CN102303879B - Method for preparing magnesium hydroxide by utilizing light calcined dolomite - Google Patents
Method for preparing magnesium hydroxide by utilizing light calcined dolomite Download PDFInfo
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Abstract
The invention relates to a method for preparing magnesium hydroxide by utilizing light calcined dolomite. The method comprises the following steps: firstly, preparing magnesium nitrate or magnesium chloride into a 0.1-4 mol/L solution; adding organic amine in the solution, and evenly stirring; reacting for 0.5-2 hours at the temperature of 10 DEG C-100 DEG C, and then filtering; and washing and drying filter residue so as to obtain magnesium hydroxide, and entering filtrate into a cycle process. The method has the advantages that 1) production raw material cost is reduced; 2) energy consumption is low, and amine can be separated from the solution through a liquid separation method, thereby avoiding the ammonia distillation operation in an ammonia-soda process and simultaneously avoiding the pollution of ammonia volatilization to environment; and 3) operation cost is low, magnesium hydroxide is precipitated with organic amine so that a certain amount of organic amine is adsorbed when magnesium hydroxide is generated, thus magnesium hydroxide has the hydrophobic characteristic, the filtration speed of magnesium hydroxide is extremely high when filtration is carried out, the filtration speed is larger than 0.01 L/s.m<2>, and magnesium hydroxide is easy to wash, thus the operation cost of the process is reduced.
Description
Technical field
The present invention relates to a kind of method of utilizing light dolomite to prepare magnesium hydroxide, belong to field of inorganic chemical engineering.
Background technology
Magnesium hydroxide is a kind of white indissoluble powder, is widely used in PE, PP, PVC, ABS, PS, HIPS, PA, PBT, unsaturated polyester, epoxy resin, rubber, the flame retardant filler of paint; As the flue gas desulfurization (FGD) agent, can replace caustic soda and lime as the neutralizing agent of acid-bearing wastewater aspect environmental protection; As oil dope, play anticorrosion and desulfidation; Be used for the refining of electron trade, medicine, granulated sugar; Be used for lagging material and make other magnesium salts product.
Utilize at present light dolomite to have much for the report that raw material prepares magnesium hydroxide, the technique that industrialization is the most successful is carborization, its main technique is first to prepare heavy magnesium water, then pyrolysis preparing light magnesium carbonate with heavy magnesium water, the pyrolysis Magnesium Carbonate Light 41-45 prepares magnesium oxide, the magnesium oxide aquation can get magnesium hydroxide, this processes cost is higher, operational path is longer, utilize in addition ammonium salt first extract calcium oxide and prepare calcium carbonate with the calcium oxide reaction, remaining solid is magnesium oxide, but this technique gained magnesium oxide purity is relatively poor.How light dolomite realizes that as a kind of calcium oxide and magnesian mixture cheap calcium magnesium is separated into a key issue.
Light dolomite usable acid after isolating calcium oxide prepares inorganic soluble magnesium salts solution, at present, the preparation method who uses inorganic soluble magnesium salts solution to prepare magnesium hydroxide mainly contains sodium hydroxide method, solvay soda process and calcium oxide method, the sodium hydroxide method cost is high, the filtration washing difficulty, solvay soda process ammonia internal circulating load is large, and energy consumption is high and the ammonia loss amount is large, equally also there is the filtration washing hard problem in the calcium oxide method, can't prepare high purity magnesium hydrate.Therefore especially as a kind of inorganic combustion inhibitor of excellent property, the market share that magnesium hydroxide occupies is always very low, and its basic reason is that production cost is high, complex process, and novel synthetic method and operational path are the active demand of market institute.
Organic amine as a kind of alkali when the precipitate metal ion and the mineral alkalis such as sodium hydroxide, calcium hydroxide and ammoniacal liquor be all the effect that OH-is provided, but the organic amine price is more expensive, so industrial precipitate metal ion that generally is rarely used in, unless the method for rational recovery organic amine is arranged, the good grade of shaking about 1992 has been reported " thermodynamics of Carbonates Manufacture by Tertiary Amine Method ", but mentioned the tertiary amine absorbing carbon dioxide, in addition, also have numerous documents and patent report organic amine such as diethanolamine, trolamine to be used for reclaiming the carbonic acid gas of industrial tail gas.The utilization of above organic amine is because the volatility of organic amine is less than ammonia, during absorbing carbon dioxide the amine loss little, and organic amine is the larger amine of water solubility, and can recycle in the aqueous solution.
Summary of the invention
Purpose of the present invention provides a kind of method of utilizing light dolomite to prepare magnesium hydroxide, its utilize the water microsolubility of organic amine realize amine moisture from, make the amine can recycle, effectively reduce the use cost of organic amine.
