CN103011209A - Ammonium chloride circulation method for producing magnesium hydroxide and calcium chloride from carbide slag and salt lake magnesium chloride - Google Patents
Ammonium chloride circulation method for producing magnesium hydroxide and calcium chloride from carbide slag and salt lake magnesium chloride Download PDFInfo
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- CN103011209A CN103011209A CN2011102894471A CN201110289447A CN103011209A CN 103011209 A CN103011209 A CN 103011209A CN 2011102894471 A CN2011102894471 A CN 2011102894471A CN 201110289447 A CN201110289447 A CN 201110289447A CN 103011209 A CN103011209 A CN 103011209A
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- magnesium
- chloride
- carbide slag
- filtrate
- ammonium chloride
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Abstract
The invention belongs to the field of waste reuse. Carbide slag is a waste generated in an acetylene production process using a calcium carbide method; and the main component is Ca(OH)2 the content of which exceeds 85%. The byproduct magnesium salt of the salt lake sylvite industry is mainly used for producing cheap magnesium chloride hexahydrate and magnesium sulfate heptahydrate, or is exported directly in a mineral form, causing waste of resources. According to the invention, high-purity magnesium hydroxide as well as anhydrous calcium chloride is produced by use of carbide slag and salt lake magnesium chloride by an ammonium chloride circulation method; and the method not only can obtain high-purity magnesium hydroxide and industrial-grade calcium chloride, but also can effectively solve the problem of environmental pollution caused by ammonia gas in magnesium hydroxide produced by an ammonia method. The study promotes energy conservation, emission reduction and low-carbon economy, and realizes great environmental benefits, social benefits and economic benefits.
Description
Denomination of invention
The ammonium chloride circulation method is produced magnesium hydroxide and calcium chloride by carbide slag and salt lake magnesium chloride
1 technical field
Trade waste recycling field.
The present invention is for taking full advantage of carbide slag and salt lake magnesium chloride, from the technique of two aspect design synthesis development and use: the first, ammonium chloride circulation method hydrogen manufacturing magnesium oxide; The second, the recovery of by product calcium chloride.
2 background technologies
One, product introduction
Carbide slag is the waste that produces in the calcium carbide legal system acetylene process.Every consumption 1t calcium carbide will produce the carbide slag about 1.5tz.The main component of carbide slag is Ca (OH)
2, its content is up to more than 85%, because the impurity level that carbide slag contains is more, composition is more complicated again, thereby makes carbide slag can not obtain high-value-use.
Traditional Comprehensive Utilization of Bittern Resources is main mainly with sylvite, and the magnesium chloride resource of annual discharging reaches more than 1,500 ten thousand t, and main with low value-added bischofite products production and sale, annual production is only about 300,000 t.A large amount of magnesium salts generally take remote discharging modes to flow back to the salt lake, still do not form so far large-scale business development utilization, even have caused salt lake composition variation to form " magnesium evil ".Accelerate the comprehensive utilization of salt lake magnesium resource, it is significant to realizing rationally utilizing of salt lake resources especially to prepare the magnesium-based products with high added value.
The method of utilizing the making from brine magnesium hydroxide of report mainly contains three kinds at present: bittern-soda processes, bittern-milk of lime process, bittern-Ammonia Process.The magnesium hydroxide products quality of producing with bittern-Ammonia Process in these three kinds of methods is the highest.But the ammonia utilization ratio of bittern-Ammonia Process is lower.Wu Xiangfeng etc. carry potassium mother liquor bittern and are raw material take the salt lake, after the purified processing, take industrial ammonia as precipitation agent, adopt direct precipitation method under normal temperature condition, made particle diameter less and be evenly distributed, the flake magnesium hydroxide powder body material of favorable dispersity.Product cut size is about 500nm and be evenly distributed, and better dispersed, pyrolysis temperature is between 340-480 ℃.Duan Yingfeng, Yuan Jianjun etc. determine that the logical ammonia of bittern prepares magnesium hydroxide optimum processing condition and is: ammonia flow 0.3m by the experimental study to several aspects such as logical ammonia react time, stir speed (S.S.), Aging Temperature and digestion times
3/ h, when mixing speed was 150r/min, behind the logical ammonia react 30min, reaction residual liquor is ageing 35min in 50 ℃ of water-baths.The magnesium transformation efficiency is more stable.Guo Shuyuan, the optimum of the synthetic filter cake shape magnesium hydroxide of the bittern ammonia process such as Zhang Yushan is: reaction 40min when temperature of reaction is 20 ℃, be warming up to 70 ℃ of ageing 60min, the dripping quantity of the ammoniacal liquor theoretical consumption more required than magnesium ion in the bittern exceeds about 65% (mol ratio), prepared filter cake shape magnesium hydroxide products is better, and the transformation efficiency of magnesium ion reaches more than 95%.
