CN108358409A - A kind of steel wire rope sludge and spent acid method for innocent treatment - Google Patents
A kind of steel wire rope sludge and spent acid method for innocent treatment Download PDFInfo
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- CN108358409A CN108358409A CN201810187073.4A CN201810187073A CN108358409A CN 108358409 A CN108358409 A CN 108358409A CN 201810187073 A CN201810187073 A CN 201810187073A CN 108358409 A CN108358409 A CN 108358409A
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- wire rope
- steel wire
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- spent acid
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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
- C02F11/00—Treatment of sludge; Devices therefor
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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
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
- C02F11/121—Treatment of sludge; Devices therefor by de-watering, drying or thickening by mechanical de-watering
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
- C02F11/14—Treatment of sludge; Devices therefor by de-watering, drying or thickening with addition of chemical agents
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention discloses a kind of steel wire rope sludge and spent acid method for innocent treatment, and using waste hydrochloric acid extraction steel wire rope metal in sludge ionic iron, lead, zinc, residue send to dangerous waste and disposes center processing；According to composition transfer in raw material spent acid and sludge, certain ionic species adjustment is carried out；By the adjusting of leaching liquor pH value and sulfide precipitation, lead, zinc ion in leaching liquor are removed；It is precipitated again by hydroxide, iron ion in leaching liquor is made to precipitate as ferric hydroxide；It after iron hydroxide is by cleaning, being dehydrated, is dissolved with electrode foil Waste Sulfuric Acid, forms ferrum sulfuricum oxydatum solutum；Supernatant after coagulating sedimentation, be high concentration calcium chloride solution, be added electrode foil Waste Sulfuric Acid reaction generate hydrogen chloride gas, gypsum solid, solution receive after filtering pipe discharge.The present invention solves the problems, such as that the sludge toxicity generated in steel wire rope production is high, harm is big, yield is big, difficult and generation secondary pollution risk.
Description
Technical field
The present invention relates to a kind of sludge and spent acid method for innocent treatment, especially a kind of steel wire rope sludge and spent acid are harmless
Change processing method.
Background technology
Waste hydrochloric acid, wherein general containing HCl>5%, while a large amount of Fe may be contained2+And a certain amount of Pb2+Or Zn2+Ion.Cause
Its acid concentration is high, has strong corrosive, is put into National Hazard waste register（HW34 spent acid）.Processing side widely used at present
Method has（1）Acid-base neutralization method, but its reagent consumption amount is big, and plurality of heavy metal sludge is will produce, form secondary pollution；（2）It is high
Warm roasting method, recycles HCl and iron oxide red, but the process contains a certain amount of lead zinc ion in the iron oxide red of generation, influences its product at height
Matter.
Steel wire rope sludge is flushing water after steel wire rope pickling, the hydroxide that is generated in processing procedure precipitation, mainly with Fe,
Based on the heavy metal hydroxides such as Ca, Zn, Pb.Because of Heavy Metal Level In Sludge height, toxicity is high, is put into National Hazard waste name
Record（HW17 surface treatment wastes）.Main processing method is cement kiln synergic processing to heavy metal sewage sludge at present, but steel wire rope is dirty
High lead, zinc, chlorinity in mud, can have an impact Cement Quality, and cooperative disposal limited ability influences Cement Quality, and water
Stall cooperative disposal can not fundamentally remove removing heavy metals, and cause the waste of resource.
It is less to steel wire rope sludge, waste hydrochloric acid and electrode foil Waste Sulfuric Acid recycling, the technical study of harmless treatment at present.
105603447 A of patent CN（A kind of system and method for steel wire rope acid-washing waste acid disposal of resources technique）Using
The method of " high pressure chlorination hydrogen separation+dehydration technology+high-temperature roasting " realizes separating hydrogen chloride, recycling precipitation lead, recycling iron oxide
The purpose of pigment, the invention have ignored quality shadow of the other impurities present in steel wire rope spent acid to precipitation lead and iron oxide pigment
It rings, meanwhile, energy consumption is high.