The present invention solves the problems of the technologies described above the technical scheme that adopts: utilize light dolomite to prepare the method for magnesium hydroxide, it is characterized in that at first magnesium nitrate or magnesium chloride are mixed with the solution of 0.1～4mol/L, then organic amine is joined in solution, stirring, is to react 0.5～2 hour under 10 ℃～100 ℃ conditions in temperature, then filters, get filter residue A and filtrate A, filter residue A obtains magnesium hydroxide through washing and drying, and filtrate A enters working cycle, and described working cycle step is:
1) reduction of amine: with filtrate A and light dolomite mix and blend, at 10 ℃～100 ℃ conditioned responses 0.5～2 hour, standing separatory, the organic amine of separation is standby, and remaining water solidliquid mixture obtains liquor B and filter residue B after filtration;
2) separation of calcium: the vitriol oil is slowly joined in liquor B, stir, then cooling filters, and gets filter residue C and liquor C, and filter residue C is through washing to get plaster stone, and liquor C is standby;
3) preparation of inorganic soluble magnesium salts solution: after liquor C and filter residue B hybrid reaction, filter, get filtrate D and filter residue D, filtrate D is inorganic soluble magnesium salts solution, and filter residue D abandons;
4) preparation of magnesium hydroxide: with step 1) separate the organic amine that obtains and join in filtrate D, stir, be to react 0.5～2 hour under 10 ℃～100 ℃ conditions in temperature, then filter, the gained filter residue is through washing and the dry magnesium hydrate powder that gets, and gained filtrate A is recycled and reused for step 1).
Press such scheme, described light dolomite raw material is for containing calcium oxide and magnesian mixture, and the mol ratio of calcium oxide and magnesium elements is 1.5～1: between 1.
Press such scheme, described inorganic soluble magnesium salts solution is that volumetric molar concentration is 0.1～4mol/L magnesium nitrate or magnesium chloride brine.It can be prepared by the light dolomite raw material.
Press such scheme, described organic amine is liquid under normal pressure, 10 ℃～100 ℃ conditions, under standard conditions, and acid dissociation constant pKa=10～11.5.
Press such scheme, described organic amine is a kind of or several mixing arbitrarily in Di-n-Butyl Amine, two n-amylamines, normal hexyl Amine and two normal hexyl Amines, and in the consumption of organic amine and light dolomite raw material, the mol ratio of contained magnesium elements amount is 2～2.4: 1.
Press such scheme, described vitriol oil consumption is 1-1.5 for the mol ratio of the organic amine in its sulfate radical content and working cycle: 2.
Present method technique is simple, and is easy to operate, cheap, can prepare high purity, and the magnesium hydroxide that easily filters.The magnesium hydroxide of present method preparation can be used for a plurality of fields such as chemical industry, environmental protection, food, medical treatment.
Raw material magnesium nitrate used in the present invention or magnesium chloride be used for to start technological cycle as initial feed, and need the loss of chlorion in the replenishment cycles process or nitrate ion.
Chemical equation involved in the present invention is as follows:
CaOMgO+2R
3NHX → CaX
2+ 2R
3N (but separatory)+H
2O+MgO
CaX
2+H
2SO
4→CaSO
4↓+2HX
MgO+2HX＝MgX
2+H
2O
MgX
2+2R
3N+2H
2O→Mg(OH)
2↓+2R
3NHX
X=Cl wherein
-Or NO
3 -, R=H, alkyl, but R can not be all H or alkyl.
The magnesium hydroxide heating dehydration of gained of the present invention is got final product to get high-purity magnesium oxide.
The preparation method of magnesium hydroxide provided by the present invention compares with traditional method, has the following advantages: 1) cost is low, and organic amine recycles as precipitation agent, and the amine internal circulating load is little simultaneously, and deposition efficiency is high, has reduced the raw materials for production cost; 2) energy consumption is low, and amine can separate by the method for separatory with solution, has avoided the ammonia still process operation in the solvay soda process, has also avoided the pollution of ammonia volatilization to environment simultaneously; 3) process cost is low, and the method organic amine precipitated magnesium hydroxide makes magnesium hydroxide certain organic amine of absorption when generating, thereby has hydrophobic property, and when filtering, filtration velocity is very fast, and filtration velocity is greater than 0.01L/sm
2, and easily wash, reduced the process cost of technique.
Description of drawings
Fig. 1 is the process flow diagram of preparation magnesium hydroxide of the present invention;
Fig. 2 is the scanning electron microscope (SEM) photograph of the magnesium hydroxide of embodiment 1 gained, and on figure, signify hydrogen magnesium oxide is sheet, and size distribution is even, between 0.1-5 μ m.
