CN103395810A - 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
- CN103395810A CN103395810A CN2013103395291A CN201310339529A CN103395810A CN 103395810 A CN103395810 A CN 103395810A CN 2013103395291 A CN2013103395291 A CN 2013103395291A CN 201310339529 A CN201310339529 A CN 201310339529A CN 103395810 A CN103395810 A CN 103395810A
- 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.)
- Granted
Links
Landscapes
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
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 producing expansible black lead to prepare industrial aluminum sulphate.
Background technology
The production method of expansible black lead has multiple, and chemical oxidization method commonly used, with HNO
3, H
2SO
4Make oxygenant, using sodium dichromate 99, potassium permanganate, Potcrate etc. as intercalator, with the graphite reaction, make expansible black lead, 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 just plays oxygenizement in the whole reaction process of producing, and the quality of itself does not change.And in whole reaction process, decompose as the raw material of intercalator the active oxygen that discharges, enter graphite layers and form compound between graphite layers-expansible black lead.After reaction completed, a large amount of acid solutions needed water to clean, and for making the PH=7 of the expansible black lead of producing, one ton of expansible black lead of every production will produce 20～30m
3Acid-bearing wastewater, if directly discharging or discharge after simple neutralizing treatment can cause environmental pollution and the wasting of resources, this is also that the 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 contain a large amount of sulfuric acid, but also contain a large amount of trivalent chromic ions and a small amount of hexavalent chromium, more serious to the pollution that environment causes.The major defect that therefore existing graphite production technology exists: the one, the large concentration of spent acid liquid measure that produces in the graphite production process is large, thereby intractability is also large.These waste water, as without processing, be discharged in environment, 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 the sulfuric acid consumption is large, the 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 discharging that can solve spent acid solution in the 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 producing expansible black lead to prepare industrial aluminum sulphate of a large amount of sulfuric acid and water resources.
The technical scheme of taking for achieving the above object is: this processing method comprises the following steps:
Step 1, acidification: the sulfuric acid, the concentration that by natural flake graphite, concentration, are 98% are the hydrogen peroxide more than 28%, the reactor that adds the band stirring according to the weight proportion of Shi Mo ︰ Liu Suan ︰ hydrogen peroxide=1 ︰ 2.3 ︰ 0.15, temperature of reaction is controlled at 60 ℃ ± 5 ℃, 30 minutes reaction times, adding concentration is 65～70% sulfuric acid again, the sulfuric acid that is 98% of concentration in reactor is diluted to when concentration is 80～85% and gets final product, stirring is cooled to 25 ℃ of normal temperature, after reaction completes, make the mixed liquor of expansible black lead and sulphuric acid soln;
step 2, depickling, washing is processed: the reacted mixed liquor of step 1 is put into to 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 that extrudes is sent into agitation vat, adding concentration is 20～40% dilute sulphuric acid, stir, put into suction washer and carry out the depickling washing, the add-on of dilute sulphuric acid gets final product take 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 the pH value of the expansible black lead filter cake after the depickling washing=7 o'clock, stop the depickling washing, make the expansible black lead wet feed, and during the acid strength of repetitive scrubbing≤20%, 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 carried out drying, and drying temperature is 55～65 ℃, when being dried to the graphite water content and being 0.5～1%, is the expansible black lead finished product;
The processing of step 4, spent acid solution: get concentration that in No. 1 acidproof tank in step 2, depickling is press-filtered out and be concentration that in 80%～85% spent acid solution and No. 2 acidproof tanks, depickling is washed out and be 30～45% washing spent acid solution, the two proportioning gets final product while by acid strength after mixing, being 55～60%, makes mix acid liquor;
Step 5, prepare alum liquor: mix acid liquor is added to reactor, pass into steam heating, when temperature reaches 80 ℃, according to Hun, close the weight proportion of Suan Ye ︰ aluminium hydroxide=1 ︰ 0.32, slowly add aluminium hydroxide, when temperature of reaction reaches 120 ℃ ± 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.
According to utilization of the present invention, produce the processing method that the expansible black lead spent acid solution prepares industrial aluminum sulphate, its beneficial effect is:
(1) can effectively solve the severe contamination that the discharging of spent acid solution in the 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 fully.
(2) can will prepare the spent acid solution that produces in the expansible black lead process all for the production of the Tai-Ace S 150 of a large amount of needs of industry, can solve the recycling of expansible black lead production process spent acid solution, realize the zero release of spent acid solution, can effectively stop the pollution of high pollution industry to environment again, and can also save a large amount of sulfuric acid and water resources, greatly reduce production cost, can obtain larger economic benefit and environmental benefit thus.
