CN102020378A - Purification and decoloration process method of concentrated brine - Google Patents
Purification and decoloration process method of concentrated brine Download PDFInfo
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- CN102020378A CN102020378A CN 201010522504 CN201010522504A CN102020378A CN 102020378 A CN102020378 A CN 102020378A CN 201010522504 CN201010522504 CN 201010522504 CN 201010522504 A CN201010522504 A CN 201010522504A CN 102020378 A CN102020378 A CN 102020378A
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- brine
- zirconium hydroxide
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Abstract
The invention relates to a purification and decoloration process method of concentrated brine, comprising the following steps of: oxidizing the brine by using hydrogen peroxide at room temperature, wherein the using amount of the hydrogen peroxide is 1-3 percent of the processing amount of the brine according to volume ratio; adsorbing and decoloring the oxidized brine for 1-2 hours through zirconium hydroxide under the condition that a pH value is 2-3; and then filtering the adsorbed brine to separate the zirconium hydroxide so as to obtain refined discolored brine, wherein the separated zirconium hydroxide can be recycled after being subjected to desorption processing, therefore economic cost is greatly reduced. The purification and decoloration process method of the concentrated brine can obtain stable and high-quality brine by effectively removing organic color materials and inorganic color-developing ions which are contained in the brine, thereby greatly enhancing the purity and the quality of subsequent developed products of the brine; and in addition, the invention has simple equipment and short process flow without environmental pollution.
Description
Technical field
The present invention relates to a kind of purification and decoloration technology, relate in particular to a kind of use oxidation, absorption, filtering integrated processes, a kind of concentrated brine purification and decoloration processing method of exploitation higher-grade magnesium Chemicals pre-treatment.
Background technology
Seawater and salt lake are carried after the salt and are contained abundant magnesium resource in the concentrated brine, are the important source material of magnesium Chemicals exploitation.The magnesium Chemicals of developed country such as the U.S., Japan more than 90% are raw material with liquid ore deposits such as seawater, salt lake brines; China's sea salt output ranks first in the world, and produces sea salt 2,300 ten thousand t per year, about 2,000 ten thousand m of by-product bittern
3/ a, wherein magnesium chloride, sal epsom stock number reach 379.2 ten thousand t/a and 175.2 ten thousand t/a respectively; In addition, the magnesium salts reserves reach 48.16 hundred million t in China's salt lake brine, wherein magnesium chloride 31.43 hundred million t, sal epsom 16.73 hundred million t, the only annual by-product bittern in Cha Erhan salt lake 3,200 ten thousand t, wherein magnesium chloride more than 1,100 ten thousand t.But organic chromonic material of the large amount of complex that contains in the bittern and inorganic chromogenic ion, make bittern in the exploitation concentration process, not only present dense color, and increased the viscosity of bittern, the output and the quality of China's magnesium Chemicals have been had a strong impact on, be difficult to reach the top grade product, all large-tonnage, low value-added raw material type product are main to cause the magnesium Chemicals of China, greatly reduce competitive power in the world market, the more important thing is this low-level a large amount of exploitations of bittern resource, caused the serious waste of resource.Therefore how to purify concentrated brine, remove coloring matter, thereby the magnesium Chemicals of production higher-grade, high added value are difficult problems that needs to be resolved hurrily.
Bittern the exploitation concentration process in enrichment a large amount of complicated organism, these organism are mainly derived from aquatic organism meta-bolites and soil ulmin etc., its composition is based on the fragrant same clan and derived material, nitrogen heterocyclic ring class material, catenanes material (comprising acid, alkane, alcohol, fat etc.) and polycyclic naphthene hydrocarbons etc., these organism and other some inorganic chromogenic ions make bittern present dense color, in addition, because bittern salinity height, viscosity after concentrating are big, make its colorful wastewater be difficult to more handle than other.At present, about the corresponding report of bittern purifying and decolorizing technology and few, and exist many problems, as: Yu Cheng Mr. Zuo Chun adopts air supporting, cascade filtration to remove dust and suspended substance in the bittern among the Japanese Patent CN 1182406A, its turbidity is reduced, but decolorizing effect is also not obvious, and processing cost is higher, the actual motion poor effect.Professor Wang Haizeng of Qingdao Marine University adopts the polyacrylamide flocculating settling earlier, remove a part of complicated organism, adsorb with polymeric adsorbent GDX-102 (nonpolar micropore polystyrene) back, decolorizing effect is comparatively obvious, but the decolouring poor stability of this method is mainly reflected in that flco forms difficulty in the flocculation process, and settling property is poor, be difficult to effective separation, and the magnesium ion loss is big.Employing XDA-1 resin absorption such as Jinpeng's health of Xi'an University of Architecture and Technology and catalyzed oxidation combination process decolour to bittern, be under 1～2 the condition at pH, bittern is earlier through the XDA-1 resin absorption, (the hydrogen peroxide dosage is 3g/L to carry out catalytic oxidation of hydrogen peroxide again, the ozone dosage is 0.5g/L) handle, handle back bittern and pass through XDA-1 type resin absorption once more, bittern organic removal rate after the processing is 70%, but this method complex process, operation easier is big, and the loss amount of magnesium ion is big.Among the patent CN 101164886A bang dragon etc. with bittern earlier through sand filtration, remove bigger suspended particulate, at room temperature, with the bittern after the sand filtration with hydrogen peroxide oxidation 0.5～1.5h (the hydrogen peroxide consumption by mass ratio be the bittern consumption 1.5%～3.5%), bittern after the oxidation again through gac in 60～90 ℃ of adsorption bleaching 2～9h, bittern after the absorption is obtaining refining decolouring bittern after filtration, this method bittern percent of decolourization can reach 80～90%, but the decolorization required time is long, the energy consumption height, and sorbent material is disposable use, and the processing cost height is difficult to realize industrial applications.
