CN1321086C - Modified bentonite chromium remover and its manufacturing method - Google Patents
Modified bentonite chromium remover and its manufacturing method Download PDFInfo
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- CN1321086C CN1321086C CNB2005100213437A CN200510021343A CN1321086C CN 1321086 C CN1321086 C CN 1321086C CN B2005100213437 A CNB2005100213437 A CN B2005100213437A CN 200510021343 A CN200510021343 A CN 200510021343A CN 1321086 C CN1321086 C CN 1321086C
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Abstract
The present invention to a modified bentonite chromium remover and a manufacturing method thereof. The manufacturing method has the following steps that 1) raw ores of bentonite are pulverized and are prepared into slurry by mixing with water; 2) soluble salt is dissolved in water are uniformly stirred to obtain soluble salt solution with 5 to 60% of mass concentration; 3) the soluble salt solution is added to the bentonite slurry liquid and is thoroughly mixed; then, the pH value of the obtained mixed solution is regulated between 5 and 9, and the mixed solution is aged; 4) after the aging, the mixed solution is heated to a temperature of 60 to 100 DEG C for further reaction, and the heating reaction time is within 8 to 24 hours; 5) after the heating, the mixed solution is dried to obtain the modified bentonite chromium remover which can be further formed into grainy modified bentonite chromium remover. When the modified bentonite chromium remover obtained by the modification of the bentonite by the manufacturing method of the present invention is used for treating chrome containted waste water, the modified bentonite chromium remover can greatly improve the removal rate of hexavalent chrome; after the modification, the chromium removal rate of the modified bentonite chromium remover for the chrome containted waste water can be improved to more than 98 %.
Description
(1) technical field:
The present invention relates to a kind of chromium remover, particularly a kind of modified bentonite chromium remover; The invention still further relates to the manufacture method of this modified bentonite chromium remover.
(2) background technology:
Water is indispensable physical resources in human lives and the activity in production.In recent years, along with socioeconomic fast development, water pollution is more and more serious, threatens the healthy and eubiosis of people gradually, and wherein heavy metal contamination has become puzzlement human society public hazards for many years.These heavy metal ion can not biological degradation in environment, can finally enter human body by the food link network, accumulates in human body.Wherein most of heavy metal ion is carcinogenic, teratogenesis, mutagenic highly toxic substance, is a kind of carcinogenic substance as sexavalent chrome, can cause digestive tract cancer after entering human body.Become problem anxious to be solved so how to improve the water body quality.Cr in the general electroplating wastewater
6+Concentration is 45～180mg/L, Cr in the percolate
6+Concentration is 0.002～1m/L.At problem how to remove pollution of chromium in the water body, people have carried out the research of a large amount of method for removing chromium, have drawn the method for a lot of processing waste water containing chrome.By its action principle, can be divided into physical method, chemical process, physico-chemical process, biological method four classes.Physical method uses seldom separately generally just as a link in other treatment processs.Chemical process is to add chemical agent in waste water, changes the chemical property of the pollutent of waste water by chemical reaction, makes it become innoxious substance or be easy to material with water sepn, the method for further removing again from waste water.This method has that operation is simple and reliable, less investment, can bear advantages such as big yield and high density load, but has secondary pollution problem.Bioremediation is to utilize the vital movement process of microorganism that pollutants in waste water is shifted and transformation, thus the treatment process that waste water is purified, and this method of laboratory study is more, but does not all reach actual application level.Physico-chemical process is the method that waste water is purified by physics and chemical comprehensive action, can be divided into ion exchange method, extraction process, absorption method and electrolytic process etc. again, and these methods all have relative merits separately.What use always in the absorption method is active carbon adsorption, but the regeneration difficulty of gac, and it also is not very extensive therefore using.
(3) summary of the invention:
The present invention will disclose a kind of with low cost, effective, simple modified bentonite chromium remover of manufacturing process of removal sexavalent chrome; The present invention also will disclose this method for preparation of modified alta-mud.