(3) in the preparation process of Tai-Ace S 150, adopt spray crystallization to replace conventional crystallisation by cooling and pulverizing process, production efficiency is improved greatly, energy consumption reduces greatly.
Embodiment
The present invention will be further described below in conjunction with embodiment.
the present invention utilizes the spent acid solution of producing the expansible black lead generation to prepare the processing method of industrial aluminum sulphate, in method take natural flake graphite as raw material, with the vitriol oil, make oxygenant, with hydrogen peroxide, make intercalator, its method is: get natural flake graphite (C), concentration is that 98% sulfuric acid and concentration are the hydrogen peroxide more than 28%, and add according to the weight proportion of Shi Mo ︰ Liu Suan ︰ hydrogen peroxide=1 ︰ 2.3 ︰ 0.15 reactor of being with stirring, temperature of reaction is controlled at 60 ℃ ± 5 ℃, 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 after diluted acid when stirring the diluting concentrated sulfuric acid that makes in reactor and being 80～85% to concentration, be cooled to 25 ℃ of normal temperature, reaction equation is: H
2SO
4+ 2H
2O
2=H
2SO
4+ 2H
2O+O
2, in reaction, take the vitriol oil as oxygenant, take hydrogen peroxide as intercalator, decompose the active oxygen and the natural flake graphite reaction that discharge and generate expansible black lead, after reaction completes, make the mixed liquor of expansible black lead and sulphuric acid soln, again this mixed liquor is put into to pressure filter and carry out the 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 that extrudes 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 gets final product take 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 the depickling washing, until the pH value of expansible black lead filter cake=7 o'clock, the depickling washing is complete, make the 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 uses suction washer can improve detersive efficiency, the bath water amount greatly reduces.Then the expansible black lead wet feed is sent in drying machine and carried out drying, drying temperature is 55～65 ℃, when being dried to the graphite water content and being 0.5～1%, is the expansible black lead finished product; Finally carry out the processing of spent acid solution, get concentration that in No. 1 acidproof tank, depickling is press-filtered out and be concentration that in 80%～85% spent acid solution and No. 2 acidproof tanks, depickling is washed out and be 30～45% washing spent acid solution, the two proportioning gets final product while by acid strength after mixing, being 55～60%, make mix acid liquor, this mix acid liquor is added to reactor, pass into steam heating, when temperature reaches 80 ℃, according to Hun, close Suan Ye ︰ aluminium hydroxide Al (OH)
3The weight proportion of=1 ︰ 0.32, slowly add aluminium hydroxide Al (OH)
3, when temperature of reaction reaches 120 ℃ ± 5 °, be incubated 2 hours, make alum liquor, the alum liquor that makes 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, 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 that is widely used in wastewater treatment, also be used to the tap water of purifying, in paper industry, is used as the oar agent.
Claims (1)
1. processing method of utilizing the spent acid solution of producing expansible black lead to prepare industrial aluminum sulphate, it is characterized in that: the method comprises the following steps:
Step 1, acidification: the sulfuric acid, the concentration that by natural flake graphite, concentration, are 98% are the hydrogen peroxide more than 28%, the reactor that adds the band stirring according to the weight proportion of Shi Mo ︰ Liu Suan ︰ hydrogen peroxide=1 ︰ 2.3 ︰ 0.15, temperature of reaction is controlled at 60 ℃ ± 5 ℃, 30 minutes reaction times, adding concentration is 65～70% sulfuric acid again, the sulfuric acid that is 98% of concentration in reactor is diluted to when concentration is 80～85% and gets final product, stirring is cooled to 25 ℃ of normal temperature, after reaction completes, make the mixed liquor of expansible black lead and sulphuric acid soln;
step 2, depickling, washing is processed: the reacted mixed liquor of step 1 is put into to 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 that extrudes is sent into agitation vat, adding concentration is 20～40% dilute sulphuric acid, stir, put into suction washer and carry out the depickling washing, the add-on of dilute sulphuric acid gets final product take 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 the pH value of the expansible black lead filter cake after the depickling washing=7 o'clock, stop the depickling washing, make the expansible black lead wet feed, and during the acid strength of repetitive scrubbing≤20%, 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 carried out drying, and drying temperature is 55～65 ℃, when being dried to the graphite water content and being 0.5～1%, is the expansible black lead finished product;
The processing of step 4, spent acid solution: get in step 2 concentration that in No. 1 acidproof tank, depickling is press-filtered out and be concentration that in 80%～85% spent acid solution and No. 2 acidproof tanks, depickling is washed out and be 30～45% washing spent acid solution, the two proportioning gets final product while by acid strength after mixing, being 55～60%, makes mix acid liquor;
Step 5, prepare alum liquor: mix acid liquor is added to reactor, pass into steam heating, when temperature reaches 80 ℃, according to Hun, close the weight proportion of Suan Ye ︰ aluminium hydroxide=1 ︰ 0.32, slowly add aluminium hydroxide, when temperature of reaction reaches 120 ℃ ± 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.