Embodiment
The present invention will be further described in detail below in conjunction with drawings and Examples.
Embodiment 1
Raw material used in the present invention has 1 part of a. light dolomite raw material, measures calcium, magnesium ion content in raw material before using, and the mol ratio of calcium oxide and magnesium elements was at 1: 1 after measured, and the amount that calcium oxide and magnesium oxide use is 1mol; B. organic amine is 1 part, and organic amine is Di-n-Butyl Amine, and in the consumption of 1 part of organic amine and 1 part of light dolomite raw material, the mol ratio of contained magnesium elements amount is 2.1: 1, uses the amount of organic amine to be 2.1mol; C. sulfuric acid, 1 part, measure sulfate radical content in raw material before using, the mol ratio of the organic amine in its sulfate radical content and working cycle is 1: 2 after measured, usage quantity is 1.05mol; D. magnesium nitrate is 1 part, and amount used is 1mol.Magnesium nitrate be used for to start technological cycle as initial feed, and the loss of nitrate ion in the replenishment cycles process.
at first the setting up procedure of technological cycle of the present invention for being mixed with magnesium nitrate the solution of 1mol/L, then organic amine is joined in solution, stir, be to react 0.5 hour under 20 ℃ of conditions in temperature, then filter, get filter residue A and filtrate A, filter residue A obtains magnesium hydroxide through washing and drying, filtrate A enters working cycle, described working cycle step is: the 1) reduction of amine: with filtrate A (being the nitric acid dibutylamine aqueous solution) and light dolomite mix and blend, 20 ℃ of conditioned responses 2 hours, standing separatory, the organic amine that separates is standby, remaining water solidliquid mixture after filtration, obtain liquor B (being ca nitrate soln) and filter residue B (being the magnesium oxide solid), 2) separation of calcium: the vitriol oil is slowly joined in liquor B, stir, then cooling filters, and gets filter residue C (being plaster stone) and liquor C (being salpeter solution), and filter residue is through washing to get plaster stone, and liquor C is standby, 3) preparation of inorganic soluble magnesium salts solution: after liquor C and filter residue B hybrid reaction, filter, get filtrate D (being magnesium nitrate solution) and filter residue D (being the acid non-soluble substance impurity in light dolomite), filter residue D abandons, 4) preparation of magnesium hydroxide: with step 1) separate the organic amine that obtains and join in filtrate D, stirring, is to react 0.5 hour under 20 ℃ of conditions in temperature, then filters, the gained filter residue is through washing and the dry magnesium hydrate powder that gets, and gained filtrate A is recycled and reused for step 1).
Get magnesium hydroxide 53.3 grams through above-mentioned steps, yield is 90%, and purity is 98%, and the heating dehydration can get high-purity magnesium oxide.Fig. 2 is the scanning electron microscope (SEM) photograph of the magnesium hydroxide of embodiment 1 gained, and on figure, signify hydrogen magnesium oxide is sheet, and size distribution is even, between 0.1-5 μ m.
Embodiment 2
Raw material used in the present invention has 1 part of a. light dolomite raw material, measures calcium, magnesium ion content in raw material before using, and the mol ratio of calcium oxide and magnesium elements was at 1.5: 1 after measured, and the amount that calcium oxide and magnesium oxide use is respectively 1.5mol, 1mol; B. organic amine is 1 part, and organic amine is normal hexyl Amine, and in the consumption of 1 part of organic amine and 1 part of light dolomite raw material, the mol ratio of contained magnesium elements amount is 2.4: 1, uses the amount of organic amine to be 2.4mol; C. sulfuric acid, 1 part, measure sulfate radical content in raw material before using, the mol ratio of the organic amine in its sulfate radical content and working cycle is 1.5: 2 after measured, usage quantity is 1.8mol; D. magnesium nitrate is 1 part, and amount used is 1mol.Magnesium nitrate be used for to start technological cycle as initial feed, and the loss of nitrate ion in the replenishment cycles process.
