CN103395810B - Process for preparation of industrial aluminum sulfate by use of waste acid solution produced during production of expandable graphite - Google Patents
Process for preparation of industrial aluminum sulfate by use of waste acid solution produced during production of expandable graphite Download PDFInfo
- Publication number
- CN103395810B CN103395810B CN201310339529.1A CN201310339529A CN103395810B CN 103395810 B CN103395810 B CN 103395810B CN 201310339529 A CN201310339529 A CN 201310339529A CN 103395810 B CN103395810 B CN 103395810B
- Authority
- CN
- China
- Prior art keywords
- acid solution
- concentration
- washing
- depickling
- black lead
- 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
Abstract
The invention relates to a process method for production of industrial aluminum sulfate by use of a waste acid solution produced during production of expandable graphite; in the method, natural flake graphite is used as a raw material, concentrated sulfuric acid is used as an oxidizing agent, hydrogen peroxide is used as an intercalator, and then the expandable graphite is obtained by acidifying treatment, depickling, washing treatment and drying treatment, recycling treatment of all the waste acid solution produced during the production process of the expandable graphite is carried out, and the waste acid solution is directly used for production of the aluminum sulfate much-needed in industry. The serious environment pollution caused by discharge of the waste acid solution during the production process of the expandable graphite can be solved, and the produced waste acid solution can be completely recycled and changed from waste into treasure without production of any waste matter. A large amount of sulfuric acid and water resources can be saved and the production cost is greatly reduced.
Description
Technical field
The invention belongs to expansible black lead factory effluent recovery and utilization technology field, be specifically related to a kind of processing method of utilizing the spent acid solution of production expansible black lead to prepare industrial aluminum sulphate.
Background technology
The production method of expansible black lead has multiple, conventional chemical oxidization method, with HNO
3, H
2sO
4make oxygenant, using sodium dichromate 99, potassium permanganate, Potcrate etc. as intercalator, react and make expansible black lead with graphite, in its production process, one ton of expansible black lead of every production need to consume 1.5 tons～2.4 tons, the sulfuric acid of 98% concentration, and the vitriol oil is in the whole reaction process of producing, just play oxygenizement, the quality of itself does not change.Enter graphite layers formation compound between graphite layers-expansible black lead and decompose as the raw material of intercalator the active oxygen discharging in whole reaction process.After having reacted, a large amount of acid solutions needs water to clean, and is the pH=7 of the expansible black lead that makes to produce, and one ton of expansible black lead of every production will produce 20～30m
3acid-bearing wastewater, if directly discharge or through simply discharging after neutralizing treatment can cause environmental pollution and the wasting of resources, this is also that graphite production industry perplexs technical barrier for a long time.Especially intercalator adopts sodium dichromate 99 (Na
2cr
2o
7) time, in washes, not only containing a large amount of sulfuric acid, but also contain a large amount of trivalent chromic ions and a small amount of hexavalent chromium, the pollution causing to environment is more serious.Therefore the major defect that existing graphite production technology exists: the one, the large concentration of spent acid liquid measure producing in graphite production process is large, thereby intractability is also large.These waste water, as being discharged in environment without processing, will cause serious pollution to environment.The 2nd, because the usage quantity of sulfuric acid is large, can not recycle, directly cause the increase of production cost; The 3rd, because sulfuric acid consumption is large, washing water consumption increases, and causes the waste of water resources.
Summary of the invention
The severe contamination that the object of the present invention is to provide a kind of discharge that can solve spent acid solution in expansible black lead production process to cause environment, the spent acid solution of generation all can be recycled again, turn waste into wealth, do not produce any refuse, can also save a kind of processing method of utilizing the spent acid solution of production expansible black lead to prepare industrial aluminum sulphate of a large amount of sulfuric acid and water resources.