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 true CN103395810A (en) | 2013-11-20 |
| CN103395810B 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) |
Cited By (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 |
| CN108545737A (en) * | 2018-05-30 | 2018-09-18 | 清华大学 | A kind of soft graphite preparation method without high-temperature expansion |
| CN110092375A (en) * | 2019-06-11 | 2019-08-06 | 张学忠 | A kind of expansible graphite processing method of no waste water and dregs discharge |
| CN111807360A (en) * | 2020-07-28 | 2020-10-23 | 韶山润泽新能源科技有限公司 | Purification treatment system and process for natural graphite negative electrode powder |
| CN115849369A (en) * | 2023-02-24 | 2023-03-28 | 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 (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5438292A (en) * | 1977-09-01 | 1979-03-22 | Chuo Kasei Kk | Method of making thermally 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) |
| 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 |
-
2013
- 2013-08-07 CN CN201310339529.1A patent/CN103395810B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5438292A (en) * | 1977-09-01 | 1979-03-22 | Chuo Kasei Kk | Method of making thermally expandable graphite |
| 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 (2)
| Title |
|---|
| 林雪梅: "可膨胀石墨的化学氧化法制备研究进展", 《炭素》 * |
| 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》 * |
Cited By (10)
| 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 |
| CN108545737A (en) * | 2018-05-30 | 2018-09-18 | 清华大学 | A kind of soft graphite preparation method without high-temperature expansion |
| CN110092375A (en) * | 2019-06-11 | 2019-08-06 | 张学忠 | A kind of expansible graphite processing method of no waste water and dregs discharge |
| CN110092375B (en) * | 2019-06-11 | 2022-08-30 | 张学忠 | Processing method of expandable graphite without wastewater and waste residue discharge |
| CN111807360A (en) * | 2020-07-28 | 2020-10-23 | 韶山润泽新能源科技有限公司 | Purification treatment system and process for natural graphite negative electrode powder |
| 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 |
| CN115849369A (en) * | 2023-02-24 | 2023-03-28 | 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103395810B (en) | 2014-09-17 |
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 | |
| CN106006732A (en) | Method for preparing ammonium polyvanadate from high concentration vanadium liquid | |
| CN101659444B (en) | Clean production method for preparing sodium chromate from chromite | |
| CN106395904A (en) | Method utilizing chromium-containing sodium bisulfate to produce chromium oxide green | |
| CN103833155A (en) | Chromium-containing wastewater treatment technology | |
| CN109928872B (en) | Method for high-purity synthesis of anthraquinone and co-production of magnesium sulfate | |
| CN101428841A (en) | Process for producing basic copper carbonate | |
| WO2013174063A1 (en) | Method for pre-treating phosphorus rock by titanium dioxide waste acid | |
| WO2021088459A1 (en) | Method for producing amino trimethylene phosphonic acid as water treatment agent | |
| CN102020316B (en) | Method for preparing chromic anhydride from potassium chromate | |
| CN103964512B (en) | Titanium white by product product spent acid and ferrous sulfate is utilized to prepare iron oxide black | |
| CN101905892A (en) | Process method for preparing 4A zeolite by recycling silica slag and aluminium slag | |
| CN109987637A (en) | A method of iron oxide yellow is prepared using red soil | |
| CN105000563A (en) | Method for preparing sodium fluosilicate by using fluorine-containing silicon slag | |
| CN105293796A (en) | Method for co-production of sodalumite and gypsum through activated clay production mother liquid | |
| CN103435091A (en) | Method for preparing superfine cuprous chloride | |
| CN102825058B (en) | Method for recycling calcium sulfate waste residues generated in titanium dioxide acidic waste water | |
| CN102627306A (en) | Novel method for preparing solid aluminum sulfate by using waste | |
| CN104628605A (en) | Continuous catalytic sulfonation method of naphthalene and device thereof | |
| CN104230844A (en) | Preparation method of vulcanization accelerator CZ | |
| CN103738967A (en) | Method for production of sodium fluosilicate from fluorine-containing acidic wastewater | |
| CN107902699A (en) | A kind of decomposition method of continuous pressure self-heating liquid phase oxidation chromite | |
| CN105016306A (en) | Preparation method of high-purity low-nitrogen potassium persulfate | |
| CN106430247A (en) | Method for preparing high-concentration sodium hydroxide by ultrasonically intensifying sodium sulfate |
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 |