107098556 A of patent CN（The method of recycling sludge recycling metal in Wire Rope Production）Using electrolysis
Steel wire rope sludge spent acid mixed liquor is handled, solution of ferrous chloride is made after then handling in recycling wherein heavy metal ion, electrolyte.Steel
Torpescence metal in cord sludge spent acid mixed liquor（Copper, lead etc.）Total content 0.5% hereinafter, handled using electrolysis, electricity
Energy consumption is excessively high.
106186445 A of patent CN（A kind of steel wire rope acid-washing waste acid and it is total to disposal system and technique containing high zinc, lead sludge）
Sulphide precipitation processing steel wire rope spent acid and the mixed liquor containing high zinc, lead sludge are directly used, steel wire rope spent acid is had ignored
Present in a large amount of influences of the iron ion to lead zinc sulfide precipitation, and do not refer to containing other heavy metals in high zinc, lead sludge from
Son.
Invention content
Technical problem to be solved by the invention is to provide a kind of steel wire rope sludge and spent acid method for innocent treatment, solve
The sludge toxicity that is generated in steel wire rope production is high, harm is big, yield is big, difficult and generate asking for secondary pollution risk
Topic, and surface treatment spent acid yield is big, corrosivity is high, endangers the problems such as big.
In order to solve the above technical problems, the technical solution adopted in the present invention is：
A kind of steel wire rope sludge and spent acid method for innocent treatment, it is characterised in that comprise the steps of：
Step 1：By steel wire rope sludge and waste hydrochloric acid with 1:3~1:10 ratio is uniformly mixed in extraction reaction kettle, is fully soaked
It carries, extraction time 1~4 hour, undissolved sludge residue send to dangerous waste and disposes center processing；
Step 2：Leaching liquor enters ion reforming system in step 1, according to steel wire rope sludge and waste hydrochloric acid material composition, determines
Added amount of chemical；
Step 3：Leaching liquor after step 2 intermediate ion is reformed enters coagulating sedimentation system, and leaching liquor pH value is first adjusted to 1.0
~3.0, then vulcanized sodium is added, so that lead zinc ion is precipitated with sulphided form, the lead zinc sludge of precipitation is cleaned, sent to smelting after drying
As lead-zinc smelting raw material, supernatant liquor enters step four and is further processed for refinery；
Step 4：The water outlet of coagulating sedimentation in step 3 precipitates into two-stage coagulation, by feeding lime milk solution, makes solution
Middle iron ion precipitates as ferric hydroxide, and the water outlet after precipitation enters step five and is further processed, ferric hydroxide precipitate
Six are entered step to be further processed；
Step 5：Electrode foil Waste Sulfuric Acid is added in water outlet after being precipitated in step 4, and reaction generates hydrogen chloride gas, gypsum solid,
Solution receive after filtering pipe discharge；
Step 6：The ferric hydroxide precipitate generated in step 4 after cleaned, drying and other treatment, is dissolved, shape with electrode foil Waste Sulfuric Acid
At ferrum sulfuricum oxydatum solutum, it is used to prepare water purification agent bodied ferric sulfate；
Step 7：The hydrogen sulfide gas that generation is reacted in step 3 is inhaled by two level packed absorber and active carbon deodorization device
It receives.
Further, the step 2 carries out reduction reaction, and the medicament added is iron powder, and ferric ion is reduced into two
Valence iron ion.
Further, the step 3 pH adjustings are adjusted using 3%~30% sodium hydroxide solution, and the residence time 30~
60 minutes；The vulcanized sodium, using 10%~30% sodium sulfide solution, 30~60 minutes reaction time；Lead zinc after the drying
In precipitation, lead total content 6%~15%, zinc total content 7%~11%.
