CN102139899B - Method for preparing magnesium sulfate monohydrate and co-producing manganese sulfate and calcium sulfate by using boric sludge - Google Patents
Method for preparing magnesium sulfate monohydrate and co-producing manganese sulfate and calcium sulfate by using boric sludge Download PDFInfo
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- CN102139899B CN102139899B CN201010558899A CN201010558899A CN102139899B CN 102139899 B CN102139899 B CN 102139899B CN 201010558899 A CN201010558899 A CN 201010558899A CN 201010558899 A CN201010558899 A CN 201010558899A CN 102139899 B CN102139899 B CN 102139899B
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- sulfate
- hydrochloric acid
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- boric sludge
- monohydrate
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- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 22
- 239000010802 sludge Substances 0.000 title claims abstract description 17
- 229940076230 magnesium sulfate monohydrate Drugs 0.000 title claims abstract description 15
- LFCFXZHKDRJMNS-UHFFFAOYSA-L magnesium;sulfate;hydrate Chemical compound O.[Mg+2].[O-]S([O-])(=O)=O LFCFXZHKDRJMNS-UHFFFAOYSA-L 0.000 title claims abstract description 15
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 title claims abstract description 8
- 229940099596 manganese sulfate Drugs 0.000 title claims abstract description 5
- 239000011702 manganese sulphate Substances 0.000 title claims abstract description 5
- 235000007079 manganese sulphate Nutrition 0.000 title claims abstract 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000001816 cooling Methods 0.000 claims abstract description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 19
- 229910052796 boron Inorganic materials 0.000 claims description 19
- 235000011132 calcium sulphate Nutrition 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 10
- KNLQKHUBPCXPQD-UHFFFAOYSA-N manganese;sulfuric acid Chemical compound [Mn].OS(O)(=O)=O KNLQKHUBPCXPQD-UHFFFAOYSA-N 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 10
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 238000005260 corrosion Methods 0.000 claims description 6
- 230000007797 corrosion Effects 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 4
- 238000010298 pulverizing process Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims 3
- 239000012065 filter cake Substances 0.000 claims 2
- 238000001914 filtration Methods 0.000 claims 2
- 239000007788 liquid Substances 0.000 claims 2
- WRUGWIBCXHJTDG-UHFFFAOYSA-L magnesium sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Mg+2].[O-]S([O-])(=O)=O WRUGWIBCXHJTDG-UHFFFAOYSA-L 0.000 claims 2
- 238000003756 stirring Methods 0.000 claims 2
- 206010013786 Dry skin Diseases 0.000 claims 1
- KGMNHOOXYBNYQT-UHFFFAOYSA-N [Mg].O.S(O)(O)(=O)=O Chemical compound [Mg].O.S(O)(O)(=O)=O KGMNHOOXYBNYQT-UHFFFAOYSA-N 0.000 claims 1
- 239000011259 mixed solution Substances 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 239000011541 reaction mixture Substances 0.000 claims 1
- 238000000926 separation method Methods 0.000 claims 1
- 239000011973 solid acid Substances 0.000 claims 1
- 239000001117 sulphuric acid Substances 0.000 claims 1
- 235000011149 sulphuric acid Nutrition 0.000 claims 1
- 239000002699 waste material Substances 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 229940095672 calcium sulfate Drugs 0.000 abstract 1
- 229910021538 borax Inorganic materials 0.000 description 6
- 239000004328 sodium tetraborate Substances 0.000 description 6
- 235000010339 sodium tetraborate Nutrition 0.000 description 6
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 3
- 229940091250 magnesium supplement Drugs 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229910052810 boron oxide Inorganic materials 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- 235000012255 calcium oxide Nutrition 0.000 description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 239000004484 Briquette Substances 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- QHUNZUWQAIPCAS-UHFFFAOYSA-N [P].[Mg].[B] Chemical compound [P].[Mg].[B] QHUNZUWQAIPCAS-UHFFFAOYSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 235000014380 magnesium carbonate Nutrition 0.000 description 1
- 229960001708 magnesium carbonate Drugs 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- ZATZOOLBPDMARD-UHFFFAOYSA-N magnesium;hydrate Chemical compound O.[Mg] ZATZOOLBPDMARD-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
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- Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
- Removal Of Specific Substances (AREA)
- Heat Treatment Of Water, Waste Water Or Sewage (AREA)
Abstract
The invention belongs to the technical field of inorganic chemical three-waste treatment and comprehensive utilization and in particular relates to a method for preparing magnesium sulfate monohydrate and co-producing manganese sulfate and calcium sulfate by using boric sludge. The method mainly comprises the following steps of: heating the boric sludge with vapor; separating the boric sludge; reacting the boric sludge and hydrochloric acid; and distilling and cooling according to the difference of the solubility of substances, and separating to obtain the product. By the method, waste residues of the boric sludge can be cleanly removed; the pollution of the waste residues of the boric sludge to the environment is reduced; and valuable magnesium sulfate monohydrate, manganese sulfate and calcium sulfate products can be prepared. The method has obvious social and economical benefits, and is a relatively practical treating and using method, and the process and production equipment are simple.