Summary of the invention
The object of the present invention is to provide that a kind of technology is simple and direct, stable, Financial cost is low and can effectively remove a kind of concentrated brine purification and decoloration processing method that magnesium Chemicals that colourity makes bittern behind the purification and decoloration reach processing higher-grade, high added value require.
The processing method of a kind of concentrated brine purification and decoloration provided by the invention, step comprise oxidation, absorption and filtering link, are purified the bittern of decolouring.
The technical scheme that the present invention takes for the technical problem that exists in the solution known technology is: these technology branch following steps are implemented:
(1). at room temperature, with bittern hydrogen peroxide oxidation 2～3h, the hydrogen peroxide consumption is 1%～3% of bittern treatment capacity by volume;
(2). the bittern after the oxidation is through zirconium hydroxide adsorption bleaching 1～2h in the pH value under 2～3 the condition;
(3). the bittern after the absorption more after filtration, the separation of hydrogen zirconium white obtains the bittern of refining decolouring;
(4). the zirconium hydroxide of filtering separation recycles after desorption is handled.
The present invention can also adopt following technical scheme:
In the described step (1), hydrogen peroxide is the technical grade hydrogen peroxide, and mass concentration is 30%;
In the described step (2), zirconium hydroxide is the technical grade zirconium hydroxide, and zirconium hydroxide content is not less than 76%;
In the described step (2), the pH value mass concentration of bittern is 2% hydrochloric acid adjusting;
In the described step (3), bittern filters with pressure filter;
In the described step (4), the zirconium hydroxide mass concentration of filtering separation is 5% sodium hydroxide desorption, and the desorption time of zirconium hydroxide is 1～2h;
Zirconium hydroxide behind the described desorption is washed till neutrality with suitable quantity of water.
Advantage and positively effect that the present invention has are: good decolorizing effect, and the brine quality after the decolouring is stable, and turbidity hangs down 1NTU, and colourity is lower than 5 degree, can satisfy the requirement that bittern is further processed the magnesium Chemicals of higher-grade, high added value; The magnesium ion rate of loss is lower than 1%, has improved the magnesium ion utilization ratio, is convenient to the exploitation of follow-up magnesium Chemicals; Sorbent material zirconium hydroxide in the decoloration process can recycle, and has reduced technology running cost, has overall economic efficiency preferably; Processing unit processing is simple, reduced investment, and attended operation is convenient, is easy to realize suitability for industrialized production.
Description of drawings
Fig. 1 is the process flow diagram of the purification and decoloration technology of concentrated brine of the present invention.
Among the figure: 1. hydrogen peroxide oxidation, 2. zirconium hydroxide absorption is 3. filtered, 4. zirconium hydroxide desorption, 5. bittern quality inspection.
