CN104261443A - Process for calcium-method production of magnesium hydrate by using nanofiltration membrane - Google Patents
Process for calcium-method production of magnesium hydrate by using nanofiltration membrane Download PDFInfo
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- CN104261443A CN104261443A CN201410499291.3A CN201410499291A CN104261443A CN 104261443 A CN104261443 A CN 104261443A CN 201410499291 A CN201410499291 A CN 201410499291A CN 104261443 A CN104261443 A CN 104261443A
- Authority
- CN
- China
- Prior art keywords
- calcium
- solution
- nanofiltration membrane
- chloride
- magnesium hydroxide
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- 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.)
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Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/14—Magnesium hydroxide
- C01F5/22—Magnesium hydroxide from magnesium compounds with alkali hydroxides or alkaline- earth oxides or hydroxides
Abstract
The invention relates to a process for calcium-method production of magnesium hydrate by using a nanofiltration membrane. The process comprises the following steps: (1) adding a calcium chloride solution to wastewater containing magnesium sulfate, reacting and precipitating; (2) filtering, and obtaining a gypsum product and a solution containing magnesium chloride; (3) adding a calcium hydroxide solution to the solution containing magnesium chloride separated and obtained in the step (2), reacting and precipitating; (4) filtering, and obtaining a magnesium hydroxide product and a solution containing calcium chloride; and (5) preparing the calcium hydroxide solution by one part of solution containing calcium chloride separated and obtained in the step (4), and concentrating one part of solution by using the nanofiltration membrane, circulating the concentrated solution containing calcium chloride to the step (1), discharging the filtrate or utilizing as industrial water. The process is simple, free of crystallization, and low in energy consumption; the filtrate filtered by the nanofiltration membrane can be used as common industrial water or cleaning water; intermediate products can be recycled; no other waste is generated; discharge of the wastewater containing magnesium sulfate is solved; and calcium sulphate gypsum and a magnesium hydrate product are obtained.
Description
Technical field
The present invention relates to a kind of calcium method of nanofiltration membrane that utilizes and produce magnesium sulfate technique, belong to high-salt wastewater and crisis salt chemical product production field.
Background technology
Now the most frequently used production magnesium hydroxide technique is calcium method and ammonia process, calcium method is that magnesium chloride solution adding calcium hydroxide generates magnesium hydroxide and calcium chloride, wherein magnesium hydroxide is solid particulate, and calcium chloride is dissolved substance, obtains oxyhydroxide by solid-liquid separation and washing.Ammonia process adds ammoniacal liquor in magnesium chloride or Adlerika to generate magnesium hydroxide and ammonium chloride or ammonium sulfate, and magnesium hydroxide is solid particulate, and liquid is ammonium sulfate or aqueous ammonium chloride solution.
No matter calcium method or ammonia process, while producing magnesium hydroxide, need to process calcic or the waste water containing ammonium, the common method of wastewater treatment is evaporating, concentrating and crystallizing, and operation energy consumption is high, and production cost is large.
Summary of the invention
The object of the invention is to the defect overcoming prior art, there is provided one with industrial sulphuric acid magnesium waste water for raw material, take calcium chloride as intercycle thing, consume calcium hydroxide produces calcium sulfate gypsum and magnesium hydroxide products, and chloride containing calcium waste water adopts sodium filter membrane to concentrate, and enriched material calcium chloride recycles, filtrate uses as service water, both magnesium sulfate containing waste water discharge had been solved, the reuse of purification Posterior circle, got back calcium sulfate gypsum and magnesium hydroxide products.
The present invention is achieved by the following technical solutions:
Utilize a producing magnesium hydroxide by calcium method technique for nanofiltration membrane, comprise the following steps:
(1) in the waste water of containing magnesium sulfate, calcium chloride solution is added, reaction precipitation;
(2) filter, obtain the solution of gypsum product and magnesium chloride containing;
(3) be separated in step (2) in the solution of the magnesium chloride containing obtained and add aqua calcis, reaction precipitation;
(4) filter, obtain the solution of magnesium hydroxide products and chloride containing calcium;
(5) step (4) is separated the solvent portions of chloride containing calcium that obtains for preparing aqua calcis, all the other concentrate by nanofiltration membrane, chloride containing calcium solution after concentrated is circulated to step (1), and filtrate is arranged outward or as process water.
Wherein,
Preferably, in step (1), in the waste water of described containing magnesium sulfate, the concentration of magnesium sulfate is 50-150g/L.
Preferably, in step (1), in described calcium chloride solution, the concentration of calcium chloride is 50-100g/L.
Preferably, in step (1), in the waste water of described containing magnesium sulfate, drop into calcium chloride solution, ingredient proportion presses SO
4 2-ion and CaCl
2mol ratio is 1:1.05-1.15; Be more preferably 1:1.10.