at first the setting up procedure of technological cycle of the present invention for being mixed with magnesium nitrate the solution of 4mol/L, then organic amine is joined in solution, stir, be to react 2 hours under 70 ℃ of conditions in temperature, then filter, get filter residue A and filtrate A, filter residue A obtains magnesium hydroxide through washing and drying, filtrate A enters working cycle, described working cycle step is: the 1) reduction of amine: with filtrate A (being the nitric acid normal hexyl Amine aqueous solution) and light dolomite mix and blend, 60 ℃ of conditioned responses 2 hours, standing separatory, the organic amine that separates is standby, remaining water solidliquid mixture after filtration, obtain liquor B (being ca nitrate soln) and filter residue B (being the magnesium oxide solid), 2) separation of calcium: the vitriol oil is slowly joined in liquor B, stir, then cooling filters, and gets filter residue C (being plaster stone) and liquor C (being salpeter solution), and filter residue is through washing to get plaster stone, and liquor C is standby, 3) preparation of inorganic soluble magnesium salts solution: after liquor C and filter residue B hybrid reaction, filter, get filtrate D (being magnesium nitrate solution) and filter residue D (being the acid non-soluble substance impurity in light dolomite), filter residue D abandons, 4) preparation of magnesium hydroxide: with step 1) separate the organic amine that obtains and join in filtrate D, stirring, is to react 2 hours under 70 ℃ of conditions in temperature, then filters, the gained filter residue is through washing and the dry magnesium hydrate powder that gets, and gained filtrate A is recycled and reused for step 1).
Get magnesium hydroxide 54 grams through above-mentioned steps, yield is 93%, and purity is 98%, and the heating dehydration can get high-purity magnesium oxide.
Embodiment 3
Raw material used in the present invention has 1 part of a. light dolomite raw material, measures calcium, magnesium ion content in raw material before using, and the mol ratio of calcium oxide and magnesium elements was at 1.2: 1 after measured, and the amount that calcium oxide and magnesium oxide use is respectively 1.2mol, 1mol; B. organic amine is 1 part, and organic amine is two n-amylamines, and in the consumption of 1 part of organic amine and 1 part of light dolomite raw material, the mol ratio of contained magnesium elements amount is 2.2: 1, uses the amount of organic amine to be 2.2mol; C. sulfuric acid, 1 part, measure sulfate radical content in raw material before using, the mol ratio of the organic amine in its sulfate radical content and working cycle is 1.3: 2 after measured, usage quantity is 1.43mol; D. magnesium nitrate is 1 part, and amount used is 1mol.Magnesium nitrate be used for to start technological cycle as initial feed, and the loss of nitrate ion in the replenishment cycles process.
at first the setting up procedure of technological cycle of the present invention for being mixed with magnesium nitrate the solution of 0.1mol/L, then organic amine is joined in solution, stir, be to react 1 hour under 40 ℃ of conditions in temperature, then filter, get filter residue A and filtrate A, filter residue A obtains magnesium hydroxide through washing and drying, filtrate A enters working cycle, described working cycle step is: the 1) reduction of amine: with filtrate A (being the nitric acid two n-amylamine aqueous solution) and light dolomite mix and blend, 30 ℃ of conditioned responses 2 hours, standing separatory, the organic amine that separates is standby, remaining water solidliquid mixture after filtration, obtain liquor B (being ca nitrate soln) and filter residue B (being the magnesium oxide solid), 2) separation of calcium: the vitriol oil is slowly joined in liquor B, stir, then cooling filters, and gets filter residue C (being plaster stone) and liquor C (being salpeter solution), and filter residue is through washing to get plaster stone, and liquor C is standby, 3) preparation of inorganic soluble magnesium salts solution: after liquor C and filter residue B hybrid reaction, filter, get filtrate D (being magnesium nitrate solution) and filter residue D (being the acid non-soluble substance impurity in light dolomite), filter residue D abandons, 4) preparation of magnesium hydroxide: with step 1) separate the organic amine that obtains and join in filtrate D, stirring, is to react 1 hour under 40 ℃ of conditions in temperature, then filters, the gained filter residue is through washing and the dry magnesium hydrate powder that gets, and gained filtrate A is recycled and reused for step 1).
Get magnesium hydroxide 53 grams through above-mentioned steps, yield is 89%, and purity is 98%, and the heating dehydration can get high-purity magnesium oxide.
Embodiment 4
Raw material used in the present invention has 1 part of a. light dolomite raw material, measures calcium, magnesium ion content in raw material before using, and the mol ratio of calcium oxide and magnesium elements was at 1.3: 1 after measured, and the amount that calcium oxide and magnesium oxide use is respectively 1.3mol, 1mol; B. organic amine is 1 part, and organic amine is two normal hexyl Amines, and in the consumption of 1 part of organic amine and 1 part of light dolomite raw material, the mol ratio of contained magnesium elements amount is 2.3: 1, uses the amount of organic amine to be 2.3mol; C. sulfuric acid, 1 part, measure sulfate radical content in raw material before using, the mol ratio of the organic amine in its sulfate radical content and working cycle is 1.2: 2 after measured, usage quantity is 1.38mol; D. magnesium nitrate is 1 part, and amount used is 1mol.Magnesium nitrate be used for to start technological cycle as initial feed, and the loss of nitrate ion in the replenishment cycles process.