The technical scheme taked is for achieving the above object: this processing method comprises the following steps:
Step 1, acidification: the sulfuric acid, the concentration that are 98% by natural flake graphite, concentration are more than 28% hydrogen peroxide, the reactor that adds band to stir according to the weight proportion of Shi Mo ︰ Liu Suan ︰ hydrogen peroxide=1 ︰ 2.3 ︰ 0.15, temperature of reaction is controlled at 60 DEG C ± 5 DEG C, 30 minutes reaction times, adding concentration is 65～70% sulfuric acid again, when the sulfuric acid that is 98% by concentration in reactor is diluted to concentration and is 80～85%, stirring is cooled to 25 DEG C of normal temperature, after having reacted, make the mixed liquor of expansible black lead and sulphuric acid soln;
Step 2, depickling, washing is processed: reacted step 1 mixed liquor is put into pressure filter and carry out depickling, leach concentration and be 80～85% spent acid solution be input in No. 1 acidproof tank, continue to employ pending, the expansible black lead filter cake extruding is sent into agitation vat, adding concentration is 20～40% dilute sulphuric acid, stir, put into suction washer and carry out depickling washing, the add-on of dilute sulphuric acid is taking the washing acid strength deviate from as 30%～45%, by this washing spent acid solution be input in No. 2 acidproof tanks, continue to employ pending, then add water and proceed the washing of depickling repeatedly, until pH value=7 o'clock of the expansible black lead filter cake after depickling washing, stop depickling washing, make expansible black lead wet feed, and when acid strength≤20% of repetitive scrubbing, this washing acid solution is returned to suction washer as recycling,
Step 3, drying treatment: the expansible black lead wet feed of step 2 is sent in drying machine and is dried, and drying temperature is 55～65 DEG C, when being dried to graphite water content and being 0.5～1%, be expansible black lead finished product;
The processing of step 4, spent acid solution: the washing spent acid solution that the concentration that in the spent acid solution that to get concentration that in No. 1 acidproof tank in step 2, depickling is press-filtered out be 80%～85% and No. 2 acidproof tanks, depickling is washed out is 30～45%, when the two proportioning is 55～60% by acid strength after mixing, make mix acid liquor;
Step 5, prepare alum liquor: mix acid liquor is added to reactor, pass into steam heating, in the time that temperature reaches 80 DEG C, close the weight proportion of Suan Ye ︰ aluminium hydroxide=1 ︰ 0.32 according to Hun, slowly add aluminium hydroxide, in the time that temperature of reaction reaches 120 DEG C ± 5 °, be incubated 2 hours, make alum liquor;
Step 6, the alum liquor that step 5 is made are put in spray crystallizer, carry out at normal temperatures spray crystallization, obtain grains Tai-Ace S 150 finished product.
Produce according to utilization of the present invention the processing method that expansible black lead spent acid solution is prepared industrial aluminum sulphate, its beneficial effect is:
(1) can effectively solve the severe contamination that the discharge of spent acid solution in expansible black lead production process causes environment, the spent acid solution of generation all can be recycled, be directly used in the production of Tai-Ace S 150, Waste Sulfuric Acid is turned waste into wealth, do not produce any refuse, recovery processing technique is simple simultaneously, and cost is lower, and the Tai-Ace S 150 quality of output reaches the requirement of commodity Tai-Ace S 150 completely.
(2) can will prepare the spent acid solution producing in expansible black lead process all for the production of the industry Tai-Ace S 150 of needs in a large number, can solve the recycling of expansible black lead production process spent acid solution, realize the zero release of spent acid solution, can effectively stop again the pollution of high pollution industry to environment, and can also save a large amount of sulfuric acid and water resources, greatly reduce production cost, can obtain thus larger economic benefit and environmental benefit.
(3) in the preparation process of Tai-Ace S 150, adopt spray crystallization to replace conventional crystallisation by cooling and pulverizing process, make thus production efficiency greatly improve, energy consumption reduces greatly.
Embodiment
Below in conjunction with embodiment, the present invention will be further described.