Preferably, in step (2), be separated in the solution obtaining magnesium chloride containing, the content of calcium chloride is 1-10g/L.This requires that the calcium chloride added in step (1) is suitably excessive.In actual production process, by detecting the mode of the concentration of the described calcium chloride be separated in the solution obtaining magnesium chloride containing, the judgement of precipitation terminal can be carried out or carries out the adjustment that step (1) calcium chloride adds ratio.
Preferably, in step (3), in described aqua calcis, the concentration of calcium hydroxide is 80-200g/L, is more preferably 100-130g/L.
Preferably, in step (3), in the solution of described magnesium chloride containing, add aqua calcis, ingredient proportion is according to MgCl
2with Ca (OH)
2mol ratio be 1:0.8-0.95, be more preferably 1:0.9.
Preferably, in step (4), be separated in the solution of the chloride containing calcium obtained, the content of magnesium ion is 0.1-5g/L.This prevents calcium hydroxide precipitation, and is unlikely to the quality affecting magnesium hydroxide while being conducive to forming magnesium hydrate precipitate.In actual production process, can by detect judgement that the described content of Chlorine in Solution magnesium being separated the chloride containing calcium obtained carries out precipitating terminal with or carry out aqua calcis in step (3) and add the adjustment of ratio.
Preferably, in step (5), the described solvent portions being separated the chloride containing calcium obtained is used for preparing aqua calcis (calcification slurry), be actually the preparation utilizing the moisture in calcium chloride solution to carry out calcification slurry, and other external source need not be introduced, and the calcium chloride be mixed in aqua calcis can not affect the reaction of step (3) precipitated magnesium hydroxide on the one hand, on the other hand along with the circulation of technique returns again step (1) generation calcium sulfate gypsum.Generally, be separated the 20-50wt% of solution of the chloride containing calcium obtained for configuring aqua calcis, but can according to prepare aqua calcis need carry out practical adjustments, this proportional range can be not limited to.
Preferably, in step (5), before entering nanofiltration membrane and filtering, the pH regulating the solution of described chloride containing calcium with hydrochloric acid is 3.0-7.0, prevents the fouling of membrane concentration process calcium.Being more preferably and being adjusted to pH is 5-7.
Preferably, the equipment that step (2) and step (4) are filtered is selected from the solid-liquid separating equipments such as plate-and-frame filter press, tubular filter, band filter, more preferably plate-and-frame filter press.
Technique effect of the present invention and advantage are:
Present invention is directed at the process of magnesium sulfate containing waste water, be actually and just consume calcium hydroxide, and calcium chloride is as intermediate product recycle, technique is simple, without the need to crystallization, energy consumption is low, the filtrate of nanofiltration membrane can be used as general industry water or rinse water uses, and intermediate product reusable edible, does not have other refuse to produce, both magnesium sulfate containing waste water discharge had been solved, got back calcium sulfate gypsum and magnesium hydroxide products.
Accompanying drawing explanation
A kind of calcium method of nanofiltration membrane that utilizes of Fig. 1 produces magnesium sulfate process flow sheet
Embodiment
Below by way of specific specific examples, technical scheme of the present invention is described.Should be understood that one or more method stepss that the present invention mentions do not repel and before and after described combination step, also to there is additive method step or can also insert additive method step between these steps clearly mentioned; Should also be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.And, except as otherwise noted, the numbering of various method steps is only the convenient tool differentiating various method steps, but not be ordering or the enforceable scope of restriction the present invention of restriction various method steps, the change of its relativeness or adjustment, when changing technology contents without essence, when being also considered as the enforceable category of the present invention.