Further, in the step 4 ferric hydroxide precipitate use 10%~30% lime milk solution, when coagulating sedimentation
Between 1~2 hour；The water outlet calcium chloride concentration is 10%~40%.
Further, reaction carries out under the conditions of 0 DEG C~100 DEG C in the step 5,30~60 minutes reaction time, raw
At hydrogen chloride gas water or dilute hydrochloric acid can be used to absorb after be used for steel wire rope pickling zone；The gypsum solid of generation is as plasterboard
Equal construction materials；Water outlet reaches municipal sewage treatment and receives after pipe requirement after tubular type Microfiltration Unit removes suspended solid, discharge；
Tubular type Microfiltration Unit is 1 with return water ratio using inner pressed, single tube micro-filtration membrane module, water outlet:6~1:12.
Further, the ferrum sulfuricum oxydatum solutum a concentration of 10%~15% formed in the step 6.
Further, in the step 7 hydrogen sulfide absorption use 5%~20% sodium hydroxide solution, the vulcanized sodium of generation
Reuse is to coagulating sedimentation system.
Compared with prior art, the present invention haing the following advantages and effect：
1. the ion reforming step of the present invention, can effectively realize the separation of lead zinc and iron, the frerrous chloride after sulfide precipitation
Pb contents in solution<5mg/L, Zn content<100mg/L.
2. the dissolving polymerization procedure of iron hydroxide in the present invention, effectively realizes ferro element and electrode in steel wire rope sludge
Innoxious, the recycling treatment of foil Waste Sulfuric Acid.
3. the advanced treating step of the coagulating sedimentation water outlet in the present invention effectively realizes the recycling profit of electrode foil spent acid
With the hydrogen chloride of generation can be back to wire rope factory and is surface-treated, and the gypsum of generation can be used as the building materials such as plasterboard.
4. maximum precipitation of the invention realizes steel wire rope sludge, hydrochlorate acid, the harmlessness disposing of electrode foil Waste Sulfuric Acid and money
Sourceization utilizes.
Description of the drawings
Fig. 1 is the schematic diagram of a kind of the steel wire rope sludge and spent acid method for innocent treatment of the present invention.
Specific implementation mode
The present invention is described in further detail below in conjunction with the accompanying drawings and by embodiment, and following embodiment is to this hair
Bright explanation and the invention is not limited in following embodiments.
Waste hydrochloric acid, HCl contents are>5%, it can the foreign ions such as iron content, lead, zinc；The steel wire rope sludge, iron content 11%
~20%, lead content is 0.1%~0.4%, and Zn content is 3%~7%；The electrode foil Waste Sulfuric Acid, H2SO4 contents are 15%~30%,
Aluminium composition 0.4%~1.0%.Metal ion exists in a chloride-form in steel wire rope spent acid, golden in the steel wire rope sludge
Category exists with hydroxide form.
As shown in Figure 1, a kind of steel wire rope sludge and spent acid method for innocent treatment of the present invention, it is characterised in that comprising with
Lower step：
Step 1：By steel wire rope sludge and waste hydrochloric acid with 1:3~1:10 ratio is uniformly mixed in extraction reaction kettle, is fully soaked
It carries, extraction time 1~4 hour, undissolved sludge residue send to dangerous waste and disposes center processing；Steel wire rope sludge is mixed with waste hydrochloric acid
Ratio is matched according to material composition.
Step 2：Leaching liquor enters ion reforming system in step 1, according to steel wire rope sludge and waste hydrochloric acid material composition,
Determine added amount of chemical；General to carry out reduction reaction, the medicament added is iron powder, by ferric ion be reduced into ferrous iron from
Son.
