CN102092796B - Process for producing polyferric sulfate by utilizing zinc sulfate oxidation waste sludge - Google Patents
Process for producing polyferric sulfate by utilizing zinc sulfate oxidation waste sludge Download PDFInfo
- Publication number
- CN102092796B CN102092796B CN201010264730A CN201010264730A CN102092796B CN 102092796 B CN102092796 B CN 102092796B CN 201010264730 A CN201010264730 A CN 201010264730A CN 201010264730 A CN201010264730 A CN 201010264730A CN 102092796 B CN102092796 B CN 102092796B
- Authority
- CN
- China
- Prior art keywords
- mud
- zinc sulfate
- sulfate
- oxidation
- zinc
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to a process for producing polyferric sulfate by recycling zinc sulfate oxidation waste sludge as a raw material, which comprises the following steps of: rinsing raw zinc sulfate oxidation waste sludge by using water, performing pressure filtration to recover cadmium, nickel and zinc from rinsing water, and performing acidification, pressure filtration, condensation, hydrolysis and polymerization to produce the polyferric sulfate, wherein the rinsed zinc sulfate oxidation waste sludge to be treated comprises the following components in percentage by weight: 40 to 45 percent of ferric hydroxide, 54.5 to 59.5 percent of dehydrate calcium sulfate and 0.3 to 0.5 percent of other substances. The process effectively solves the problem that the zinc sulfate oxidation waste sludge cannot be recycled as the raw material to produce the polyferric sulfate in the conventional process, simultaneously regenerates iron resources, eliminates environmental pollutions caused by the waste residues, develops circular economy and is favorable for constructing the two-oriented society.
Description
Technical field
The present invention relates to the useless mud of a kind of recycle zinc sulfate oxidation is the process method of raw material production bodied ferric sulfate.
Background technology
Bodied ferric sulfate is a kind of important inorganic macromolecule compound; Owing to can produce multiple high price multinuclear complex ion after the hydrolysis; Combine with the negative charge of colloidal sol and suspended substance in the former water, impel water-borne glue body particulate and suspended substance to form thick floc sedimentation and sedimentation, thereby water is purified.Thereby extensively be used as life and process water, industry and municipal sewage treatment agent.
Existing polyaluminum sulfate process for making iron mainly contains two kinds: a kind of is to be after raw material is processed ferrous sulfate with iron filings; With the Sodium Nitrite is catalyzer; Bubbling air forms product with ferrous sulfate oxidation post polymerization; Another kind is to be raw material with the ferrous sulfate, is catalyzer with VAL-DROP, and bubbling air forms product with ferrous sulfate oxidation post polymerization.Above-mentioned two kinds of process methodes need be raw material with iron all, consume a large amount of Mineral resources, not only uneconomical but also not environmental protection.
Summary of the invention
The object of the present invention is to provide a kind of technology of utilizing the useless mud of zinc sulfate oxidation to produce bodied ferric sulfate.
The objective of the invention is to realize through following approach:
A kind of technology of utilizing the useless mud of zinc sulfate oxidation to produce bodied ferric sulfate; The useless mud of described original zinc sulfate oxidation elder generation water carries out rinsing, reclaims cadmium, nickel, zinc in the rinse water through press filtration, the pending useless mud of zinc sulfate oxidation after the rinsing; Its composition is by weight percentage: ironic hydroxide 40-45%; Terra alba 54.5-59.5%, other materials 0.3-0.5%, the treatment step of this technology is following:
A. acidifying
The wet mud that in the reactor drum that has stirrer, adds the useless mud of entry and zinc sulfate oxidation; The ratio that adds is the wet mud that 1 cubic metre of water is joined the useless mud of 1 ton of zinc sulfate oxidation; The wet mud of the useless mud of this zinc sulfate oxidation is its water cut 45-55% by weight percentage, stirs while feeding intake, and mud is stirred add sulfuric acid behind the pulp and carry out acidification reaction; The sulfuric acid that is added and the institute zinc sulfate oxidation of throwing are given up, and the weight ratio of ironic hydroxide is 1:1.2-1.5 in the mud; Temperature of reaction is 60-70 ℃, and the reaction times is 30 minutes, and the reaction terminating pH value is 2;
B. press filtration
After breasting the tape, stirred 30 minutes acidification reaction; Carry out press filtration again; Sulfate precipitate calcium is separated in press filtration, and calcium sulfate reclaims ferric sulfate wherein through rinsing, and the rinse water that contain ferric sulfate of recovery turn back to the acidizing process of front and make mother liquor; Calcium sulfate after the rinsing is made his usefulness in addition, and the ferrum sulfuricum oxydatum solutum that press filtration is separated changes next procedure over to;
C. concentrate, hydrolysis, polymerization
Above-mentioned ferrum sulfuricum oxydatum solutum is heated to 80-100 ℃, it is concentrated and generation hydrolysis and polyreaction,, form bodied ferric sulfate aqua finished product when being concentrated into 40-45Be ' time.