Embodiment 1
With certain wet method Laterite-nickel Ore smelter waste discharge for raw material, utilize the producing magnesium hydroxide by calcium method of nanofiltration membrane;
Technological process (schema is as shown in Figure 1):
(1) at certain wet method Laterite-nickel Ore smelter waste discharge (MgSO
4121g/L, Na
2sO
412g/L), SO in molar ratio
4 2-: CaCl
2=1:1.10, adds calcium chloride solution (concentration 85g/L), generates calcium sulfate gypsum;
(2) after reaction, solution filter press is separated gypsum, and filtrate is MgCl in molar ratio
2: Ca (OH)
2=1:0.9, adds aqua calcis (concentration 100g/L), generates magnesium hydrate precipitate;
(3) employing filter press solid-liquid separation, washing obtain magnesium hydroxide, and a sheet frame filtrate part is used for the use of calcification slurry, and all the other add HCl and regulate pH to 6, enters sodium filter membrane system and filters, sodium filter membrane operating parameter: concentration ratio 5:3, producing water ratio 40%; (concentration ratio is stoste and concentrated solution volume ratio; Producing water ratio is filtrate and the ratio of stoste volume)
(4) concentrated solution calcium chloride concentration is 85g/L, is back to step (1) and produces calcium sulfate gypsum; Calcium chloride 2.9g/L, sodium-chlor 9.2g/L in filtrate component, outer row or make process water;
Embodiment 2
With certain plating mud hydrometallurgy factory efflux wastewater for raw material, utilize the producing magnesium hydroxide by calcium method of nanofiltration membrane;
Technological process:
(1) at certain plating mud hydrometallurgy factory efflux wastewater (MgSO
472g/L, NaCl23g/L, Na
2sO
417g/L), SO in molar ratio
4 2-: CaCl
2=1:10 adds calcium chloride solution (concentration 78g/L), generates calcium sulfate gypsum;
(2) be separated gypsum through filter press, filtrate is MgCl in molar ratio
2: Ca (OH)
2=1:0.9, adds aqua calcis (concentration 130g/L), generates magnesium hydrate precipitate;
(3) through filter press, washing obtains magnesium hydroxide; A sheet frame filtrate part is for preparing the calcification slurry of calcium hydroxide, and all the other regulate pH to 3, enter sodium filter membrane system and filter, sodium filter membrane operating parameter: sodium filter membrane concentrated solution and filtered liquid are than being 1:1, producing water ratio 50%;
(4) calcium chloride concentration of concentrated solution is 78g/L, is back to step (1) and produces calcium sulfate gypsum; Filtered liquid calcium chloride concentration is 2.3g/L, sodium chloride concentration 32g/L, outer row or make process water.
The above; be only preferred embodiment of the present invention; not to any formal and substantial restriction of the present invention; should be understood that; for those skilled in the art; under the prerequisite not departing from the inventive method, also can make some improvement and supplement, these improve and supplement and also should be considered as protection scope of the present invention.All those skilled in the art, without departing from the spirit and scope of the present invention, a little change made when utilizing disclosed above technology contents, the equivalent variations of modifying and developing, be Equivalent embodiments of the present invention; Meanwhile, all according to substantial technological of the present invention to the change of any equivalent variations that above-described embodiment is done, modify and differentiation, all still belong in the scope of technical scheme of the present invention.
Claims (10)
1. utilize a producing magnesium hydroxide by calcium method technique for nanofiltration membrane, comprise the following steps:
(1) in the waste water of containing magnesium sulfate, calcium chloride solution is added, reaction precipitation;
(2) filter, obtain the solution of gypsum product and magnesium chloride containing;
(3) be separated in step (2) in the solution of the magnesium chloride containing obtained and add aqua calcis, reaction precipitation;
(4) filter, obtain the solution of magnesium hydroxide products and chloride containing calcium;
(5) step (4) is separated the solvent portions of chloride containing calcium that obtains for preparing aqua calcis, all the other concentrate by nanofiltration membrane, the solution circulated of the chloride containing calcium after concentrated is to step (1), and filtrate is arranged outward or as process water.
2. a kind of producing magnesium hydroxide by calcium method technique utilizing nanofiltration membrane as claimed in claim 1, it is characterized in that, in step (1), in the waste water of described containing magnesium sulfate, the concentration of magnesium sulfate is 50-150g/L.
3. a kind of producing magnesium hydroxide by calcium method technique utilizing nanofiltration membrane as claimed in claim 2, it is characterized in that, in step (1), in described calcium chloride solution, the concentration of calcium chloride is 50-100g/L.
4. a kind of producing magnesium hydroxide by calcium method technique utilizing nanofiltration membrane as claimed in claim 1, it is characterized in that, in step (1), in the waste water of described containing magnesium sulfate, drop into calcium chloride solution, ingredient proportion presses SO
4 2-ion and CaCl
2mol ratio is 1:1.05-1.15.
5. a kind of producing magnesium hydroxide by calcium method technique utilizing nanofiltration membrane as claimed in claim 1, is characterized in that, in step (2), be separated in the solution obtaining magnesium chloride containing, the content of calcium chloride is 1-10g/L.
6. a kind of producing magnesium hydroxide by calcium method technique utilizing nanofiltration membrane as claimed in claim 4, it is characterized in that, in step (3), in described aqua calcis, the concentration of calcium hydroxide is 80-200g/L.
7. a kind of producing magnesium hydroxide by calcium method technique utilizing nanofiltration membrane as claimed in claim 1, it is characterized in that, in step (3), in the solution of described magnesium chloride containing, add aqua calcis, ingredient proportion is according to MgCl
2with Ca (OH)
2mol ratio be 1:0.8-0.95.
8. a kind of producing magnesium hydroxide by calcium method technique utilizing nanofiltration membrane as claimed in claim 1, is characterized in that, in step (4), be separated in the solution of the chloride containing calcium obtained, the content of magnesium ion is 0.1-5g/L.