The patent application of Chen Baoyue etc. (CN03112355.4 technology of producing modified magnesium hydroxide) discloses a kind of technology of producing modified magnesium hydroxide.Determined rational bittern: the ammoniacal liquor material ratio is 1: 0.9-0.95,38 ℃-42 ℃ of rational temperature of reaction and 3 hours-5 hours reaction times have been determined, in the magnesium hydroxide that generates, the 1.5-3% such as the properties-correcting agent-silane coupling agent that brings Selection In, through washing, filtration, dry, pulverizing, make qualified modified magnesium hydroxide finished product again.The Shen patent application of Li Guoxiang etc. (CN02107661.8 ammonia total recycle process is produced magnesium hydroxide and magnesian technique), its technique enters the extraction distillation column bottom and carries out the parallel distillation of extractive reaction for containing after MgO raw material and ammonium liquid are sized mixing, the ammonia that produces and steam steam to the tower middle part and will enter tower top after the ammonia concentrate, enter supercharging blower as the building-up reactions raw material through ammonium liquid preheater and condenser.Discharging ammonia that magnesium liquid comes with supercharging blower after separation, impurity removal matter under the tower synthesizes and makes Mg (OH)
2, MgO after the roasting; By Mg (OH)
2The ammonium liquid that separates recycles as extraction liquid.The patent application of Shandong Haihua Group Co., Ltd (method of CN 01127343.7 One-step production magnesium hydroxide); the bittern that will contain magnesium chloride is 1 according to magnesium chloride with the mol ratio of free ammonia with ammoniacal liquor: the ratio of 1.3-2.0 is mixed; and mixture was reacted 5-30 minute in the environment that 45 degree-90 Celsius are spent, will obtain solid hydrogen magnesium oxide after the filtration of reaction solution process, washing, drying, the pulverizing.The patent application of Song Yunhua etc. (01141787.0 1 kinds of preparation process of magnesium hydroxide fire-retarding nanomaterial of CN), utilize purified magnesium chloride solution that old bittern or magnesite obtains and industrial ammonia or ammonia to be raw material, perhaps utilize Adlerika and industrial ammonia or ammonia to be raw material, adopt hypergravity (rotating packed bed) technology, utilize liquid-liquid phase reaction or gas and liquid phase reactive mode, the preparation magnesium hydroxide fire-retarding nanomaterial.The patent application of Xu Jiujun etc. (method of CN200810010336.0 liquefied ammonia ammoniacal liquor duplex deposition of high-purity magnesium hydroxide), the method of producing continuously high purity magnesium hydroxide as precipitation agent take bischofite as raw material, take ammonia and ammoniacal liquor, bischofite after treatment is mixed with 0.5mol/L～4.5mol/L solution, the initial reaction stage precipitation agent is provided by ammonia, then precipitation agent is provided by the ammoniacal liquor of reaction product ammonium chloride recovery, ammonia replenishes surplus, reaction process is carried out continuously, also can be interrupted and carry out.Can obtain granularity between 10 microns-100 microns, the magnesium hydroxide of purity between 99%-99.999%.Product ammonium chloride adopts alkali decomposition additive, vacuum jet to inhale ammonia and reclaims ammonia, preparation ammoniacal liquor and recycle.
.3 summary of the invention
3.1 ammonium chloride circulation method hydrogen manufacturing magnesium oxide
Main production comprises: with carbide slag process high-temperature heating treatment and grinding, the salt lake magnesium chloride is through dissolving, remove by filter water-insoluble, filtrate is passed through evaporating, concentrating and crystallizing purification 2-3 time again, and the magnesium chloride of purifying is mixed with certain density magnesium chloride solution.The reaction under 85-100 ℃ with pretreated excessive carbide slag and certain density ammonium chloride solution, the ammonia that generates is passed in the certain density magnesium chloride solution, behind the reaction certain hour, generate the magnesium hydrate precipitate of white, precipitation namely gets magnesium hydroxide products through operations such as ageing, centrifugal, washing, drying, pulverizing.