Embodiment:
For further understanding summary of the invention of the present invention, characteristics and effect, exemplify following examples now, and conjunction with figs. is described in detail as follows:
Embodiment 1
To contain Mg
2+114.5g/L, colourity 684 degree, the concentrated brine 1L of turbidity 230NTU, send in the reactor of oxidizing process section 1 shown in Figure 1, the hydrogen peroxide that adds bittern amount 1.0% (being 10mL) by volume, appropriateness stirs under the room temperature, behind the oxidation 2h, bittern is delivered to zirconium hydroxide absorbing process section 2 processes, and adds the 60g zirconium hydroxide in reactor, (this moment, the pH value of bittern can be stabilized in 2～3 scopes just in the appropriateness stirring under the room temperature, if the pH value is too high, the hydrochloric acid of available quality concentration 2% is regulated), behind the absorption 1h, sending into filtration process section 3 filters, filter the isolating zirconium hydroxide in back and deliver to zirconium hydroxide separating process section 4 processes, add the sodium hydroxide of 100mL mass concentration 5% in reactor, appropriateness stirs under the room temperature, behind the desorption 1h, with suitable quantity of water zirconium hydroxide is washed till neutrality, delivers to absorbing process section 2 processes and recycle, the bittern after the purification is delivered to bittern quality inspection process section 5 processes, bittern is tested the result: bittern Mg
2+Content 113.9g/L, colourity 2.9 degree, turbidity 3NTU, chroma removal rate 99.6%, Mg
2+Rate of loss 0.52%.The chroma removal rate of bittern and Mg
2+Rate of loss all is higher than present current technology, satisfies the further requirement of the high-grade magnesium Chemicals of processing.
Its advantage is: good decolorizing effect, and the brine quality after the decolouring is stable, and turbidity hangs down 1NTU, and colourity is lower than 5 degree, can satisfy the requirement that bittern is further processed the magnesium Chemicals of higher-grade, high added value; The magnesium ion rate of loss is lower than 1%, has improved the magnesium ion utilization ratio, is convenient to the exploitation of follow-up magnesium Chemicals; Sorbent material zirconium hydroxide in the decoloration process can recycle, and has reduced technology running cost, has overall economic efficiency preferably; Processing unit processing is simple, reduced investment, and attended operation is convenient, is easy to realize suitability for industrialized production.
Embodiment 2
Its specific operation process and advantage are with embodiment 1, only the zirconium hydroxide that absorbing process section 2 processes are added is changed into the zirconium hydroxide that recycles behind the desorption, and other condition is all identical with embodiment 1, and the bittern after the purification is delivered to bittern quality inspection process section 5, bittern is tested the result: bittern Mg
2+Content 113.7g/L, colourity 3.1 degree, turbidity 3NTU, chroma removal rate 99.5%, Mg
2+Rate of loss 0.69%.As seen, the zirconium hydroxide that recycles behind the desorption, its adsorptive power does not descend, and still has good decolorizing effect, and technology stability is fine.
Embodiment 3
Its specific operation process and advantage are with embodiment 1, only to change into 0.1%, 0.25%, 0.5%, 1.0%, 2.0%, 4.0%, 8.0% other condition all identical with embodiment 1 for the hydrogen peroxide that oxidizing process section 2 processes are added, the bittern that adsorption cleaning is crossed is tested, be the results are shown in Table 1.As seen, when the hydrogen peroxide dosage was lower than 0.5%, because oxidized thorough inadequately of organism in the bittern, chroma removal rate was very low, only is about 70%; After the hydrogen peroxide dosage was higher than 2%, the bittern chroma removal rate was kept constant substantially, but the magnesium ion rate of loss increases to some extent.Take all factors into consideration factors such as decolorizing effect, magnesium ion rate of loss and working cost, the present invention selects for use and adds bittern amount 1.0% hydrogen peroxide by volume bittern is carried out oxidation.
Table 1
Embodiment 4
Its specific operation process and advantage are with embodiment 1, only the dosage of absorbing process section (3) process zirconium hydroxide is changed into 20g, 40g, 60g, 80g, 100g, 120g, other condition is all identical with embodiment 1, and the bittern that adsorption cleaning is crossed is tested, and the results are shown in Table 2.As seen, when the dosage of zirconium hydroxide was lower than 40g, because organic chromonic material and inorganic chromogenic ion can not be adsorbed removal fully in the bittern, chroma removal rate was very low, only is about 75%; After the zirconium hydroxide dosage was higher than 80g, the bittern chroma removal rate was kept constant substantially, but the rate of loss of magnesium ion sharply increases along with the increasing of zirconium hydroxide dosage.Take all factors into consideration factors such as decolorizing effect, magnesium ion rate of loss and working cost, the present invention selects for use every 1L bittern to add the bittern of 60g zirconium hydroxide after to oxidation to adsorb.
Table 2
Above-described embodiment is described preferred implementation of the present invention; be not that scope of the present invention is limited; design under the prerequisite of spirit not breaking away from the present invention; various distortion and improvement that those of ordinary skills make technical scheme of the present invention all should fall in the definite protection domain of claims of the present invention.
Claims (7)
1. a concentrated brine purification and decoloration processing method is characterized in that, this technology divides following steps to implement:
(1). at room temperature, with bittern hydrogen peroxide oxidation 2～3h, the hydrogen peroxide consumption is 1%～3% of bittern treatment capacity by volume;
(2). the bittern after the oxidation is through zirconium hydroxide adsorption bleaching 1～2h in the pH value under 2～3 the condition;
(3). the bittern after the absorption more after filtration, the separation of hydrogen zirconium white obtains the bittern of refining decolouring;
(4). the zirconium hydroxide of filtering separation recycles after desorption is handled.