The present invention utilizes the spent acid solution of production expansible black lead generation to prepare the processing method of industrial aluminum sulphate, in method taking natural flake graphite as raw material, make oxygenant with the vitriol oil, make intercalator with hydrogen peroxide, its method is: get natural flake graphite (C), concentration is that 98% sulfuric acid and concentration are more than 28% hydrogen peroxide, and the reactor that adds band to stir according to the weight proportion of Shi Mo ︰ Liu Suan ︰ hydrogen peroxide=1 ︰ 2.3 ︰ 0.15, temperature of reaction is controlled at 60 DEG C ± 5 DEG C, 30 minutes reaction times, adding concentration is 65～70% sulfuric acid again, the add-on of this sulfuric acid is that to add concentration in reactor be that the weight of 98% sulfuric acid is benchmark, by the calculating to concentration and weight, calculating concentration in reactor is 98% sulfuric acid required add-on when being diluted to concentration and being 80～85%, concrete calculating can be calculated as follows: N=G
1n
1+ G
2n
2/ G
1+ G
2, wherein: N is for using acid concentration, N1 is concentrated acid concentration, N2 is dilute acid concentration, G1 is concentrated acid weight, G2 is diluted acid weight, add when stirring the diluting concentrated sulfuric acid making in reactor after diluted acid and being 80～85% to concentration, be cooled to 25 DEG C of normal temperature, reaction equation is: H
2sO
4+ 2H
2o
2=H
2sO
4+ 2H
2o+O
2, in reaction, taking the vitriol oil as oxygenant, taking hydrogen peroxide as intercalator, decompose the active oxygen discharging and react generation expansible black lead with natural flake graphite, after having reacted, make the mixed liquor of expansible black lead and sulphuric acid soln, again this mixed liquor is put into pressure filter and carry out press filtration depickling, leach concentration and be 80～85% spent acid solution be delivered in No. 1 acidproof tank, continue to employ pending, the expansible black lead filter cake extruding is sent into agitation vat, adding concentration is 20～40% dilute sulphuric acid, stir, put into suction washer and carry out the depickling washing of 1～2 time, the add-on of dilute sulphuric acid is taking the washing acid strength deviate from as 30%～45%, by this washing spent acid solution be delivered in No. 2 acidproof tanks, continue to employ pending, then add water and proceed repeatedly to repeat depickling washing, until pH value=7 o'clock of expansible black lead filter cake, depickling washing is complete, make expansible black lead wet feed, and through the acid strength of vacuum filter repetitive scrubbing below 20%, this washing acid solution is returned to suction washer as recycling, this step is used suction washer can improve detersive efficiency, bath water amount greatly reduces.Then expansible black lead wet feed is sent in drying machine and is dried, drying temperature is 55～65 DEG C, when being dried to graphite water content and being 0.5～1%, is expansible black lead finished product; Finally carry out the processing of spent acid solution, the washing spent acid solution that the concentration that in the spent acid solution that to get concentration that in No. 1 acidproof tank, depickling is press-filtered out be 80%～85% and No. 2 acidproof tanks, depickling is washed out is 30～45%, when the two proportioning is 55～60% by acid strength after mixing, make mix acid liquor, this mix acid liquor is added to reactor, pass into steam heating, in the time that temperature reaches 80 DEG C, close Suan Ye ︰ aluminium hydroxide Al (OH) according to Hun
3the weight proportion of=1 ︰ 0.32, slowly adds aluminium hydroxide Al (OH)
3, in the time that temperature of reaction reaches 120 DEG C ± 5 °, be incubated 2 hours, make alum liquor, the alum liquor making is put in spray crystallizer, carry out at normal temperatures spray crystallization, obtain grains Tai-Ace S 150 finished product.Chemical equation is: 2Al (OH)
3+ 3H
2sO
4+ 12H
2o=Al
2(SO
4)
318H
2o, is found out by reaction formula, and in reaction process, the whole crystallizations of sulfuric acid and water are product 18 water Tai-Ace S 150, thereby turn waste into wealth.18 water Tai-Ace S 150 is a kind of flocculation agent being widely used in wastewater treatment, also for the tap water of purifying, is used as oar agent in paper industry.In the present invention, the percentage concentration of the raw material of using is mass percentage concentration.