9. a kind of producing magnesium hydroxide by calcium method technique utilizing nanofiltration membrane as claimed in claim 1, it is characterized in that, in step (5), before entering nanofiltration membrane and filtering, the pH regulating the solution of described chloride containing calcium with hydrochloric acid is 3.0-7.0, prevents the fouling of membrane concentration process calcium.
10. a kind of producing magnesium hydroxide by calcium method technique utilizing nanofiltration membrane as claimed in claim 1, it is characterized in that, the equipment that step (2) and step (4) are filtered is selected from plate-and-frame filter press, tubular filter and band filter.
Priority Applications (1)
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|---|---|---|---|
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| CN201410499291.3A CN104261443A (en) | 2014-09-25 | 2014-09-25 | Process for calcium-method production of magnesium hydrate by using nanofiltration membrane |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105274622A (en) * | 2015-11-16 | 2016-01-27 | 武汉工程大学 | Method for preparing magnesium hydrate crystal whiskers and calcium sulfate with phosphate tailings as raw material |
| CN111484178A (en) * | 2019-01-29 | 2020-08-04 | 洁海瑞泉膜技术（天津）有限公司 | Comprehensive treatment method for seawater or strong brine |
| CN111675229A (en) * | 2020-04-27 | 2020-09-18 | 广东粤电靖海发电有限公司 | Process for purifying magnesium hydroxide from desulfurization wastewater of coal-fired power plant |
| CN112357939A (en) * | 2020-07-22 | 2021-02-12 | 北京国电龙源环保工程有限公司 | Method for preparing magnesium hydroxide and calcium chloride by treating desulfurization wastewater of coal-fired power plant |
| CN116354454A (en) * | 2022-11-16 | 2023-06-30 | 内蒙古滟晴环境技术有限公司 | Nanofiltration system, system and method for treating high-concentration brine |
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| WO2000029327A1 (en) * | 1998-11-13 | 2000-05-25 | Norsk Hydro Asa | Method for production of magnesium chloride from sea water |
| CN101157464A (en) * | 2007-09-17 | 2008-04-09 | 河北科技大学 | Dolomite wet process comprehensive utilization technique |
| CN102874851A (en) * | 2012-09-28 | 2013-01-16 | 沈阳化工大学 | Method of utilizing brine to coproduce magnesium hydroxide and calcium sulfate whisker |
| CN103880211A (en) * | 2014-03-14 | 2014-06-25 | 浙江迪邦化工有限公司 | Process for resourceful treatment of high-salt wastewater containing magnesium |
| CN103950957A (en) * | 2014-04-22 | 2014-07-30 | 彭振超 | Process method for preparing magnesium hydroxide from magnesium sulfate |
-
2014
- 2014-09-25 CN CN201410499291.3A patent/CN104261443A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000029327A1 (en) * | 1998-11-13 | 2000-05-25 | Norsk Hydro Asa | Method for production of magnesium chloride from sea water |
| CN101157464A (en) * | 2007-09-17 | 2008-04-09 | 河北科技大学 | Dolomite wet process comprehensive utilization technique |
| CN102874851A (en) * | 2012-09-28 | 2013-01-16 | 沈阳化工大学 | Method of utilizing brine to coproduce magnesium hydroxide and calcium sulfate whisker |
| CN103880211A (en) * | 2014-03-14 | 2014-06-25 | 浙江迪邦化工有限公司 | Process for resourceful treatment of high-salt wastewater containing magnesium |
| CN103950957A (en) * | 2014-04-22 | 2014-07-30 | 彭振超 | Process method for preparing magnesium hydroxide from magnesium sulfate |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105274622A (en) * | 2015-11-16 | 2016-01-27 | 武汉工程大学 | Method for preparing magnesium hydrate crystal whiskers and calcium sulfate with phosphate tailings as raw material |
| CN111484178A (en) * | 2019-01-29 | 2020-08-04 | 洁海瑞泉膜技术（天津）有限公司 | Comprehensive treatment method for seawater or strong brine |
| CN111484178B (en) * | 2019-01-29 | 2022-05-17 | 洁海瑞泉膜技术（天津）有限公司 | Comprehensive treatment method for seawater or strong brine |
| CN111675229A (en) * | 2020-04-27 | 2020-09-18 | 广东粤电靖海发电有限公司 | Process for purifying magnesium hydroxide from desulfurization wastewater of coal-fired power plant |
| CN112357939A (en) * | 2020-07-22 | 2021-02-12 | 北京国电龙源环保工程有限公司 | Method for preparing magnesium hydroxide and calcium chloride by treating desulfurization wastewater of coal-fired power plant |
| CN116354454A (en) * | 2022-11-16 | 2023-06-30 | 内蒙古滟晴环境技术有限公司 | Nanofiltration system, system and method for treating high-concentration brine |
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Application publication date: 20150107 |