Description
Technical field
The invention belongs to the technical field of the inorganic chemical industry disposal of three wastes and comprehensive utilization, particularly a kind of method that is equipped with magnesium sulfate monohydrate co-producing sulfuric acid manganese and calcium sulfate with boric sludge.
Technical background
Producing the waste residue that products such as boric acid, borax produce, is with szaibelyite (MgOB
2O
3H
2O) be raw material, through roasting, pulverizing, mix, take the carbon water law to produce borax (Na with soda ash
2B
4O
710H
2O), washing again, crystallisation process extract the solid waste that is left behind the borax; This solid waste is pearl, yellow-white powdery solid, is alkalescence, contains components such as boron oxide and Natural manganese dioxide, is commonly called as " boron mud ".One ton of borax of boron mud production can produce 4 tons of boron mud, and a borax of producing 8000 tons produces, and can produce 3.2 ten thousand tons in boron mud every year.The disposal of storing up of boron mud not only takies a large amount of soils, and can make near the alkalization of soils the stockyard and cause that the migration of boron transforms, and causes environmental pollution.Because the quantity discharged of boron mud is bigger, the present domestic multiple comprehensive Utilization Ways of taking except that producing Magnesium Carbonate Light 41-45 and Natural manganese dioxide and plastic and rubber filler, also has the coal of producing boron magnesium phosphorus composite fertilizer, making honeycomb briquette to add labor and materials and do architectural borax etc.Though these methods are handled filter residue certain effect being arranged, all be to want the buy-birth prodn. art complicated, or the product that generates is comparatively single; Boric sludge also of no use is equipped with the relevant report of the method for magnesium sulfate monohydrate co-producing sulfuric acid manganese and calcium sulfate at present.
Summary of the invention
The invention provides the method that is equipped with magnesium sulfate monohydrate co-producing sulfuric acid manganese and calcium sulfate with boric sludge, this method can not only effectively be handled waste residue, can also make multiple value product.
In order to reach above-mentioned purpose, technical scheme of the present invention is:
A kind ofly be equipped with the method for magnesium sulfate monohydrate co-producing sulfuric acid manganese and calcium sulfate, comprise being prepared as follows step with boric sludge:
Steps A, boron mud is transferred in the reaction kettle, heats, when temperature reaches 60 ℃～80 ℃, be incubated 1～2 hour with steam;
Step B, with in the steps A heat boron mud carry out solid-liquid separation with the drying whizzer, liquid is sent to deep processing;
Step C, separating obtained boron mud solid among the step B is sent into first corrosion-resistant reactor, add hydrochloric acid soln toward first corrosion-resistant reactor simultaneously, stir and make it to react; Said boron mud solid and hydrochloric acid soln react with the pure mass ratio of converting 1: 1.63～2.03; Wherein, said boron mud solid calculates by Natural manganese dioxide; Reaction generates magnesian hydrate;
Step D, gained reaction mixture among the step C is filtered with first strainer, filter cake is sent to deep processing;
Step e, drop into successively in second corrosion-resistant reactor with pure mass ratio 1: 0.83～1.23 with sulfuric acid and stir filtering gained filtrating among the step D, reaction generates magnesium sulfate monohydrate, calcium sulfate, manganous sulfate and hydrochloric acid mixed solution;
Step F, gained mixing solutions in the step e is filtered with second strainer;
Step F, the white filter cake that filters gained in the step e washed to check the weight after dryings, drying and the pulverizing with first washing and spin-drying machine, first moisture eliminator and first kibbler successively be packaged to be two H 2 O calcium sulphates;
Step G, the filtrating of filtering gained in the step F sent into carry out underpressure distillation in the underpressure distillation device; When solution reaches protection concentration; Obtain the MAGNESIUM SULPHATE HEPTAHYDRATE 99.5 crystal, continue distillation and obtain manganous sulfate, manganous sulfate is discharged and is sent into the cooling tower cooling; The gained crystal with second washing and spin-drying machine, second moisture eliminator and second kibbler wash drying, dry and pulverize after check the weight and be packaged to be manganese sulfate product, the hydrochloric acid soln that distills returns first corrosion-resistant reactor and recycles;
Step H, MAGNESIUM SULPHATE HEPTAHYDRATE 99.5 crystal among the step G is discharged, carry out drying with the 3rd moisture eliminator, checking the weight after the pulverizing is packaged to be the sulfuric acid monohydrate magnesium products.