Claims (1)
1. utilize the spent acid solution of production expansible black lead to prepare a processing method for industrial aluminum sulphate, it is characterized in that: the method comprises the following steps:
Step 1, acidification: the sulfuric acid, the concentration that are 98% by natural flake graphite, concentration are more than 28% hydrogen peroxide, the reactor that adds band to stir according to the weight proportion of Shi Mo ︰ Liu Suan ︰ hydrogen peroxide=1 ︰ 2.3 ︰ 0.15, temperature of reaction is controlled at 60 DEG C ± 5 DEG C, 30 minutes reaction times, adding concentration is 65～70% sulfuric acid again, when the sulfuric acid that is 98% by concentration in reactor is diluted to concentration and is 80～85%, stirring is cooled to 25 DEG C of normal temperature, after having reacted, make the mixed liquor of expansible black lead and sulphuric acid soln;
Step 2, depickling, washing is processed: reacted step 1 mixed liquor is put into pressure filter and carry out depickling, leach concentration and be 80～85% spent acid solution be input in No. 1 acidproof tank, continue to employ pending, the expansible black lead filter cake extruding is sent into agitation vat, adding concentration is 20～40% dilute sulphuric acid, stir, put into suction washer and carry out depickling washing, the add-on of dilute sulphuric acid is taking the washing acid strength deviate from as 30%～45%, by this washing spent acid solution be input in No. 2 acidproof tanks, continue to employ pending, then add water and proceed the washing of depickling repeatedly, until pH value=7 o'clock of the expansible black lead filter cake after depickling washing, stop depickling washing, make expansible black lead wet feed, and when acid strength≤20% of repetitive scrubbing, this washing acid solution is returned to suction washer as recycling,
Step 3, drying treatment: the expansible black lead wet feed of step 2 is sent in drying machine and is dried, and drying temperature is 55～65 DEG C, when being dried to graphite water content and being 0.5～1%, be expansible black lead finished product;
The processing of step 4, spent acid solution: the washing spent acid solution that the concentration that in the spent acid solution that to get in step 2 concentration that in No. 1 acidproof tank, depickling is press-filtered out be 80%～85% and No. 2 acidproof tanks, depickling is washed out is 30～45%, when the two proportioning is 55～60% by acid strength after mixing, make mix acid liquor;
Step 5, prepare alum liquor: mix acid liquor is added to reactor, pass into steam heating, in the time that temperature reaches 80 DEG C, close the weight proportion of Suan Ye ︰ aluminium hydroxide=1 ︰ 0.32 according to Hun, slowly add aluminium hydroxide, in the time that temperature of reaction reaches 120 DEG C ± 5 DEG C, be incubated 2 hours, make alum liquor;
Step 6, the alum liquor that step 5 is made are put in spray crystallizer, carry out at normal temperatures spray crystallization, obtain grains Tai-Ace S 150 finished product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310339529.1A CN103395810B (en) | 2013-08-07 | 2013-08-07 | Process for preparation of industrial aluminum sulfate by use of waste acid solution produced during production of expandable graphite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310339529.1A CN103395810B (en) | 2013-08-07 | 2013-08-07 | Process for preparation of industrial aluminum sulfate by use of waste acid solution produced during production of expandable graphite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103395810A CN103395810A (en) | 2013-11-20 |
| CN103395810B true CN103395810B (en) | 2014-09-17 |
Family
ID=49559608
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310339529.1A Expired - Fee Related CN103395810B (en) | 2013-08-07 | 2013-08-07 | Process for preparation of industrial aluminum sulfate by use of waste acid solution produced during production of expandable graphite |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103395810B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103928772A (en) * | 2014-04-21 | 2014-07-16 | 王要增 | Graphite grounding electrode |
| CN105347339A (en) * | 2015-12-11 | 2016-02-24 | 中国科学院兰州化学物理研究所 | Preparation method of expanded graphite |
| CN107500327A (en) * | 2017-10-11 | 2017-12-22 | 铜陵市吉烨净水材料有限公司 | A kind of aluminium sulphate production device and method |
| CN108277537A (en) * | 2018-01-26 | 2018-07-13 | 黑龙江科技大学 | A method of preparing hemihydrate calcium sulfate crystal whisker using expanded graphite production waste water |
| CN108545737B (en) * | 2018-05-30 | 2021-03-16 | 清华大学 | Preparation method of flexible graphite without high-temperature expansion |
| CN110092375B (en) * | 2019-06-11 | 2022-08-30 | *** | Processing method of expandable graphite without wastewater and waste residue discharge |