at first the setting up procedure of technological cycle of the present invention for being mixed with magnesium nitrate the solution of 1.5mol/L, then organic amine is joined in solution, stir, be to react 0.5 hour under 65 ℃ of conditions in temperature, then filter, get filter residue A and filtrate A, filter residue A obtains magnesium hydroxide through washing and drying, filtrate A enters working cycle, described working cycle step is: the 1) reduction of amine: with filtrate A (being the nitric acid two normal hexyl Amine aqueous solution) and light dolomite mix and blend, 45 ℃ of conditioned responses 2 hours, standing separatory, the organic amine that separates is standby, remaining water solidliquid mixture after filtration, obtain liquor B (being ca nitrate soln) and filter residue B (being the magnesium oxide solid), 2) separation of calcium: the vitriol oil is slowly joined in liquor B, stir, then cooling filters, and gets filter residue C (being plaster stone) and liquor C (being salpeter solution), and filter residue is through washing to get plaster stone, and liquor C is standby, 3) preparation of inorganic soluble magnesium salts solution: after liquor C and filter residue B hybrid reaction, filter, get filtrate D (being magnesium nitrate solution) and filter residue D (being the acid non-soluble substance impurity in light dolomite), filter residue D abandons, 4) preparation of magnesium hydroxide: with step 1) separate the organic amine that obtains and join in filtrate D, stirring, is to react 0.5 hour under 65 ℃ of conditions in temperature, then filters, the gained filter residue is through washing and the dry magnesium hydrate powder that gets, and gained filtrate A is recycled and reused for step 1).
Get magnesium hydroxide 55 grams through above-mentioned steps, yield is 94%, and purity is 98%, and the heating dehydration can get high-purity magnesium oxide.
Embodiment 5
Raw material used in the present invention has 1 part of a. light dolomite raw material, measures calcium, magnesium ion content in raw material before using, and the mol ratio of calcium oxide and magnesium elements was at 1: 1 after measured, and the amount that calcium oxide and magnesium oxide use is 1mol; B. organic amine is 1 part, and organic amine is Di-n-Butyl Amine, and in the consumption of 1 part of organic amine and 1 part of light dolomite raw material, the mol ratio of contained magnesium elements amount is 2.1: 1, uses the amount of organic amine to be 2.1mol; C. sulfuric acid, 1 part, measure sulfate radical content in raw material before using, the mol ratio of the organic amine in its sulfate radical content and working cycle is 1: 2 after measured, usage quantity is 1.05mol; D. magnesium chloride is 1 part, and amount used is 1mol.Magnesium chloride be used for to start technological cycle as initial feed, and the loss of chlorion in the replenishment cycles process.
at first the setting up procedure of technological cycle of the present invention for being mixed with magnesium chloride the solution of 0.5mol/L, then organic amine is joined in solution, stir, be to react 1 hour under 20 ℃ of conditions in temperature, then filter, get filter residue A and filtrate A, filter residue A obtains magnesium hydroxide through washing and drying, filtrate A enters working cycle, described working cycle step is: the 1) reduction of amine: with filtrate A (being the chlorination Di-n-Butyl Amine aqueous solution) and light dolomite mix and blend, 40 ℃ of conditioned responses 2 hours, standing separatory, the organic amine that separates is standby, remaining water solidliquid mixture after filtration, obtain liquor B (being calcium chloride solution) and filter residue B (being the magnesium oxide solid), 2) separation of calcium: the vitriol oil is slowly joined in liquor B, stir, then cooling filters, and gets filter residue C (being plaster stone) and liquor C (being hydrochloric acid soln), and filter residue is through washing to get plaster stone, and liquor C is standby, 3) preparation of inorganic soluble magnesium salts solution: after liquor C and filter residue B hybrid reaction, filter, get filtrate D (being magnesium chloride solution) and filter residue D (being the acid non-soluble substance impurity in light dolomite), filter residue D abandons, 4) preparation of magnesium hydroxide: with step 1) separate the organic amine that obtains and join in filtrate D, stirring, is to react 1 hour under 20 ℃ of conditions in temperature, then filters, the gained filter residue is through washing and the dry magnesium hydrate powder that gets, and gained filtrate A is recycled and reused for step 1).
Get magnesium hydroxide 54 grams through above-mentioned steps, yield is 91%, and purity is 98%, and the heating dehydration can get high-purity magnesium oxide.