Wherein, the hydrochloric acid soln among the said step C is that volumetric concentration is 30%～60% hydrochloric acid soln.
Sulfuric acid in the said step e is that volumetric concentration is 10%～20% sulphuric acid soln.
Magnesium in the boron mud generally all is that the form with magnesiumcarbonate exists, and is sometimes also different and difference arranged along with the mineral products of szaibelyite.The component of producing Magnesium Carbonate Light 41-45 boron mud is such: Natural manganese dioxide 38%, silicon-dioxide 20%, carbonic acid gas 17%, boron oxide 3%, quicklime 3% manganese oxide 0.11%, other are moisture.
The present invention is that to be raw material make it to become oxide compound through hydrochloric acid forms solution with boron mud, removes the compound that non-solubility impurity obtains magnesium.At the compound of other magnesium of processing, also has compound of boron or the like then.Therefore, with regard to the purity of producing, be impeccable, quality also reaches a standard.Mainly be earlier boron mud to be used steam heating, separate then, react with hydrochloric acid again, distill cooling according to the difference of substance dissolves degree at last, separate obtaining product; The present invention can as clean as a pennyly gulp down boron mud waste residue, alleviates the pollution of boron mud waste residue to environment; Can make valuable magnesium sulfate monohydrate, manganous sulfate and calcium sulfate product again, not only have remarkable social benefit and economic benefit, and technology and production unit are simple, be a kind of relatively actual processing and utilize method.
Reaction principle of the present invention is:
MgO+2HCl＝MgCl
2+H
2O
MgCl
2+H
2SO
2+H
2O＝Mg?SO
4·7H
2O+2HCl
CaO+2HCl＝CaCl
2+H
2O
CaCl
2+H
2SO
4＝Ca?SO
4+2HCl
MnO+2HCl＝MnCl
2+H
2O
MnCl
2+H
2SO
4＝MnSO
4+2HCl
Description of drawings
Fig. 1 is the process flow sheet that is equipped with the method for magnesium sulfate monohydrate co-producing sulfuric acid manganese and calcium sulfate with boric sludge; Wherein:
The 1-reaction kettle, 2-dries whizzer, 3-first corrosion-resistant reactor, 4-first strainer, 5-second corrosion-resistant reactor; 6-second strainer, 7-first washing and spin-drying machine, 8-first moisture eliminator, 9-first kibbler, 10-two H 2 O calcium sulphates; 11-underpressure distillation device, 12-cooling tower, 13-second washing and spin-drying machine, 14-second moisture eliminator; 15-second kibbler, 16-manganese sulfate product, 17-the 3rd moisture eliminator, 17-sulfuric acid monohydrate magnesium products.
Concrete embodiment
A kind ofly be equipped with the method for magnesium sulfate monohydrate co-producing sulfuric acid manganese and calcium sulfate, it is characterized in that, comprise being prepared as follows step with boric sludge:
Steps A, boron mud 1000Kg is transferred in the reaction kettle 1, heats, when temperature reaches 60 ℃～80 ℃, be incubated 1～2 hour with steam; Wherein, Natural manganese dioxide 38% (380Kg), silicon-dioxide 20%, carbonic acid gas 17%, boron oxide 3%, quicklime 3% (30Kg) manganese oxide 0.11% (1.1Kg), other are moisture.