Further, the wet mud of the useless mud of zinc sulfate oxidation its water cut 50% by weight percentage in the acidification reaction of above-mentioned technology, the sulfuric acid that is added and the institute zinc sulfate oxidation of throwing are given up, and the weight ratio of ironic hydroxide is 1:1.3 in the mud.
Further, the wet mud of the useless mud of zinc sulfate oxidation its water cut 52% by weight percentage in the acidification reaction of above-mentioned technology, the sulfuric acid that is added and the institute zinc sulfate oxidation of throwing are given up, and the weight ratio of ironic hydroxide is 1:1.4 in the mud.
Further, the bodied ferric sulfate aqua of technology gained is through concentrating, promptly obtaining the ferric polysulfate solid article after the drying.
The useless mud of zinc sulfate oxidation is the waste residue of discharging in zinc sulfide white, zinc carbonate, the zinc sulfate production process, and its major ingredient is an ironic hydroxide, and content is about 40%.The process method that the useless mud of a kind of recycle zinc sulfate of the invention oxidation is produced bodied ferric sulfate; Having solved existing process method effectively can not the useless mud of recycle zinc sulfate oxidation be the difficult problem of raw material production bodied ferric sulfate; Regenerated the simultaneously resource of iron; Eliminated of the pollution of this waste residue, developed recycling economy, the construction of favourable " amphitypy " society environment.
Description of drawings
Below in conjunction with accompanying drawing the present invention is done further explain:
Fig. 1 is a process flow sheet of the present invention.
Embodiment
Embodiment one, and is as shown in Figure 1, the technology that the present invention utilizes the useless mud of zinc sulfate oxidation to produce bodied ferric sulfate; The useless mud of described original zinc sulfate oxidation elder generation water carries out rinsing, reclaims cadmium, nickel, zinc in the rinse water through press filtration, the pending useless mud of zinc sulfate oxidation after the rinsing; Its composition is by weight percentage: ironic hydroxide 45%; Terra alba 54.5%, other materials 0.5%, the treatment step of this technology is following:
A. acidifying
The wet mud that in the reactor drum that has stirrer, adds the useless mud of entry and zinc sulfate oxidation; The ratio that adds is the wet mud that 1 cubic metre of water is joined the useless mud of 1 ton of zinc sulfate oxidation; The wet mud of the useless mud of this zinc sulfate oxidation is its water cut 50% by weight percentage, stirs while feeding intake, and mud is stirred add sulfuric acid behind the pulp and carry out acidification reaction; The sulfuric acid that is added and the institute zinc sulfate oxidation of throwing are given up, and the weight ratio of ironic hydroxide is 1:1.3 in the mud; Temperature of reaction is 60-70 ℃, and the reaction times is 30 minutes, and the reaction terminating pH value is 2; The reaction formula of acidification reaction is following:
2Fe（OH）
3+3H
2SO
4=Fe
2（SO
4）
3+6H
2O；
B. press filtration
After breasting the tape, stirred 30 minutes acidification reaction; Carry out press filtration again; Sulfate precipitate calcium is separated in press filtration, and calcium sulfate reclaims ferric sulfate wherein through rinsing, and the rinse water that contain ferric sulfate of recovery turn back to the acidizing process of front and make mother liquor; Calcium sulfate after the rinsing mud manufacturer that can supply water makes additive, and the ferrum sulfuricum oxydatum solutum that press filtration is separated changes next procedure over to;
C. concentrate, hydrolysis, polymerization
Above-mentioned ferrum sulfuricum oxydatum solutum is heated to 80-100 ℃, it is concentrated and generation hydrolysis and polyreaction,, form bodied ferric sulfate aqua finished product when being concentrated into 40-45Be ' time.The reaction that is taken place therebetween is following:
Fe
2（SO
4）
3+nH
2O?→?Fe
2（OH）
n（SO
4）
3-n/2+?n/
2?H
2SO
4
m[Fe
2（OH）
n（SO
4）
3-n/2]?→[Fe
2（OH）
n（SO
4）
3-n/2]
m 。
Embodiment two, and is as shown in Figure 1, the technology that the present invention utilizes the useless mud of zinc sulfate oxidation to produce bodied ferric sulfate; The useless mud of described original zinc sulfate oxidation elder generation water carries out rinsing, reclaims cadmium, nickel, zinc in the rinse water through press filtration, the pending useless mud of zinc sulfate oxidation after the rinsing; Its composition is by weight percentage: ironic hydroxide 45%; Terra alba 54.5%, other materials 0.5%, the treatment step of this technology is following:
A. acidifying