Step 3：Leaching liquor after step 2 intermediate ion is reformed enters coagulating sedimentation system, first adjusts leaching liquor pH value
To 1.0~3.0, then vulcanized sodium is added, lead zinc ion is made to be precipitated with sulphided form, the lead zinc sludge of precipitation cleans, after drying
It send to smeltery as lead-zinc smelting raw material, supernatant liquor enters step four and is further processed；PH adjusts using 3%~
30% sodium hydroxide solution is adjusted, 30~60 minutes residence times；The vulcanized sodium, using 10%~30% sodium sulfide solution,
30~60 minutes reaction time；In lead zinc precipitation after the drying, lead total content 6%~15%, zinc total content 7%~11%.
Step 4：The water outlet of coagulating sedimentation in step 3 precipitates into two-stage coagulation, by feeding lime milk solution, makes
Iron ion precipitates as ferric hydroxide in solution, and the water outlet after precipitation enters step five and is further processed, iron hydroxide
Precipitation enters step six and is further processed；Ferric hydroxide precipitate uses 10%~30% lime milk solution, when coagulating sedimentation
Between 1~2 hour；The water outlet calcium chloride concentration is 10%~40%.
Step 5：Water outlet after being precipitated in step 4, is added electrode foil Waste Sulfuric Acid, and reaction generates hydrogen chloride gas, gypsum
Solid, solution receive after filtering pipe discharge；Reaction carries out under the conditions of 0 DEG C~100 DEG C, and 30~60 minutes reaction time generated
Hydrogen chloride gas water or dilute hydrochloric acid can be used to absorb after be used for steel wire rope pickling zone；The gypsum solid of generation is as plasterboard etc.
Construction material；Water outlet reaches municipal sewage treatment and receives after pipe requirement after tubular type Microfiltration Unit removes suspended solid, discharge；Pipe
Formula Microfiltration Unit is 1 with return water ratio using inner pressed, single tube micro-filtration membrane module, water outlet:6~1:12.
Step 6：The ferric hydroxide precipitate generated in step 4, it is molten with electrode foil Waste Sulfuric Acid after cleaned, drying and other treatment
Solution forms ferrum sulfuricum oxydatum solutum, is used to prepare water purification agent bodied ferric sulfate；The ferrum sulfuricum oxydatum solutum a concentration of 10%~15% of formation.
Step 7：The hydrogen sulfide gas that generation is reacted in step 3 is filled by two level packed absorber and active carbon deodorizing
Set absorption.Hydrogen sulfide absorption uses 5%~20% sodium hydroxide solution, the vulcanized sodium reuse of generation to coagulating sedimentation system.
The present invention is further illustrated below by specific embodiment；
Steel wire rope sludge components are as follows：Moisture content 61.9%, iron content 13.7%, lead content 0.4%, Zn content 2.6%；Steel wire rope acid
It is as follows to wash abraum salt sour component：HCl contents 9.5%, iron content 8.2%, lead content 3.7g/L, Zn content 2.0g/L；Electrode foil sulfur waste
Acid is at as follows：H2SO4Content is 25.8%, aluminium content 0.6%.
Entire technique is tested with handling 1kg steel wire ropes sludge：
4L steel wire rope acid-washing waste acids are added in heavy metal sewage sludge extraction reactor, 1kg steel wire rope sludge is added, is sufficiently stirred 2
Hour；Supernatant enters reduction reactor, 80g reduced iron powders is added, after being sufficiently stirred 2 hours；Supernatant enters coagulating sedimentation
The sodium hydroxide solution of about 250mL a concentration of 20% is gradually added dropwise in device, adjusts pH to 2.4, then gradually dropwise addition 150mL is a concentration of
20% sodium sulfide solution is sufficiently stirred 30 minutes；The lead zinc of generation precipitates once purged drying；Supernatant, which enters second, to be mixed
Solidifying settler is added the milk of lime that 200g is configured to 30%, is fully aerated, after the cleaned dehydration of ferric hydroxide precipitate of generation,
Into dissolving paradigmatic system, 400mL electrode foil Waste Sulfuric Acids are added, polymerization generates water purification agent bodied ferric sulfate；Supernatant enters depth
Change processing reaction kettle, is continuously added 1000mL electrode foil Waste Sulfuric Acids in whipping process, 55 ± 2 DEG C of reaction temperature, the reaction time 1 is small
When, the hydrogen chloride gas of generation is emptied after three-level absorption bottle by water-circulating pump, precipitates once purged dehydration, is done at 40 ± 2 DEG C
It is dry, form gypsum solid.