2. a kind of concentrated brine purification and decoloration processing method as claimed in claim 1 is characterized in that in the described step (1), hydrogen peroxide is the technical grade hydrogen peroxide, and mass concentration is 30%.
3. a kind of concentrated brine purification and decoloration processing method as claimed in claim 1 is characterized in that in the described step (2), zirconium hydroxide is the technical grade zirconium hydroxide, and zirconium hydroxide content is not less than 76%.
4. a kind of concentrated brine purification and decoloration processing method as claimed in claim 1 is characterized in that, in the described step (2), the pH value mass concentration of bittern is 2% hydrochloric acid adjusting.
5. a kind of concentrated brine purification and decoloration processing method as claimed in claim 1 is characterized in that in the described step (3), bittern filters with pressure filter.
6. a kind of concentrated brine purification and decoloration processing method as claimed in claim 1 is characterized in that, in the described step (4), the zirconium hydroxide mass concentration of filtering separation is 5% sodium hydroxide desorption, and the desorption time of zirconium hydroxide is 1～2h.
7. a kind of concentrated brine purification and decoloration processing method as claimed in claim 6 is characterized in that the zirconium hydroxide behind the desorption washes with water to neutrality.
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| CN 201010522504 CN102020378A (en) | 2010-10-28 | 2010-10-28 | Purification and decoloration process method of concentrated brine |
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| CN 201010522504 CN102020378A (en) | 2010-10-28 | 2010-10-28 | Purification and decoloration process method of concentrated brine |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103637160A (en) * | 2013-12-23 | 2014-03-19 | 中盐皓龙盐化有限责任公司 | Preparation process of liquid edible salt |
| CN107399747A (en) * | 2017-08-17 | 2017-11-28 | 江苏久吾高科技股份有限公司 | A kind of method and device that lithium is carried from salt lake brine with high magnesium-lithium ratio |
| CN110790423A (en) * | 2019-10-29 | 2020-02-14 | 江苏昌吉利新能源科技有限公司 | Lithium-containing brine decoloring and impurity removing process |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6010630A (en) * | 1993-08-26 | 2000-01-04 | Kemira Kemi Ab | Method for recovering at least one metal from an acidified waste water sludge |
| CN101164886A (en) * | 2007-09-28 | 2008-04-23 | 山西大学 | Method for purifying and decoloring salt lake brine |
| CN101195501A (en) * | 2007-12-11 | 2008-06-11 | 深圳市龙澄高科技环保有限公司 | Fecal sewage decolorizing method and device |
| CN101665302A (en) * | 2009-09-17 | 2010-03-10 | 宁波万华聚氨酯有限公司 | Processing method of effluent brine produced in MDI production process |
-
2010
- 2010-10-28 CN CN 201010522504 patent/CN102020378A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6010630A (en) * | 1993-08-26 | 2000-01-04 | Kemira Kemi Ab | Method for recovering at least one metal from an acidified waste water sludge |
| CN101164886A (en) * | 2007-09-28 | 2008-04-23 | 山西大学 | Method for purifying and decoloring salt lake brine |
| CN101195501A (en) * | 2007-12-11 | 2008-06-11 | 深圳市龙澄高科技环保有限公司 | Fecal sewage decolorizing method and device |
| CN101665302A (en) * | 2009-09-17 | 2010-03-10 | 宁波万华聚氨酯有限公司 | Processing method of effluent brine produced in MDI production process |
Non-Patent Citations (1)
| Title |
|---|
| 《江苏化工》 20061231 刘泼等 联碱生产洗盐水中硫酸根的脱除工艺研究 第14-16页 1-7 , 第15期 2 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103637160A (en) * | 2013-12-23 | 2014-03-19 | 中盐皓龙盐化有限责任公司 | Preparation process of liquid edible salt |
| CN107399747A (en) * | 2017-08-17 | 2017-11-28 | 江苏久吾高科技股份有限公司 | A kind of method and device that lithium is carried from salt lake brine with high magnesium-lithium ratio |
| CN107399747B (en) * | 2017-08-17 | 2023-11-07 | 江苏久吾高科技股份有限公司 | Method and device for extracting lithium from salt lake brine with high magnesium-lithium ratio |
| CN110790423A (en) * | 2019-10-29 | 2020-02-14 | 江苏昌吉利新能源科技有限公司 | Lithium-containing brine decoloring and impurity removing process |
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Application publication date: 20110420 |