The wet mud that in the reactor drum that has stirrer, adds the useless mud of entry and zinc sulfate oxidation; The ratio that adds is the wet mud that 1 cubic metre of water is joined the useless mud of 1 ton of zinc sulfate oxidation; The wet mud of the useless mud of this zinc sulfate oxidation is its water cut 52% by weight percentage, stirs while feeding intake, and mud is stirred add sulfuric acid behind the pulp and carry out acidification reaction; The sulfuric acid that is added and the institute zinc sulfate oxidation of throwing are given up, and the weight ratio of ironic hydroxide is 1:1.4 in the mud; Temperature of reaction is 60-70 ℃, and the reaction times is 30 minutes, and the reaction terminating pH value is 2; The reaction formula of acidification reaction is following:
2Fe（OH）
3+3H
2SO
4=Fe
2（SO
4）
3+6H
2O；
B. press filtration
After breasting the tape, stirred 30 minutes acidification reaction; Carry out press filtration again; Sulfate precipitate calcium is separated in press filtration, and calcium sulfate reclaims ferric sulfate wherein through rinsing, and the rinse water that contain ferric sulfate of recovery turn back to the acidizing process of front and make mother liquor; Calcium sulfate after the rinsing mud manufacturer that can supply water makes additive, and the ferrum sulfuricum oxydatum solutum that press filtration is separated changes next procedure over to;
C. concentrate, hydrolysis, polymerization
Above-mentioned ferrum sulfuricum oxydatum solutum is heated to 80-100 ℃, it is concentrated and generation hydrolysis and polyreaction,, form bodied ferric sulfate aqua finished product when being concentrated into 40-45Be ' time.The reaction that is taken place therebetween is following:
Fe
2（SO
4）
3+nH
2O?→?Fe
2（OH）
n（SO
4）
3-n/2+?n/
2?H
2SO
4
m[Fe
2（OH）
n（SO
4）
3-n/2]?→[Fe
2（OH）
n（SO
4）
3-n/2]
m 。
Claims (4)
1. technology of utilizing the useless mud of zinc sulfate oxidation to produce bodied ferric sulfate; The useless mud of original zinc sulfate oxidation elder generation water carries out rinsing, reclaims cadmium, nickel, zinc in the rinse water through press filtration, the pending useless mud of zinc sulfate oxidation after the rinsing; Its composition is by weight percentage: ironic hydroxide 40-45%; Terra alba 54.5-59.5%, other materials 0.3-0.5% is characterized in that: the treatment step of this technology is following:
A. acidifying
The wet mud that in the reactor drum that has stirrer, adds the useless mud of zinc sulfate oxidation pending after entry and the rinsing; The ratio that adds is the wet mud that 1 cubic metre of water is joined the useless mud of 1 ton of zinc sulfate oxidation; The wet mud of the useless mud of this zinc sulfate oxidation is its water cut 45-55% by weight percentage, stirs while feeding intake, and mud is stirred add sulfuric acid behind the pulp and carry out acidification reaction; The sulfuric acid that is added and the institute zinc sulfate oxidation of throwing are given up, and the weight ratio of ironic hydroxide is 1:1.2-1.5 in the mud; Temperature of reaction is 60-70 ℃, and the reaction times is 30 minutes, and reaction terminating pH value is 2;
B. press filtration
After breasting the tape, stirred 30 minutes acidification reaction; Carry out press filtration again; Sulfate precipitate calcium is separated in press filtration, and calcium sulfate reclaims ferric sulfate wherein through rinsing, and the rinse water that contain ferric sulfate of recovery turn back to the acidizing process of front and make mother liquor; Calcium sulfate after the rinsing is made his usefulness in addition, and the ferrum sulfuricum oxydatum solutum that press filtration is separated changes next procedure over to;
C. concentrate, hydrolysis, polymerization
Above-mentioned ferrum sulfuricum oxydatum solutum is heated to 80-100 ℃, it is concentrated and generation hydrolysis and polyreaction,, form bodied ferric sulfate aqua finished product when being concentrated into 40-45Be ' time.
2. the technology of utilizing the useless mud of zinc sulfate oxidation to produce bodied ferric sulfate as claimed in claim 1; It is characterized in that: the wet mud of the useless mud of zinc sulfate oxidation its water cut 50% by weight percentage in the acidification reaction of above-mentioned technology, the sulfuric acid that is added and the institute zinc sulfate oxidation of throwing are given up, and the weight ratio of ironic hydroxide is 1:1.3 in the mud.
3. the technology of utilizing the useless mud of zinc sulfate oxidation to produce bodied ferric sulfate as claimed in claim 1; It is characterized in that: the wet mud of the useless mud of zinc sulfate oxidation its water cut 52% by weight percentage in the acidification reaction of above-mentioned technology, the sulfuric acid that is added and the institute zinc sulfate oxidation of throwing are given up, and the weight ratio of ironic hydroxide is 1:1.4 in the mud.