The lead zinc of generation precipitates 212g, wherein lead content 12.06%, Zn content 9.61%；In the ferrum sulfuricum oxydatum solutum of generation,
Iron concentration 11.8%；The concentration of hydrochloric acid 24.6% of generation；The gypsum moisture content 9.8% of generation.
Described in this specification above content is only illustrations made for the present invention.Technology belonging to the present invention
The technical staff in field can do various modifications or supplement to described specific embodiment or substitute by a similar method, only
The guarantor of the present invention should all be belonged to without departing from the content or beyond the scope defined by this claim of description of the invention
Protect range.
Claims (7)
1. a kind of steel wire rope sludge and spent acid method for innocent treatment, it is characterised in that comprise the steps of：
Step 1：By steel wire rope sludge and waste hydrochloric acid with 1:3~1:10 ratio is uniformly mixed in extraction reaction kettle, is fully soaked
It carries, extraction time 1~4 hour, undissolved sludge residue send to dangerous waste and disposes center processing；
Step 2：Leaching liquor enters ion reforming system in step 1, according to steel wire rope sludge and waste hydrochloric acid material composition, determines
Added amount of chemical；
Step 3：Leaching liquor after step 2 intermediate ion is reformed enters coagulating sedimentation system, and leaching liquor pH value is first adjusted to 1.0
~3.0, then vulcanized sodium is added, so that lead zinc ion is precipitated with sulphided form, the lead zinc sludge of precipitation is cleaned, sent to smelting after drying
As lead-zinc smelting raw material, supernatant liquor enters step four and is further processed for refinery；
Step 4：The water outlet of coagulating sedimentation in step 3 precipitates into two-stage coagulation, by feeding lime milk solution, makes solution
Middle iron ion precipitates as ferric hydroxide, and the water outlet after precipitation enters step five and is further processed, ferric hydroxide precipitate
Six are entered step to be further processed；
Step 5：Electrode foil Waste Sulfuric Acid is added in water outlet after being precipitated in step 4, and reaction generates hydrogen chloride gas, gypsum solid,
Solution receive after filtering pipe discharge；
Step 6：The ferric hydroxide precipitate generated in step 4 after cleaned, drying and other treatment, is dissolved, shape with electrode foil Waste Sulfuric Acid
At ferrum sulfuricum oxydatum solutum, it is used to prepare water purification agent bodied ferric sulfate；
Step 7：The hydrogen sulfide gas that generation is reacted in step 3 is inhaled by two level packed absorber and active carbon deodorization device
It receives.
2. a kind of steel wire rope sludge described in accordance with the claim 1 and spent acid method for innocent treatment, it is characterised in that：The step
Rapid two carry out reduction reaction, and the medicament added is iron powder, and ferric ion is reduced into ferrous ion.
3. a kind of steel wire rope sludge described in accordance with the claim 1 and spent acid method for innocent treatment, it is characterised in that：The step
Rapid three pH adjustings are adjusted using 3%~30% sodium hydroxide solution, 30~60 minutes residence times；The vulcanized sodium uses
10%~30% sodium sulfide solution, 30~60 minutes reaction time；In lead zinc precipitation after the drying, lead total content 6%~15%,
Zinc total content 7%~11%.
4. a kind of steel wire rope sludge described in accordance with the claim 1 and spent acid method for innocent treatment, it is characterised in that：The step
Ferric hydroxide precipitate uses 10%~30% lime milk solution, 1~2 hour coagulating sedimentation time in rapid four；The water outlet chlorination
Calcium concentration is 10%~40%.