Step B, with in the steps A heat boron mud with the drying whizzer 2 carry out solid-liquid separation, liquid is sent to deep processing;
Step C, separating obtained boron mud solid among the step B is sent into first corrosion-resistant reactor 3, add hydrochloric acid solns toward first corrosion-resistant reactor 3 simultaneously, stir and make it to react; Said boron mud solid and hydrochloric acid soln react with the pure mass ratio of converting at 1: 1.63; Wherein, said boron mud solid calculates by Natural manganese dioxide; Reaction generates magnesian hydrate; Said hydrochloric acid soln is that volumetric concentration is 30% hydrochloric acid soln.
Step D, gained reaction mixture among the step C is filtered with first strainer 4, filter cake is sent to deep processing;
Step e, successively drop into second corrosion-resistant reactor with sulfuric acid at 1: 0.83 with pure mass ratio and stir for 5 li filtering gained filtrating among the step D, reaction generates magnesium sulfate monohydrate, calcium sulfate, manganous sulfate and hydrochloric acid mixed solution; Sulfuric acid in the said step e is that volumetric concentration is 10% sulphuric acid soln.
Step F, gained mixing solutions in the step e is filtered with second strainer 6;
Step F, the white filter cake that filters gained in the step e washed to check the weight after dryings, drying and the pulverizing with first washing and spin-drying machine 7, first moisture eliminator 8 and first kibbler 9 successively be packaged to be 45.12Kg two H 2 O calcium sulphates 10;
Step G, the filtrating of filtering gained in the step F sent into carry out underpressure distillation in the underpressure distillation device 11; When solution reaches protection concentration; Obtain the MAGNESIUM SULPHATE HEPTAHYDRATE 99.5 crystal; Continue distillation and obtain manganous sulfate; Manganous sulfate is discharged and to be sent into cooling tower 12 coolings, and the gained crystal washs to check the weight after dryings, drying and the pulverizing with second washing and spin-drying machine 13, second moisture eliminator 14 and second kibbler 15 and is packaged to be 2.08Kg manganese sulfate product 16, and the hydrochloric acid soln that distills returns first corrosion-resistant reactor 3 and recycles;
Step H, MAGNESIUM SULPHATE HEPTAHYDRATE 99.5 crystal among the step G is discharged, carry out drying with the 3rd moisture eliminator 17, checking the weight after the pulverizing is packaged to be 407.87Kg sulfuric acid monohydrate magnesium products 18.
Embodiment 2
A kind ofly be equipped with the method for magnesium sulfate monohydrate co-producing sulfuric acid manganese and calcium sulfate, it is characterized in that, comprise being prepared as follows step with boric sludge:
Steps A, boron mud 1000Kg is transferred in the reaction kettle 1, heats, when temperature reaches 60 ℃～80 ℃, be incubated 1～2 hour with steam; Wherein, Natural manganese dioxide 38% (380Kg), silicon-dioxide 20%, carbonic acid gas 17%, boron oxide 3%, quicklime 3% (30Kg) manganese oxide 0.11% (1.1Kg), other are moisture.
Step B, with in the steps A heat boron mud with the drying whizzer 2 carry out solid-liquid separation, liquid is sent to deep processing;
Step C, separating obtained boron mud solid among the step B is sent into first corrosion-resistant reactor 3, add hydrochloric acid solns toward first corrosion-resistant reactor 3 simultaneously, stir and make it to react; Said boron mud solid and hydrochloric acid soln react with the pure mass ratio of converting at 1: 2.13; Wherein, said boron mud solid calculates by Natural manganese dioxide; Reaction generates magnesian hydrate; Said hydrochloric acid soln is that volumetric concentration is 40% hydrochloric acid soln.
Step D, gained reaction mixture among the step C is filtered with first strainer 4, filter cake is sent to deep processing;
Step e, successively drop into second corrosion-resistant reactor with sulfuric acid at 1: 1.03 with pure mass ratio and stir for 5 li filtering gained filtrating among the step D, reaction generates magnesium sulfate monohydrate, calcium sulfate, manganous sulfate and hydrochloric acid mixed solution; Sulfuric acid in the said step e is that volumetric concentration is 15% sulphuric acid soln.