In recent years, based on research to aspects such as the surfactivity of natural mineral, ultra-fine effect, Chemical Composition, crystalline structure, physical technique and modification technologies thereof, find that mineral have good environment attribute, can be by the heavy metal ion in surface adsorption effect, ion exchange and the chemically reactive removal water body.Utilize of a great variety, reserves abundant, the simple relatively natural minerals of cheap, treatment process carries out wastewater treatment, has advantages such as less investment, effective and secondary pollution are little.It is a wide wastewater treatment engineering of amount multiaspect that water pollution is administered, and it is not that general environmental pollution treatment technology can support, and the cheap natural minerals of cost of development to be used for waste water control be a feasible way that reaches the scale pollution treatment.Thereby in recent years mineral material has been become the domestic and international research focus as water treatment absorbent, wherein wilkinite is first-selections of research because the structure of himself is given their a lot of particular performances.Wilkinite be a kind of be the essential mineral composition with the montmorillonite, contain the mixture that a small amount of illite, kaolinite, illite/montmorillonite mix clay mineral such as layer and other detrital mineral composition.Montmorillonite is by two one of the tetrahedral si-o film therebetween that connects of top layer silicate minerals of forming of the aluminum oxide octahedral sheet that connects of limit altogether altogether, and its crystalline structure formula is (M
xNH
2O) (Al
2-xMg
x) [Si
4O
10] (OH)
2Monolithic layer in its structure is the very big thin slice of aspect ratio, and diameter is about 100～200nm, and thickness only is 1nm.5～10 layers of such thin slice constitute bigger irregular group by these basic granuleses, thereby wilkinite has laminate structure by the interlayer cation formation basic granules that combines.Aluminium can cause negative charge (being layer charge) surplus in the structural unit layer to the isomorphism alternate ion exchange to aluminium of silicon and magnesium in the structure, for reaching the balance of positive and negative charge, needs the positively charged ion of some amount to compensate and is positioned at interlayer region.These positively charged ions are with ion bonding force connecting structure unit layer, and are active, and its key is more much bigger than molecular linkage or hydrogen bond by force.Therefore when smectite structure unit layer internal charge does not reach balance, will come filling by a certain amount of positively charged ion in the space between unit layer, thereby (sun) ion exchange will take place.Montmorillonite since in the broken key, lattice isomorph replace and to be adsorbed on its surperficial soil ulmin disassociation etc. former thereby electronegative, thereby cause between lattice layer in conjunction with loose, meet water and easily expand into fragment, particles dispersed degree height, have huge internal surface area and a large amount of exchangeable cations, (its cation exchange capacity is about 70～130mmol/100g) to make it have good adsorption performance and ion-exchange performance.Can be widely used in industries such as foundry industry, drilling well, building, light industry, be used for iron ore pellets in a large number and be used for all trades and professions as sorbent material.At present, studies show that in a large number: the application prospect of wilkinite in the waste water treatment industry is boundless, but wilkinite is used for the processing aspect of chromate waste water, does not see the report of practical application.
The present invention can increase substantially wilkinite and remove chromic ability, thereby when processing waste water containing chrome, can reach good effect by to bentonite modified, can carry out practical application; The manufacture method of modified bentonite chromium remover of the present invention, step is as follows:
1) the bentonite origin breeze is broken, add water furnishing pulpous state; Generally need the bentonite origin breeze is broken into 20～200 orders, so that add water furnishing pulpous state; When adding water wilkinite being sized mixing, the solid-liquid mass ratio of wilkinite and water is generally 1: 4～15; For reaching best effect, the solid-liquid mass ratio of wilkinite and water is preferably 1: 9;
2) soluble salt is soluble in water, stir, obtain mass concentration and be 5～60% soluble salt solution; Described soluble salt is preferably magnesium salts or soluble ferric iron salt or aluminum soluble salt or soluble sodium salt or the solubility polymerization molysite or the solubility polymerization aluminium salt of solubility; For example: aluminum chloride or ferrous sulfate or polymerize aluminum chloride or sodium-chlor etc.; The mass concentration of soluble salt solution is preferably 50%;
3) the soluble salt solution of gained is added in the bentonite slurry, and make both thorough mixing, regulate pH value to 5～9 of gained mixing solutions then, and with its old putting the regular hour; Wherein, the ratio of the metallic cation of soluble salt is generally 1g: 1～20mmol in the wilkinite in the bentonite slurry and the soluble salt solution, is preferably 1g: 15mmol; The old time of putting of mixing solutions was generally 1～5 hour, and the pH value of control mixing solutions is 7, and oldly puts best results 5 hours;
4) mixing solutions with old postpone is heated to 60～100 ℃, makes its further reaction; The reacting by heating time was generally 8～24 hours; For reaching better reaction effect, Heating temperature is preferably 80 ℃, and the reacting by heating time is preferably 10 hours;
5) mixing solutions after will heating carries out drying, obtains being used for the modified alta-mud for the treatment of refuse percolate; For the ease of the moulding of bentonite chromium remover, can earlier the mixing solutions after the heating be dried to a certain degree, generally being dried to its water content is 10～25%, extrusion moulding, and then, obtain granular modified bentonite chromium remover with its oven dry; Described dry mixed solution, exsiccant temperature are generally 100～120 ℃, and the exsiccant time is 6～20 hours; For reaching best drying effect, the exsiccant temperature is preferably 110 ℃, and the exsiccant time is preferably 12 hours.