3.2 the recovery of ammonium chloride recycle and by product calcium chloride
Filtrate behind the filtration magnesium hydroxide magnesium is through heating, the ammonia that produces directly passes into and participates in reaction in the magnesium chloride solution, contain the higher ammonium chloride of concentration in the filtrate after concentrated, react in this ammonium chloride solution carbide slag that adding is handled well again after concentrated, thus the recycle of formation ammonium chloride.Take to react in encloses container, can solve ammonia fully to the pollution problem of environment, ammonium chloride also has higher cycling rate.
Contain a large amount of calcium chloride in the filtrate after excessive carbide slag and ammonium chloride react completely, because filtrate is alkalescence, other ions such as Fe
2+, Cu
2+, Mg
2+Deng being insoluble in the filtrate, only has the higher calcium chloride of content in the filtrate.Excessive carbide slag slurry is filtered, and filtrate namely gets technical grade calcium chloride through operations such as decolouring, concentrated, crystallization, drying, pulverizing.
4 embodiments
4.1 ammonium chloride circulation method hydrogen manufacturing magnesium oxide
Carbide slag is through 100-105 ℃ of dry 2-3h, and recycling ball mill ball milling or pulverizer pulverizing are for subsequent use by the above sieve of 100 orders for fineness.Get the moisture MgCl in a certain amount of salt lake
2, adding an amount of distilled water and be heated to boil-off solution, the concentrated decrease temperature crystalline of decompress filter, filtrate while hot, a small amount of cold distilled water wash crystallization 2-3 time obtains purification of chlorinated magnesium.With the MgCl behind the recrystallization
2Being mixed with concentration is 2.0-2.5molL
-1MgCl
2Solution for standby.Get the excessive carbide slag and the NH that handle well
4Cl (mol ratio is 1.05: 2-1.2: 2) is at 85-95 ℃ of lower reaction NH processed
3, according to NH
4Cl and MgCl
2Molar ratio be 5.0 to prepare NH
3With NH
3Directly or first be stored in the ammonia tank and then pass into 20-30 ℃ MgCl
2In the solution, 40-60min is stirred in insulation, generates white Mg (OH)
2The precipitation, normal temperature ageing 2-3h, centrifugal after, use distilled water wash, be washed till in the filtrate without Cl
-Till (drip AgNO
3Solution is without obvious sediment), at 90-105 ℃ of dry 3-4h, get Mg (OH) through grinding again
2Mg (OH)
2Production rate can reach 89.08%.
4.2 the recovery of ammonium chloride recycle and by product calcium chloride
Filter Mg (OH)
2After filtrate in have a large amount of unreacted free ammonias and resultant ammonium chloride, at first solution is heated to 95-100 ℃, with NH
3Steam (the NH that steams
3Can again pass into and MgCl
2Produce Mg (OH) in the solution
2)).To steam NH
3/ 2nd to 1/3rd of a rear filtrate simmer down to original volume adds the recycle of carrying out a new round behind excessive carbide slag and the additional partial oxidation ammonium again.
Carbide slag and NH
4In the reacted filtrate of Cl a large amount of CaCl are arranged
2, because excessive alkalescence, the Fe in the carbide slag of being of carbide slag in the system
2+, Al
3+, SiO
2Be insoluble to basic solution Deng impurity, so only have CaCl in the filtrate
2With the reacted product of carbide slag after filtering, add a small amount of sodium sulphite removal of impurities in filtrate, again filter, filtrate is cooled to normal temperature through reduction vaporization after having a large amount of calcium chloride crystal to separate out, and decompress filter with a small amount of distilled water wash 1-2 time, obtains CaCl
2, at 105 ℃ of lower dry 2h, then be transferred in the cabinet-type electric furnace and continue dryly down at 260-300 ℃, till being dried to weight and no longer changing, obtain anhydrous CaCl
2
Claims (2)
1. ammonium chloride circulation method hydrogen manufacturing magnesium oxide: main production comprises: with carbide slag through high temperature and grinding pre-treatment, the salt lake magnesium chloride through thermosol, remove by filter water-insoluble, filtrate is mixed with certain density magnesium chloride solution through evaporating, concentrating and crystallizing purification 2-3 time with the magnesium chloride of purifying; The reaction under 85-100 ℃ with pretreated excessive carbide slag and certain density ammonium chloride solution, the ammonia that generates is passed in the certain density magnesium chloride solution, behind the reaction certain hour, generate white magnesium hydrate precipitate, precipitation namely gets magnesium hydroxide products through operations such as centrifugal, washing, drying, pulverizing.