Step F, gained mixing solutions in the step e is filtered with second strainer 6;
Step F, the white filter cake that filters gained in the step e washed to check the weight after dryings, drying and the pulverizing with first washing and spin-drying machine 7, first moisture eliminator 8 and first kibbler 9 successively be packaged to be 56.86Kg two H 2 O calcium sulphates 10;
Step G, the filtrating of filtering gained in the step F sent into carry out underpressure distillation in the underpressure distillation device 11; When solution reaches protection concentration; Obtain the MAGNESIUM SULPHATE HEPTAHYDRATE 99.5 crystal; Continue distillation and obtain manganous sulfate; Manganous sulfate is discharged and to be sent into cooling tower 12 coolings, and the gained crystal washs to check the weight after dryings, drying and the pulverizing with second washing and spin-drying machine 13, second moisture eliminator 14 and second kibbler 15 and is packaged to be 2.31Kg manganese sulfate product 16, and the hydrochloric acid soln that distills returns first corrosion-resistant reactor 3 and recycles;
Step H, MAGNESIUM SULPHATE HEPTAHYDRATE 99.5 crystal among the step G is discharged, carry out drying with the 3rd moisture eliminator 17, checking the weight after the pulverizing is packaged to be 599.02Kg sulfuric acid monohydrate magnesium products 18.
Embodiment 3
A kind ofly be equipped with the method for magnesium sulfate monohydrate co-producing sulfuric acid manganese and calcium sulfate, it is characterized in that, comprise being prepared as follows step with boric sludge:
Steps A, boron mud 1000Kg is transferred in the reaction kettle 1, heats, when temperature reaches 60 ℃～80 ℃, be incubated 1～2 hour with steam; Wherein, Natural manganese dioxide 38% (380Kg), silicon-dioxide 20%, carbonic acid gas 17%, boron oxide 3%, quicklime 3% (30Kg) manganese oxide 0.11% (1.1Kg), other are moisture.
Step B, with in the steps A heat boron mud with the drying whizzer 2 carry out solid-liquid separation, liquid is sent to deep processing;
Step C, separating obtained boron mud solid among the step B is sent into first corrosion-resistant reactor 3, add hydrochloric acid solns toward first corrosion-resistant reactor 3 simultaneously, stir and make it to react; Said boron mud solid and hydrochloric acid soln react with the pure mass ratio of converting at 1: 2.03; Wherein, said boron mud solid calculates by Natural manganese dioxide; Reaction generates magnesian hydrate; Said hydrochloric acid soln is that volumetric concentration is 60% hydrochloric acid soln.
Step D, gained reaction mixture among the step C is filtered with first strainer 4, filter cake is sent to deep processing;
Step e, successively drop into second corrosion-resistant reactor with sulfuric acid at 1: 1.23 with pure mass ratio and stir for 5 li filtering gained filtrating among the step D, reaction generates magnesium sulfate monohydrate, calcium sulfate, manganous sulfate and hydrochloric acid mixed solution; Sulfuric acid in the said step e is that volumetric concentration is 20% sulphuric acid soln.
Step F, gained mixing solutions in the step e is filtered with second strainer 6;
Step F, the white filter cake that filters gained in the step e washed to check the weight after dryings, drying and the pulverizing with first washing and spin-drying machine 7, first moisture eliminator 8 and first kibbler 9 successively be packaged to be 72.81Kg two H 2 O calcium sulphates 10;
Step G, the filtrating of filtering gained in the step F sent into carry out underpressure distillation in the underpressure distillation device 11; When solution reaches protection concentration; Obtain the MAGNESIUM SULPHATE HEPTAHYDRATE 99.5 crystal; Continue distillation and obtain manganous sulfate; Manganous sulfate is discharged and to be sent into cooling tower 12 coolings, and the gained crystal washs to check the weight after dryings, drying and the pulverizing with second washing and spin-drying machine 13, second moisture eliminator 14 and second kibbler 15 and is packaged to be 2.34Kg manganese sulfate product 16, and the hydrochloric acid soln that distills returns first corrosion-resistant reactor 3 and recycles;
Step H, MAGNESIUM SULPHATE HEPTAHYDRATE 99.5 crystal among the step G is discharged, carry out drying with the 3rd moisture eliminator 17, checking the weight after the pulverizing is packaged to be 1067.18Kg sulfuric acid monohydrate magnesium products 18.