Adopt manufacture method of the present invention that wilkinite is carried out resulting modified bentonite chromium remover after the modification, use it for the processing of chromate waste water, can improve it greatly chromic clearance.Detect with diphenyl carbazide spectrophotometry, the wilkinite raw ore is not removed ability to chromate waste water, by the modified alta-mud of gained after its modification clearance to chromium in the chromate waste water is risen to more than 98%, therefore this modified alta-mud extremely is suitable for the processing of chromate waste water.Because the reserves of bentonite ore are big, low price, and the production technique of bentonite modified processing is fairly simple, can directly use raw ore to carry out modification, need not purify, can avoid using great amount of water resources and large-scale equipment for separating liquid from solid, also need not any other complexity, large-scale equipment, therefore its production cost is cheap, can carry out industrialized mass production fully.
(4) embodiment:
Embodiment 1:
1) bentonite in powder is broken to 20 orders, and adds water furnishing pulpous state; In the bentonite slurry of gained, the solid-liquid mass ratio of wilkinite and water is 1: 4;
2) polymerize aluminum chloride is soluble in water, the limit edged stirs, and until both thorough mixing, obtains mass concentration and be 5% polymeric aluminum chlorides solution;
3) polymeric aluminum chlorides solution is added in the bentonite slurry, and stir, make both thorough mixing, the pH value with the gained mixing solutions transfers to 5 then, again with its ageing 5 hours; Wherein aluminum ions ratio is 1g: 15mmol in the wilkinite in the bentonite slurry and the polymeric aluminum chlorides solution;
4) above-mentioned mixing solutions is placed 80 ℃ of reactions 10 hours;
5) then with the mixing solutions of gained 100 ℃ of dryings, to its water content be 10%, extrusion moulding then 105 ℃ of dryings 12 hours, promptly gets modified bentonite chromium remover again.
Embodiment 2:
1) bentonite in powder is broken to 100 orders, and adds water furnishing pulpous state; In the bentonite slurry of gained, the solid-liquid mass ratio of wilkinite and water is 1: 15;
2) ferrous sulfate is soluble in water, stir, obtain mass concentration and be 60% copperas solution;
3) copperas solution is added in the bentonite slurry, the limit edged stirs, and until both thorough mixing, the pH value with the mixing solutions of gained transfers to 9 then, again with its ageing 1 hour; Wherein the ratio of iron ion is 1g: 1mmol in the wilkinite in the bentonite slurry and the copperas solution;
4) above-mentioned mixing solutions is placed 60 ℃ of reactions 8 hours;
5) then with the mixing solutions of gained 120 ℃ of dryings 6 hours, promptly get modified bentonite chromium remover.
Embodiment 3:
1) bentonite in powder is broken to 200 orders, and adds water furnishing pulpous state; In the bentonite slurry of gained, the solid-liquid mass ratio of wilkinite and water is 1: 9;
2) sodium-chlor is soluble in water, stir, obtain mass concentration and be 50% sodium chloride solution;
3) sodium chloride solution is added in the bentonite slurry, the limit edged stirs, and until both thorough mixing, the pH value with the mixing solutions of gained transfers to 7 then, again with its ageing 3 hours; Wherein the ratio of sodium ion is 1g: 20mmol in the wilkinite in the bentonite slurry and the sodium chloride solution;
4) above-mentioned mixing solutions is placed 100 ℃ of reactions 24 hours;
5) then with the mixing solutions of gained 110 ℃ of dryings 20 hours, promptly get modified bentonite chromium remover.
Claims (8)
1, a kind of manufacture method of modified bentonite chromium remover, step is as follows:
1) the bentonite origin breeze is broken, add water furnishing pulpous state; Wherein, the solid-liquid mass ratio of wilkinite and water is 1: 4～15;
2) soluble salt is soluble in water, stir, obtain mass concentration and be 5～60% soluble salt solution;
3) the soluble salt solution of gained is added in the bentonite slurry, and make both thorough mixing, regulate pH value to 5～9 of gained mixing solutions then, and with its old putting; The ratio of the metallic cation of soluble salt is 1g: 1～20mml in wilkinite in the described bentonite slurry and the soluble salt solution;
4) mixing solutions with old postpone is heated to 60～100 ℃, makes its further reaction, and the reacting by heating time is 8～24 hours;
5) mixing solutions after will heating carries out drying, obtains modified bentonite chromium remover.