Embodiment 6
Raw material used in the present invention has 1 part of a. light dolomite raw material, measures calcium, magnesium ion content in raw material before using, and the mol ratio of calcium oxide and magnesium elements was at 1.5: 1 after measured, and the amount that calcium oxide and magnesium oxide use is respectively 1.5mol, 1mol; B. organic amine is 1 part, and organic amine is normal hexyl Amine, and in the consumption of 1 part of organic amine and 1 part of light dolomite raw material, the mol ratio of contained magnesium elements amount is 2.4: 1, uses the amount of organic amine to be 2.4mol; C. sulfuric acid, 1 part, measure sulfate radical content in raw material before using, the mol ratio of the organic amine in its sulfate radical content and working cycle is 1.3: 2 after measured, the amount of using is 1.56mol; D. magnesium chloride is 1 part, and amount used is 1mol.Magnesium chloride be used for to start technological cycle as initial feed, and the loss of chlorion in the replenishment cycles process.
at first the setting up procedure of technological cycle of the present invention for being mixed with magnesium chloride the solution of 0.1mol/L, then organic amine is joined in solution, stir, be to react 1 hour under 60 ℃ of conditions in temperature, then filter, get filter residue A and filtrate A, filter residue A obtains magnesium hydroxide through washing and drying, filtrate A enters working cycle, described working cycle step is: the 1) reduction of amine: with filtrate A (being the chlorination normal hexyl Amine aqueous solution) and light dolomite mix and blend, 30 ℃ of conditioned responses 2 hours, standing separatory, the organic amine that separates is standby, remaining water solidliquid mixture after filtration, obtain liquor B (being calcium chloride solution) and filter residue B (being the magnesium oxide solid), 2) separation of calcium: the vitriol oil is slowly joined in liquor B, stir, then cooling filters, and gets filter residue C (being plaster stone) and liquor C (being hydrochloric acid soln), and filter residue is through washing to get plaster stone, and liquor C is standby, 3) preparation of inorganic soluble magnesium salts solution: after liquor C and filter residue B hybrid reaction, filter, get filtrate D (being magnesium chloride solution) and filter residue D (being the acid non-soluble substance impurity in light dolomite), filter residue D abandons, 4) preparation of magnesium hydroxide: with step 1) separate the organic amine that obtains and join in filtrate D, stirring, is to react 1 hour under 60 ℃ of conditions in temperature, then filters, the gained filter residue is through washing and the dry magnesium hydrate powder that gets, and gained filtrate A is recycled and reused for step 1).
Get magnesium hydroxide 53.2 grams through above-mentioned steps, yield is 90%, and purity is 98%, and the heating dehydration can get high-purity magnesium oxide.
Embodiment 7
Raw material used in the present invention has 1 part of a. light dolomite raw material, measures calcium, magnesium ion content in raw material before using, and the mol ratio of calcium oxide and magnesium elements was at 1.2: 1 after measured, and the amount that calcium oxide and magnesium oxide use is respectively 1.2mol, 1mol; B. organic amine is 1 part, and organic amine is two n-amylamines, and in the consumption of 1 part of organic amine and 1 part of light dolomite raw material, the mol ratio of contained magnesium elements amount is 2.2: 1, uses the amount of organic amine to be 2.2mol; C. sulfuric acid, 1 part, measure sulfate radical content in raw material before using, the mol ratio of the organic amine in its sulfate radical content and working cycle is 1.3: 2 after measured, the amount of using is 1.43mol; D. magnesium chloride is 1 part, and amount used is 1mol.Magnesium chloride be used for to start technological cycle as initial feed, and the loss of chlorion in the replenishment cycles process.
at first the setting up procedure of technological cycle of the present invention for being mixed with magnesium chloride the solution of 4mol/L, then organic amine is joined in solution, stir, be to react 1.5 hours under 10 ℃ of conditions in temperature, then filter, get filter residue A and filtrate A, filter residue A obtains magnesium hydroxide through washing and drying, filtrate A enters working cycle, described working cycle step is: the 1) reduction of amine: with filtrate A (being the chlorination two n-amylamine aqueous solution) and light dolomite mix and blend, 50 ℃ of conditioned responses 2 hours, standing separatory, the organic amine that separates is standby, remaining water solidliquid mixture after filtration, obtain liquor B (being calcium chloride solution) and filter residue B (being the magnesium oxide solid), 2) separation of calcium: the vitriol oil is slowly joined in liquor B, stir, then cooling filters, and gets filter residue C (being plaster stone) and liquor C (being hydrochloric acid soln), and filter residue is through washing to get plaster stone, and liquor C is standby, 3) preparation of inorganic soluble magnesium salts solution: after liquor C and filter residue B hybrid reaction, filter, get filtrate D (being magnesium chloride solution) and filter residue D (being the acid non-soluble substance impurity in light dolomite), filter residue D abandons, 4) preparation of magnesium hydroxide: with step 1) separate the organic amine that obtains and join in filtrate D, stirring, is to react 1.5 hours under 10 ℃ of conditions in temperature, then filters, the gained filter residue is through washing and the dry magnesium hydrate powder that gets, and gained filtrate A is recycled and reused for step 1).