The foregoing description is preferred embodiment of the present invention, is not to be used for limiting practical range of the present invention, so all equivalences of being done with described characteristic of claim of the present invention and principle change or modify, all should be included within the claim scope of the present invention.
Claims (3)
1. be equipped with the method for magnesium sulfate monohydrate co-producing sulfuric acid manganese and calcium sulfate with boric sludge, it is characterized in that, comprise being prepared as follows step:
Steps A, boron mud is transferred in the reaction kettle (1), heats, when temperature reaches 60 ℃～80 ℃, be incubated 1～2 hour with steam;
Step B, with in the steps A heat boron mud with the drying whizzer (2) carry out solid-liquid separation, liquid is sent to deep processing;
Step C, separating obtained boron mud solid among the step B is sent into first corrosion-resistant reactor (3), add hydrochloric acid soln toward first corrosion-resistant reactor (3) simultaneously, stir and make it to react; Said boron mud solid and hydrochloric acid soln react with pure mass ratio 1:1.63～2.03 of converting, and wherein, said boron mud solid calculates by Natural manganese dioxide;
Step D, gained reaction mixture among the step C is filtered with first strainer (4), filter cake is sent to deep processing;
Step e, drop into second corrosion-resistant reactor (5) lining with sulfuric acid successively with pure mass ratio 1:0.83～1.23 and stir filtering gained filtrating among the step D, reaction generates magnesium sulfate monohydrate, calcium sulfate, manganous sulfate and hydrochloric acid mixed solution;
Step F, gained mixing solutions in the step e is filtered with second strainer (6);
Step F, the white filter cake that filters gained in the step e used first washing and spin-drying machine (7), first moisture eliminator (8) and first kibbler (9) to wash to check the weight after dryings, drying and the pulverizing successively be packaged to be two H 2 O calcium sulphates (10);
Step G, the filtrating of filtering gained in the step F sent in the underpressure distillation device (11) carry out underpressure distillation; When solution reaches protection concentration; Obtain the MAGNESIUM SULPHATE HEPTAHYDRATE 99.5 crystal; Continue distillation and obtain manganous sulfate; Manganous sulfate is discharged and to be sent into cooling tower (12) cooling, and the gained crystal washs to check the weight after drying, drying and the pulverizing with second washing and spin-drying machine (13), second moisture eliminator (14) and second kibbler (15) and is packaged to be manganese sulfate product (16), and the hydrochloric acid soln that distills returns first corrosion-resistant reactor (3) and recycles;
Step H, MAGNESIUM SULPHATE HEPTAHYDRATE 99.5 crystal among the step G is discharged, carry out drying with the 3rd moisture eliminator (17), checking the weight after the pulverizing is packaged to be sulfuric acid monohydrate magnesium products (18).
2. according to claim 1ly be equipped with the method for magnesium sulfate monohydrate co-producing sulfuric acid manganese and calcium sulfate, it is characterized in that the hydrochloric acid soln among the said step C is that volumetric concentration is 30%～60% hydrochloric acid soln with boric sludge.
3. according to claim 1ly be equipped with the method for magnesium sulfate monohydrate co-producing sulfuric acid manganese and calcium sulfate, it is characterized in that the sulfuric acid in the said step e is that volumetric concentration is 10%～20% sulphuric acid soln with boric sludge.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010558899A CN102139899B (en) | 2010-11-25 | 2010-11-25 | Method for preparing magnesium sulfate monohydrate and co-producing manganese sulfate and calcium sulfate by using boric sludge |
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| CN201010558899A CN102139899B (en) | 2010-11-25 | 2010-11-25 | Method for preparing magnesium sulfate monohydrate and co-producing manganese sulfate and calcium sulfate by using boric sludge |
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| CN102139899B true CN102139899B (en) | 2012-09-26 |
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| JP4699622B2 (en) * | 2001-03-14 | 2011-06-15 | 株式会社三徳 | Method for separating boron-containing solution from R (rare earth) -Fe-B magnet alloy sludge |
| CN1193955C (en) * | 2001-05-18 | 2005-03-23 | 中国科学院长春应用化学研究所 | Process for preparing high-purity magnesite product series from boron contained mud |
| CN101348268B (en) * | 2007-07-19 | 2011-04-06 | 东北大学 | Two comprehensive methods of utilization of boron mud, giobertite and talc deposit for preparing magnesia and silicon dioxide |
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