2, the manufacture method of modified bentonite chromium remover according to claim 1 is characterized in that: described soluble salt is solubility magnesium salts or soluble ferric iron salt or aluminum soluble salt or soluble sodium salt or solubility polymerization molysite or solubility polymerization aluminium salt.
3, the manufacture method of modified bentonite chromium remover according to claim 2 is characterized in that: described soluble salt is aluminum chloride or ferrous sulfate or polymerize aluminum chloride or sodium-chlor.
4, according to the manufacture method of any one described modified bentonite chromium remover in the claim 1～3, it is characterized in that: in the step 5), it is 10～25% that the mixing solutions after will heating earlier is dried to its water content, extrusion moulding then, be dried again, obtain granular modified bentonite chromium remover.
5, according to the manufacture method of any one described modified bentonite chromium remover in the claim 1～3, it is characterized in that: step 2) in, the mass concentration of soluble salt solution is 50%.
6, according to the manufacture method of any one described modified bentonite chromium remover in the claim 1～3, it is characterized in that: in the step 3), after overregulating the pH value, the old time of putting of gained mixing solutions is 1～5 hour.
7, according to the manufacture method of any one described modified bentonite chromium remover in the claim 1～3, it is characterized in that: in the step 5), the mixing solutions drying temperature after the heating is 100～120 ℃; Be 6～20 hours time of drying.
8, the modified bentonite chromium remover that any one described method is made in the claim 1～7.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101348298B (en) * | 2008-09-02 | 2010-06-23 | 金堆城钼业股份有限公司 | Rapid method for removing chromium in waste water |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100448524C (en) * | 2007-04-03 | 2009-01-07 | 沈阳建筑大学 | Method for producing inorganic modified bentonite chromium remover |
| CN101781050A (en) * | 2010-03-09 | 2010-07-21 | 江汉大学 | Method for treating low-concentration chromate waste water |
| CN102327893B (en) * | 2010-07-13 | 2013-06-05 | 中国科学院研究生院 | Material for removing lead in heavy-metal soil leacheate as well as preparation method and application thereof |
| CN103555337B (en) * | 2013-11-04 | 2015-06-10 | 尹无忌 | Heavy metal ion stabilizer for ecological environment and environment restoration method |
| CN109759030B (en) * | 2019-03-08 | 2021-08-24 | 河北工业大学 | Preparation method of polyacrylic acid composite aluminum modified bentonite water treatment agent capable of adsorbing Cr (VI) |
| CN114289491A (en) * | 2021-12-27 | 2022-04-08 | 桂润环境科技股份有限公司 | Arsenic-antimony composite polluted soil remediation agent and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1059706A (en) * | 1990-09-10 | 1992-03-25 | 张庆华 | Electrochemical process is removed chromic technology and equipment in the Drinking Water |
| CN1072396A (en) * | 1992-09-28 | 1993-05-26 | 机械电子工业部北方设计研究院 | Chromic method and device thereof in a kind of removal Drinking Water |
-
2005
- 2005-07-23 CN CNB2005100213437A patent/CN1321086C/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1059706A (en) * | 1990-09-10 | 1992-03-25 | 张庆华 | Electrochemical process is removed chromic technology and equipment in the Drinking Water |
| CN1072396A (en) * | 1992-09-28 | 1993-05-26 | 机械电子工业部北方设计研究院 | Chromic method and device thereof in a kind of removal Drinking Water |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101348298B (en) * | 2008-09-02 | 2010-06-23 | 金堆城钼业股份有限公司 | Rapid method for removing chromium in waste water |
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Owner name: GUILIN RESEARCH INSTITUTE OF GEOLOGY FOR MINERAL R Free format text: FORMER NAME: GUILIN MINERALS + GEOLOGIC ACADEMY |
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Address after: 541004 the Guangxi Zhuang Autonomous Region Guilin auxiliary Star Road, No. 9 Patentee after: China Nonferrous Metal Guilin Research Institute of Geology for Mineral Resources Co., Ltd. Address before: 541004 No. 2, Star Road, Guilin, the Guangxi Zhuang Autonomous Region Patentee before: Guilin Minerals & Geologic Academy |