4. the technology of utilizing the useless mud of zinc sulfate oxidation to produce bodied ferric sulfate as claimed in claim 1 is characterized in that: the bodied ferric sulfate aqua of technology gained promptly obtains the ferric polysulfate solid article after concentrated, drying.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010264730A CN102092796B (en) | 2010-08-27 | 2010-08-27 | Process for producing polyferric sulfate by utilizing zinc sulfate oxidation waste sludge |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010264730A CN102092796B (en) | 2010-08-27 | 2010-08-27 | Process for producing polyferric sulfate by utilizing zinc sulfate oxidation waste sludge |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102092796A CN102092796A (en) | 2011-06-15 |
| CN102092796B true CN102092796B (en) | 2012-10-10 |
Family
ID=44126087
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010264730A Expired - Fee Related CN102092796B (en) | 2010-08-27 | 2010-08-27 | Process for producing polyferric sulfate by utilizing zinc sulfate oxidation waste sludge |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102092796B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102849803B (en) * | 2011-06-28 | 2014-12-03 | 鞍钢股份有限公司 | A method for recycling Fenton reaction catalyst |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1043297A (en) * | 1990-01-09 | 1990-06-27 | 谭正洪 | Technology for making polyiron sulfate |
| CN1446752A (en) * | 2002-10-22 | 2003-10-08 | 中南大学 | Method for preparing polymeric ferric sulfate by using partial oxidation process |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100492035B1 (en) * | 2002-10-28 | 2005-05-30 | 박경호 | manufacturing method of ploy ferric sulfate |
-
2010
- 2010-08-27 CN CN201010264730A patent/CN102092796B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1043297A (en) * | 1990-01-09 | 1990-06-27 | 谭正洪 | Technology for making polyiron sulfate |
| CN1446752A (en) * | 2002-10-22 | 2003-10-08 | 中南大学 | Method for preparing polymeric ferric sulfate by using partial oxidation process |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102092796A (en) | 2011-06-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104071853B (en) | Waste Sulfuric Acid and ferrous sulfate oxygen pressing is utilized to produce the method for bodied ferric sulfate | |
| CN103420430B (en) | Polyaluminum ferrous chloride purifier and production method thereof | |
| CN104437502B (en) | Magnetic fenton catalyst ferrospinel with Fenton iron containing sludge as source of iron and application | |
| CN104086027B (en) | Method for treating titanium dioxide wastewater through sulfuric acid process | |
| CN102358648A (en) | Technology for recycling of sludge obtained after neutralizing treatment of steel and iron pickling wastewater and recycling ferroferric oxide | |
| CN102921376A (en) | Magnesium hydroxide/graphene compound adsorbing material for phosphorus-containing wastewater treatment as well as preparation method and application thereof | |
| CN101760632B (en) | Method for recovering zinc from zinc sulfate solution | |
| CN104085969A (en) | Method for preparing compound type multi-element flocculating agent aluminum ferric sulfate chloride polysilicate by utilizing waste acid | |
| CN101439897A (en) | Preparation of composite flocculant for recovering phosphor in sewerage and phosphor recovering process | |
| CN102432091A (en) | Preparation method of composite flocculating agent for pretreating blue alga biogas slurry | |
| CN103183457A (en) | Method for recovering phosphorus in sewage sludge | |
| CN102718268B (en) | Method for producing solid poly ferric sulfate | |
| CN108117195A (en) | The waste water fluoride ion removing agent of polymetallic ore mountain and processing method | |
| CN103950987A (en) | Recycling method of pickling sludge | |
| US20150225253A1 (en) | Method for preparing basic zinc chloride | |
| CN101239761A (en) | Environmental protection treatment method for citric acid chemical plating waste water | |
| CN110550722A (en) | method for treating organic wastewater by preparing hydrolysis type ferromanganese reagent from ferromanganese-containing sludge and efficiently catalyzing persulfate | |
| CN109536745B (en) | Method for preparing calcium sulfate whisker and polysilicate flocculant by using medium-low grade phosphate rock powder | |
| CN102092796B (en) | Process for producing polyferric sulfate by utilizing zinc sulfate oxidation waste sludge | |
| CN102530898A (en) | Phosphate radical ion recycling method for activated carbon washes with method of phosphoric acid | |
| CN103787535A (en) | Treatment method of sludge water of underground water plant | |
| CN109319896B (en) | Method for preparing flocculating agent from fly ash and vanadium-titanium magnetite | |
| CN101759233A (en) | Method for recovering cobalt from cobalt sulfate solution | |
| CN103771629A (en) | Pretreatment technology of hot-galvanizing wastewater | |
| CN202657995U (en) | Recycling system for acid-containing wastewater |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20121010 Termination date: 20150827 |
|
| EXPY | Termination of patent right or utility model |