| CN111807360B (en) * | 2020-07-28 | 2021-03-19 | 韶山润泽新能源科技有限公司 | Purification treatment system and process for natural graphite negative electrode powder |
| CN115849369B (en) * | 2023-02-24 | 2023-05-02 | 潍坊新翰泽能源科技有限公司 | Energy-saving environment-friendly high-purity graphite deep processing production line and control method |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102320600A (en) * | 2011-08-17 | 2012-01-18 | 山东东昀石墨科技有限公司 | Preparation method of low-sulfur expandable graphite (graphite intercalation compound) |
| CN102381699A (en) * | 2011-07-26 | 2012-03-21 | 中科恒达石墨股份有限公司 | Preparation method of expandable graphite |
| CN102942177A (en) * | 2012-11-15 | 2013-02-27 | 中山大学 | Method for preparing graphene sheet |
| CN103145119A (en) * | 2013-03-14 | 2013-06-12 | 内蒙古瑞盛新能源有限公司 | Preparation method of expandable graphite |
| CN203048650U (en) * | 2012-12-02 | 2013-07-10 | 宜昌新成石墨有限责任公司 | Purification device for expansible graphite washing sewage |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6034492B2 (en) * | 1977-09-01 | 1985-08-09 | 中央化成株式会社 | Method for manufacturing thermally expandable graphite |
-
2013
- 2013-08-07 CN CN201310339529.1A patent/CN103395810B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102381699A (en) * | 2011-07-26 | 2012-03-21 | 中科恒达石墨股份有限公司 | Preparation method of expandable graphite |
| CN102320600A (en) * | 2011-08-17 | 2012-01-18 | 山东东昀石墨科技有限公司 | Preparation method of low-sulfur expandable graphite (graphite intercalation compound) |
| CN102942177A (en) * | 2012-11-15 | 2013-02-27 | 中山大学 | Method for preparing graphene sheet |
| CN203048650U (en) * | 2012-12-02 | 2013-07-10 | 宜昌新成石墨有限责任公司 | Purification device for expansible graphite washing sewage |
| CN103145119A (en) * | 2013-03-14 | 2013-06-12 | 内蒙古瑞盛新能源有限公司 | Preparation method of expandable graphite |
Non-Patent Citations (5)
| Title |
|---|
| JP昭54-38292 1979.03.22 |
| 可膨胀石墨的化学氧化法制备研究进展;林雪梅;《炭素》;20051231(第4期);第44-48页 * |
| 林雪梅.可膨胀石墨的化学氧化法制备研究进展.《炭素》.2005,(第4期),第44-48页. |
| 氧化酸液浸泡法制造可膨胀石墨过 程 中 污染治理的研究;高林;《贵州环保科技》;20011231;第7卷(第4期);第5-7页 * |
| 高林.氧化酸液浸泡法制造可膨胀石墨过 程 中 污染治理的研究.《贵州环保科技》.2001,第7卷(第4期),第5-7页. |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103395810A (en) | 2013-11-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103395810B (en) | Process for preparation of industrial aluminum sulfate by use of waste acid solution produced during production of expandable graphite | |
| CN101555033B (en) | Method for preparing cryolite and coproducing soluble glass by using hydrof luorosilicic acid | |
| CN101659444B (en) | Clean production method for preparing sodium chromate from chromite | |
| CN106006732A (en) | Method for preparing ammonium polyvanadate from high concentration vanadium liquid | |
| CN101481129B (en) | Method for producing barium sulfate | |
| CN106395904A (en) | Method utilizing chromium-containing sodium bisulfate to produce chromium oxide green | |
| CN105129830A (en) | Method for preparation of potassium alum from activated clay production mother liquor | |
| CN103833155A (en) | Chromium-containing wastewater treatment technology | |
| CN101428841A (en) | Process for producing basic copper carbonate | |
| WO2021088459A1 (en) | Method for producing amino trimethylene phosphonic acid as water treatment agent | |
| CN101481144B (en) | Clean production method for preparing potassium chromate from chromic iron | |
| CN102020316B (en) | Method for preparing chromic anhydride from potassium chromate | |
| CN109987637A (en) | A method of iron oxide yellow is prepared using red soil | |
| CN101759315B (en) | Method for recycling waste diluted sulfuric acid from acid washing solution of steel | |
| CN105271342A (en) | Method for preparing alum by utilization of activated clay waste acid mother solution | |
| CN103964512A (en) | Method for preparing iron oxide black from titanium dioxide byproducts, namely waste acid and ferrous sulfate | |
| CN101698514A (en) | Preparation method of electronic grade high-purity manganese sulfate monohydrate | |
| CN105293796A (en) | Method for co-production of sodalumite and gypsum through activated clay production mother liquid | |
| CN105502456A (en) | Method for recycling and preparing aluminum ammonium sulfate from activated clay production wastewater | |
| CN102825058B (en) | Method for recycling calcium sulfate waste residues generated in titanium dioxide acidic waste water | |
| CN104230844A (en) | Preparation method of vulcanization accelerator CZ | |
| CN104628605A (en) | Continuous catalytic sulfonation method of naphthalene and device thereof | |
| CN101503216B (en) | Method for preparing ferrate solution from red mud | |
| CN105016306A (en) | Preparation method of high-purity low-nitrogen potassium persulfate | |
| CN103738967A (en) | Method for production of sodium fluosilicate from fluorine-containing acidic 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: 20140917 Termination date: 20150807 |
|
| EXPY | Termination of patent right or utility model |