2. the recovery of ammonium chloride recycle and by product calcium chloride: will filter filtrate behind the magnesium hydroxide magnesium through heating, the ammonia that produces passes into and participates in reaction in the magnesium chloride solution, through containing the higher ammonium chloride of concentration in the filtrate after concentrated, this ammonium chloride solution again adds in the carbide slag after the processing and reacts, thereby forms the recycle of ammonium chloride; Take to react in encloses container, can solve ammonia fully to the pollution problem of environment, ammonium chloride also has higher cycling rate; Contain a large amount of calcium chloride in the filtrate after excessive carbide slag and ammonium chloride react completely, because filtrate is alkalescence, other ions such as Fe
2+, Cu
2+, Mg
2+Deng being insoluble in the filtrate, so only have the higher calcium chloride of content in the filtrate; Excessive carbide slag slurry is filtered, and filtrate namely gets technical grade calcium chloride through operations such as decolouring, concentrated, crystallization, drying, pulverizing.
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| CN2011102894471A CN103011209A (en) | 2011-09-23 | 2011-09-23 | Ammonium chloride circulation method for producing magnesium hydroxide and calcium chloride from carbide slag and salt lake magnesium chloride |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104071813A (en) * | 2014-07-08 | 2014-10-01 | 中国科学院青海盐湖研究所 | Method for preparing magnesium hydroxide |
| CN104071804A (en) * | 2014-07-08 | 2014-10-01 | 中国科学院青海盐湖研究所 | Method for preparing ammonium chloride |
| CN104261442A (en) * | 2014-07-08 | 2015-01-07 | 云天化集团有限责任公司 | Method for preparing magnesium hydroxide |
| CN110240185A (en) * | 2019-07-02 | 2019-09-17 | 天津渤化工程有限公司 | The production method of high purity magnesium hydroxide |
| CN115321565A (en) * | 2022-08-03 | 2022-11-11 | 国投新疆罗布泊钾盐有限责任公司 | Method for preparing nano magnesium hydroxide by taking salt lake brine as raw material |
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| US4720375A (en) * | 1984-11-27 | 1988-01-19 | Sulzer Brothers Limited | Process for producing magnesium oxide |
| CN101020579A (en) * | 2006-03-27 | 2007-08-22 | 中国人民解放军国防科学技术大学 | Process of preparing high purity light calcium carbonate fine powder with carbide residue |
| CN101475197A (en) * | 2009-01-09 | 2009-07-08 | 中国科学院青海盐湖研究所 | Method for preparing ultra-fine high dispersing magnesium hydrate flame retardant from saline lake bittern or bischofite |
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| US4720375A (en) * | 1984-11-27 | 1988-01-19 | Sulzer Brothers Limited | Process for producing magnesium oxide |
| CN101020579A (en) * | 2006-03-27 | 2007-08-22 | 中国人民解放军国防科学技术大学 | Process of preparing high purity light calcium carbonate fine powder with carbide residue |
| CN101475197A (en) * | 2009-01-09 | 2009-07-08 | 中国科学院青海盐湖研究所 | Method for preparing ultra-fine high dispersing magnesium hydrate flame retardant from saline lake bittern or bischofite |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104071813A (en) * | 2014-07-08 | 2014-10-01 | 中国科学院青海盐湖研究所 | Method for preparing magnesium hydroxide |
| CN104071804A (en) * | 2014-07-08 | 2014-10-01 | 中国科学院青海盐湖研究所 | Method for preparing ammonium chloride |
| CN104261442A (en) * | 2014-07-08 | 2015-01-07 | 云天化集团有限责任公司 | Method for preparing magnesium hydroxide |
| CN110240185A (en) * | 2019-07-02 | 2019-09-17 | 天津渤化工程有限公司 | The production method of high purity magnesium hydroxide |
| CN115321565A (en) * | 2022-08-03 | 2022-11-11 | 国投新疆罗布泊钾盐有限责任公司 | Method for preparing nano magnesium hydroxide by taking salt lake brine as raw material |
| CN115321565B (en) * | 2022-08-03 | 2023-10-13 | 国投新疆罗布泊钾盐有限责任公司 | Method for preparing nano magnesium hydroxide by taking salt lake brine as raw material |
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Application publication date: 20130403 |