5. a kind of steel wire rope sludge described in accordance with the claim 1 and spent acid method for innocent treatment, it is characterised in that：The step
Reaction carries out under the conditions of 0 DEG C~100 DEG C in rapid five, 30~60 minutes reaction time, the hydrogen chloride gas of generation can use water or
Dilute hydrochloric acid is used for steel wire rope pickling zone after absorbing；The gypsum solid of generation is as construction materials such as plasterboards；Water outlet is through tubular type
After Microfiltration Unit removes suspended solid, reaches municipal sewage treatment and receive after pipe requirement, discharge；Tubular type Microfiltration Unit uses internal pressure
Formula, single tube micro-filtration membrane module, water outlet are 1 with return water ratio:6~1:12.
6. a kind of steel wire rope sludge described in accordance with the claim 1 and spent acid method for innocent treatment, it is characterised in that：The step
The ferrum sulfuricum oxydatum solutum a concentration of 10%~15% formed in rapid six.
7. a kind of steel wire rope sludge described in accordance with the claim 1 and spent acid method for innocent treatment, it is characterised in that：The step
Hydrogen sulfide absorption uses 5%~20% sodium hydroxide solution, the vulcanized sodium reuse of generation to coagulating sedimentation system in rapid seven.
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| CN201810187073.4A CN108358409A (en) | 2018-03-07 | 2018-03-07 | A kind of steel wire rope sludge and spent acid method for innocent treatment |
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| CN201810187073.4A CN108358409A (en) | 2018-03-07 | 2018-03-07 | A kind of steel wire rope sludge and spent acid method for innocent treatment |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110436721A (en) * | 2019-08-12 | 2019-11-12 | 江苏荣信环保科技有限公司 | A kind of metal surface pickling sludge and spent acid comprehensive processing technique |
| CN110642347A (en) * | 2019-09-27 | 2020-01-03 | 江苏荣信环保科技有限公司 | Method for preparing industrial flocculant from acid solution containing high iron, lead and zinc |
| CN110745922A (en) * | 2019-11-01 | 2020-02-04 | 中国林业科学研究院林产化学工业研究所 | Method for preparing efficient flocculant by using waste acid and application |
| CN110963610A (en) * | 2019-12-17 | 2020-04-07 | 张家港洁利环保科技有限公司 | Method for removing lead ions in waste acid |
| CN111018192A (en) * | 2019-12-30 | 2020-04-17 | 斯瑞尔环境科技股份有限公司 | Method for preparing high-purity ferrous iron by using heavy metal ions in ferrous solution precipitated by sodium sulfide solid |
| CN114873790A (en) * | 2022-05-26 | 2022-08-09 | 天津辰创环境工程科技有限责任公司 | Steel wire rope sludge and waste acid recycling harmless treatment method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110436721A (en) * | 2019-08-12 | 2019-11-12 | 江苏荣信环保科技有限公司 | A kind of metal surface pickling sludge and spent acid comprehensive processing technique |
| CN110642347A (en) * | 2019-09-27 | 2020-01-03 | 江苏荣信环保科技有限公司 | Method for preparing industrial flocculant from acid solution containing high iron, lead and zinc |
| CN110745922A (en) * | 2019-11-01 | 2020-02-04 | 中国林业科学研究院林产化学工业研究所 | Method for preparing efficient flocculant by using waste acid and application |
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| CN111018192A (en) * | 2019-12-30 | 2020-04-17 | 斯瑞尔环境科技股份有限公司 | Method for preparing high-purity ferrous iron by using heavy metal ions in ferrous solution precipitated by sodium sulfide solid |
| CN114873790A (en) * | 2022-05-26 | 2022-08-09 | 天津辰创环境工程科技有限责任公司 | Steel wire rope sludge and waste acid recycling harmless treatment method |
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