary skill in the art,
Under the premise of not departing from present inventive concept, various modifications and improvements can be made, and these are all within the scope of protection of the present invention.
Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (8)
1. a kind of processing method of stainless steel acid cleaning waste water recycling, characterized in that it comprises the following steps:
S1: by stainless steel acid cleaning waste water after sediment is handled, the first flocculant and milk of lime are added, and adjusts pH to 4.0-
4.5 carry out flocculation reaction, filter to obtain the first filter residue and the first filtrate；
S2: putting into the first reducing agent into the first filtrate of step S1, carries out reduction treatment；
S3: it completes to add alkaline matter in liquid to the reduction reaction of step S2, and adjusts pH to 5-7, after precipitating, be separated by solid-liquid separation
To the second filter residue and the second filtrate；
S4: alkaline matter is added into the second filtrate liquid that step S3 is obtained, and adjusts pH to 8-9, after precipitating, after separation of solid and liquid
Obtain third filter residue and third filtrate；
S5: adding alkaline matter into the third filtrate that step S4 is obtained, and adjust pH to 11-11.5, after precipitating, is separated by solid-liquid separation
After obtain the 4th filter residue and the 4th filtrate；
S6: adding the second flocculant into the 4th filtrate that step S4 is obtained, and after carrying out flocculation reaction, separation of solid and liquid obtains the 5th
Filter residue and the 5th filtrate；5th filtrate is neutralized to pH 6.5-7.2, and is filtered, suspended matter is removed, can be discharged；
S7: the first filter residue, the second filter residue, third filter residue, the 4th filter residue and the 5th filter residue are respectively fed in calcining furnace, are added the
Two reducing agents, and 2-3h is calcined under 1500 DEG C of reducing atmosphere, respectively obtain the first calcined product, the second calcined product,
Three calcined products, the 4th calcined product and the 5th calcined product；
S8: the first calcined product, the second calcined product, third calcined product, the 4th calcined product and that step S6 is obtained
Five calcined products are crushed respectively, carry out separation ore-sorting by flotation or magnetic selection method, obtain the respective metal essence of siderochrome manganese
Slag.
2. the processing method of stainless steel acid cleaning waste water recycling according to claim 1, which is characterized in that first wadding
Solidifying agent is to remove fluorine flocculant, and dosage is the 2-5%wt of total waste water.
3. the processing method of stainless steel acid cleaning waste water recycling according to claim 1, which is characterized in that described first also
Former agent is metallic reducing agent, and dosage is the 1-4%wt of the first filtrate.
4. the processing method of stainless steel acid cleaning waste water recycling according to claim 1, which is characterized in that the step S3
In alkaline matter dosage be S3 reaction residual liquor 6-8%wt.
5. the processing method of stainless steel acid cleaning waste water recycling according to claim 1, which is characterized in that the step S4
In alkaline matter dosage be the second filtrate 5-7%wt.
6. the processing method of stainless steel acid cleaning waste water recycling according to claim 1, which is characterized in that the step S5
In alkaline matter dosage be third filtrate 3-5%wt.
7. the processing method of stainless steel acid cleaning waste water recycling according to claim 1, which is characterized in that second wadding
Solidifying agent is the mixture of Fred salts, high-molecule metal flocculant or both；Wherein, second flocculant be Fred salts and
When both high-molecule metal flocculants mixture, quality 1:2.5-1:4.
8. the processing method of stainless steel acid cleaning waste water recycling according to claim 1, which is characterized in that described second also
Former agent is solid carbon, straw or stalk, and the reducing atmosphere is CO or hydrogen or coal gas.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111825191A (en) * | 2020-05-22 | 2020-10-27 | 西北矿冶研究院 | Acid sewage heavy metal capture agent |
| CN115448487A (en) * | 2022-06-09 | 2022-12-09 | 江苏兴隆防腐设备有限公司 | Steel pickling wastewater circulating treatment device and wastewater treatment method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1765763A (en) * | 2004-10-28 | 2006-05-03 | 力晶半导体股份有限公司 | Method for treating fluorine-containing waste water |
| CN101811792A (en) * | 2009-02-24 | 2010-08-25 | 宝山钢铁股份有限公司 | Processing method of stainless steel cold rolling pickling wastewater |
| CN102730885A (en) * | 2012-07-23 | 2012-10-17 | 中南大学 | Efficient flocculent precipitate purification method for polymetallic ore benefication wastewater |
| CN108928953A (en) * | 2018-06-29 | 2018-12-04 | 中国科学院过程工程研究所 | A kind of method of stainless steel acid cleaning waste water recycling |
-
2019
- 2019-06-25 CN CN201910556057.2A patent/CN110306057B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1765763A (en) * | 2004-10-28 | 2006-05-03 | 力晶半导体股份有限公司 | Method for treating fluorine-containing waste water |
| CN101811792A (en) * | 2009-02-24 | 2010-08-25 | 宝山钢铁股份有限公司 | Processing method of stainless steel cold rolling pickling wastewater |
| CN102730885A (en) * | 2012-07-23 | 2012-10-17 | 中南大学 | Efficient flocculent precipitate purification method for polymetallic ore benefication wastewater |
| CN108928953A (en) * | 2018-06-29 | 2018-12-04 | 中国科学院过程工程研究所 | A kind of method of stainless steel acid cleaning waste water recycling |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111825191A (en) * | 2020-05-22 | 2020-10-27 | 西北矿冶研究院 | Acid sewage heavy metal capture agent |
| CN115448487A (en) * | 2022-06-09 | 2022-12-09 | 江苏兴隆防腐设备有限公司 | Steel pickling wastewater circulating treatment device and wastewater treatment method thereof |
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