Get magnesium hydroxide 53.1 grams through above-mentioned steps, yield is 90%, and purity is 98%, and the heating dehydration can get high-purity magnesium oxide.
Embodiment 8
Raw material used in the present invention has 1 part of a. light dolomite raw material, measures calcium, magnesium ion content in raw material before using, and the mol ratio of calcium oxide and magnesium elements was at 1.3: 1 after measured, and the amount that calcium oxide and magnesium oxide use is respectively 1.3mol, 1mol; B. organic amine is 1 part, and organic amine is two normal hexyl Amines, and in the consumption of 1 part of organic amine and 1 part of light dolomite raw material, the mol ratio of contained magnesium elements amount is 2.3: 1, uses the amount of organic amine to be 2.3mol; C. sulfuric acid, 1 part, measure sulfate radical content in raw material before using, the mol ratio of the organic amine in its sulfate radical content and working cycle is 1.2: 2 after measured, the amount of using is 1.38mol; D. magnesium chloride is 1 part, and amount used is 1mol.Magnesium chloride be used for to start technological cycle as initial feed, and the loss of chlorion in the replenishment cycles process.
at first the setting up procedure of technological cycle of the present invention for being mixed with magnesium chloride the solution of 1mol/L, then organic amine is joined in solution, stir, be to react 0.5 hour under 80 ℃ of conditions in temperature, then filter, get filter residue A and filtrate A, filter residue A obtains magnesium hydroxide through washing and drying, filtrate A enters working cycle, described working cycle step is: the 1) reduction of amine: with filtrate A (being the chlorination two normal hexyl Amine aqueous solution) and light dolomite mix and blend, 50 ℃ of conditioned responses 2 hours, standing separatory, the organic amine that separates is standby, remaining water solidliquid mixture after filtration, obtain liquor B (being calcium chloride solution) and filter residue B (being the magnesium oxide solid), 2) separation of calcium: the vitriol oil is slowly joined in liquor B, stir, then cooling filters, and gets filter residue C (being plaster stone) and liquor C (being hydrochloric acid soln), and filter residue is through washing to get plaster stone, and liquor C is standby, 3) preparation of inorganic soluble magnesium salts solution: after liquor C and filter residue B hybrid reaction, filter, get filtrate D (being magnesium chloride solution) and filter residue D (being the acid non-soluble substance impurity in light dolomite), filter residue D abandons, 4) preparation of magnesium hydroxide: with step 1) separate the organic amine that obtains and join in filtrate D, stirring, is to react 0.5 hour under 80 ℃ of conditions in temperature, then filters, the gained filter residue is through washing and the dry magnesium hydrate powder that gets, and gained filtrate A is recycled and reused for step 1).
Get magnesium hydroxide 55 grams through above-mentioned steps, yield is 94%, and purity is 98%, and the heating dehydration can get high-purity magnesium oxide.
Embodiment 9
Raw material used in the present invention has 1 part of a. light dolomite raw material, measures calcium, magnesium ion content in raw material before using, and the mol ratio of calcium oxide and magnesium elements was at 1.5: 1 after measured, and the amount that calcium oxide and magnesium oxide use is respectively 1.5mol, 1mol; B. organic amine is 1 part, and organic amine is the mixture of normal hexyl Amine and two normal hexyl Amines, and blending ratio is arbitrarily, and in the consumption of 1 part of organic amine and 1 part of light dolomite raw material, the mol ratio of contained magnesium elements amount is 2.2: 1, uses the amount of organic amine to be 2.2mol; C. sulfuric acid, 1 part, measure sulfate radical content in raw material before using, the mol ratio of the organic amine in its sulfate radical content and working cycle is 1.5: 2 after measured, usage quantity is 1.65mol; D. magnesium nitrate is 1 part, and amount used is 1mol.Magnesium nitrate be used for to start technological cycle as initial feed, and the loss of nitrate ion in the replenishment cycles process.
at first the setting up procedure of technological cycle of the present invention for being mixed with magnesium nitrate the solution of 2mol/L, then organic amine is joined in solution, stir, be to react 2 hours under 40 ℃ of conditions in temperature, then filter, get filter residue A and filtrate A, filter residue A obtains magnesium hydroxide through washing and drying, filtrate A enters working cycle, described working cycle step is: the 1) reduction of amine: with filtrate A (being the ammonium nitrate aqueous solution) and light dolomite mix and blend, 10 ℃ of conditioned responses 2 hours, standing separatory, the organic amine that separates is standby, remaining water solidliquid mixture after filtration, obtain liquor B (being ca nitrate soln) and filter residue B (being the magnesium oxide solid), 2) separation of calcium: the vitriol oil is slowly joined in liquor B, stir, then cooling filters, and gets filter residue C (being plaster stone) and liquor C (being salpeter solution), and filter residue is through washing to get plaster stone, and liquor C is standby, 3) preparation of inorganic soluble magnesium salts solution: after liquor C and filter residue B hybrid reaction, filter, get filtrate D (being magnesium nitrate solution) and filter residue D (being the acid non-soluble substance impurity in light dolomite), filter residue D abandons, 4) preparation of magnesium hydroxide: with step 1) separate the organic amine that obtains and join in filtrate D, stirring, is to react 2 hours under 40 ℃ of conditions in temperature, then filters, the gained filter residue is through washing and the dry magnesium hydrate powder that gets, and gained filtrate A is recycled and reused for step 1).
Get magnesium hydroxide 53.9 grams through above-mentioned steps, yield is 91%, and purity is 98%, and the heating dehydration can get high-purity magnesium oxide.
Claims (4)
1. utilize light dolomite to prepare the method for magnesium hydroxide, it is characterized in that at first magnesium nitrate or magnesium chloride are mixed with the solution of 0.1 ~ 4mol/L, then organic amine is joined in solution, described organic amine is Di-n-Butyl Amine, two n-amylamines, a kind of or several mixing arbitrarily in normal hexyl Amine and two normal hexyl Amines, in the consumption of organic amine and light dolomite raw material, the mol ratio of contained magnesium elements amount is 2 ~ 2.4:1, stir, be to react 0.5 ~ 2 hour under 10 ℃ ~ 100 ℃ conditions in temperature, then filter, get filter residue A and filtrate A, filter residue A obtains magnesium hydroxide through washing and drying, filtrate A enters working cycle, described working cycle step is:
1)
The reduction of amine: with filtrate A and light dolomite mix and blend, at 10 ℃ ~ 100 ℃ conditioned responses 0.5 ~ 2 hour, standing separatory, the organic amine of separation is standby, and remaining water solidliquid mixture obtains liquor B and filter residue B after filtration;
2)
The separation of calcium: the vitriol oil is slowly joined in liquor B, stir, then cooling filters, and gets filter residue C and liquor C, and filter residue C is through washing to get plaster stone, and liquor C is standby;
3)
The preparation of inorganic soluble magnesium salts solution: after liquor C and filter residue B hybrid reaction, filter, get filtrate D and filter residue D, filtrate D is inorganic soluble magnesium salts solution, and filter residue D abandons;
4)
The preparation of magnesium hydroxide: step 1) being separated the organic amine that obtains join in filtrate D, stir, is to react 0.5 ~ 2 hour under 10 ℃ ~ 100 ℃ conditions in temperature, then filters, and the gained filter residue is through washing and the dry magnesium hydrate powder that gets, and gained filtrate is recycled and reused for step 1).
2. by the method for utilizing light dolomite to prepare magnesium hydroxide claimed in claim 1, it is characterized in that described light dolomite raw material for containing calcium oxide and magnesian mixture, the mol ratio of calcium oxide and magnesium elements is between 1.5 ~ 1:1.
3. by the described method of utilizing light dolomite to prepare magnesium hydroxide of claim 1 or 2, it is characterized in that described inorganic soluble magnesium salts solution is that volumetric molar concentration is 0.1 ~ 4mol/L magnesium nitrate or magnesium chloride brine.
4. by the described method of utilizing light dolomite to prepare magnesium hydroxide of claim 1 or 2, it is characterized in that described vitriol oil consumption is 1-1.5:2 for the mol ratio of the organic amine in its sulfate radical content and working cycle.
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| CN103896313A (en) * | 2012-12-31 | 2014-07-02 | 江西江锂科技有限公司 | Method for preparing high-activity magnesium oxide by adopting old brine in salt lake as material |
| CN108529654A (en) * | 2018-05-07 | 2018-09-14 | 天津君瑞和科技有限公司 | A method of with making from brine for micro/nano level magnesium hydroxide |
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| JPH1059711A (en) * | 1996-08-12 | 1998-03-03 | Daicel Amiboshi Sangyo Kk | Magnesium hydroxide and production of aqueous liquid suspension thereof |
| CN1280196C (en) * | 2003-12-22 | 2006-10-18 | 国家***天津海水淡化与综合利用研究所 | Process for preparing magnesium hydroxide by light burning bitter spar and concentrated sea water |
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