CN109231631A - A kind of system that nanometer magnesia powder is prepared as raw material using desulfurization wastewater - Google Patents
A kind of system that nanometer magnesia powder is prepared as raw material using desulfurization wastewater Download PDFInfo
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- CN109231631A CN109231631A CN201811289953.9A CN201811289953A CN109231631A CN 109231631 A CN109231631 A CN 109231631A CN 201811289953 A CN201811289953 A CN 201811289953A CN 109231631 A CN109231631 A CN 109231631A
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- reaction tank
- tubular membrane
- pond
- desulfurization wastewater
- suction pump
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- 239000002351 wastewater Substances 0.000 title claims abstract description 53
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 40
- 230000023556 desulfurization Effects 0.000 title claims abstract description 40
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 239000000395 magnesium oxide Substances 0.000 title claims abstract description 19
- 239000002994 raw material Substances 0.000 title claims abstract description 10
- 239000000843 powder Substances 0.000 title claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 67
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 43
- 229910001424 calcium ion Inorganic materials 0.000 claims abstract description 25
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000001728 nano-filtration Methods 0.000 claims abstract description 16
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910001425 magnesium ion Inorganic materials 0.000 claims abstract description 15
- 238000001223 reverse osmosis Methods 0.000 claims abstract description 14
- 238000001354 calcination Methods 0.000 claims abstract description 12
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims abstract description 10
- 239000000347 magnesium hydroxide Substances 0.000 claims abstract description 6
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 98
- 239000012528 membrane Substances 0.000 claims description 37
- 238000001556 precipitation Methods 0.000 claims description 25
- 238000001914 filtration Methods 0.000 claims description 21
- 150000003839 salts Chemical group 0.000 claims description 10
- 230000003009 desulfurizing effect Effects 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 3
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 18
- 238000000926 separation method Methods 0.000 abstract description 15
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 abstract description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 abstract description 12
- 150000002500 ions Chemical class 0.000 abstract description 12
- 239000000047 product Substances 0.000 abstract description 10
- 229910052938 sodium sulfate Inorganic materials 0.000 abstract description 10
- 235000011152 sodium sulphate Nutrition 0.000 abstract description 10
- 229910052602 gypsum Inorganic materials 0.000 abstract description 9
- 239000010440 gypsum Substances 0.000 abstract description 9
- 239000006227 byproduct Substances 0.000 abstract description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 abstract description 6
- 238000010992 reflux Methods 0.000 abstract description 5
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 abstract description 4
- 235000019738 Limestone Nutrition 0.000 abstract description 3
- 239000006028 limestone Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000006228 supernatant Substances 0.000 description 30
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 25
- 239000007788 liquid Substances 0.000 description 18
- 229910000019 calcium carbonate Inorganic materials 0.000 description 12
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 11
- 239000007787 solid Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 8
- 239000012265 solid product Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000001704 evaporation Methods 0.000 description 7
- 230000001376 precipitating effect Effects 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 230000008020 evaporation Effects 0.000 description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 235000011132 calcium sulphate Nutrition 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 5
- 239000003546 flue gas Substances 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 239000008235 industrial water Substances 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 239000010881 fly ash Substances 0.000 description 3
- 239000013505 freshwater Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 238000010612 desalination reaction Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000003517 fume Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000008118 PEG 6000 Substances 0.000 description 1
- 229920002584 Polyethylene Glycol 6000 Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- 239000001175 calcium sulphate Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 description 1
- 230000002500 effect on skin Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000007701 flash-distillation Methods 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- -1 hydrogen Magnesium oxide Chemical class 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- 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
- C01F5/02—Magnesia
- C01F5/06—Magnesia by thermal decomposition of magnesium compounds
- C01F5/08—Magnesia by thermal decomposition of magnesium compounds by calcining magnesium hydroxide
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F2001/007—Processes including a sedimentation step
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/18—Nature of the water, waste water, sewage or sludge to be treated from the purification of gaseous effluents
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The present invention provides a kind of systems for preparing nanometer magnesia powder as raw material using desulfurization wastewater, its by homogeneous, heavy-metal ion removal, add sodium sulphate and prepare gypsum by-product, add sodium carbonate and prepare lime stone byproduct, add sodium hydroxide and prepare magnesium hydroxide, then magnesium hydroxide is prepared into magnesium oxide product after calcining, finally carries out water process by nanofiltration and reverse osmosis unit and obtains the reflux water for meeting production requirement；Calcium ions and magnesium ions separation is prepared byproduct during softening desulfurization wastewater by the present invention, realizes the comprehensive utilization of resource, meets the theory of energy-saving and emission-reduction.
Description
Technical field
The invention belongs to desulfurization wastewater processing technology fields, specifically provide a kind of using desulfurization wastewater as raw material preparation nanometer
The system of magnesium oxide powder.
Background technique
Wet Limestone gypsum method flue gas desulfurization is the commonly used coal-fired flue gas desulfurization technology in China, which accounts for China
90% or more of coal fired power plant installed capacity.It is useless that wet method fume desulfurizing system can generate a certain amount of desulfurization in actual operation
Water, the pH value of desulfurization wastewater contain a large amount of gypsum, flying dust and sulfate suspension generally between 4~6 in desulfurization wastewater
Grain, wherein chlorine ion concentration may be up to 20000mg/L, and the cation in desulfurization wastewater is mainly calcium and magnesium ion and an a small amount of huge sum of money
Belong to ion.Direct emission can bring secondary pollution to environment.Chemical precipitation-coagulation clarification technique is widely used both at home and abroad at present
Desulfurization wastewater is disposed, although suspended matter and content of beary metal in water can be effectively reduced in the technique, after processing
Waste water still contain a large amount of calcium and magnesium ion, wherein the concentration of magnesium ion is even as high as mg/L up to ten thousand, have strong corrosive and easily
The features such as fouling, waste water are unable to reach reuse standard.The terminal processing techniques of desulfurization wastewater carry out after decrement is mainly concentrated
Evaporation process, the soluble solid in desulfurization wastewater are trapped in concentration raffinate, are finally precipitated with crystal form.According to heating
The difference of form can be divided into multistage flash distillation, multiple-effect evaporation and mechanical vapor recompression technology and flue gas evaporation technique etc..Cigarette
Road gas evaporation technique is the flue between the air preheater and electric precipitator for spraying into coal-fired power station boiler after being atomized desulfurization wastewater,
Or enter in bypass vaporising device together from a part of hot fume and desulfurization wastewater is introduced into before air preheater, utilize flue gas heat
Make waste water evaporating completely, Pollutants in Wastewater is converted into the solids such as crystal or salt, is removed with the flying dust in flue gas by electricity
Dirt device is collected, to realize the zero-emission of waste water.The investment of flue evaporation technique and operating cost are lower, occupied area pole
It is small, however, the technology is the acid waste water for directly spraying into high salinity into flue, it be easy to cause the corrosion or product of downstream flue
Ash, and flyash quality is caused to decline, influence the comprehensive utilization of flyash.Evaporative crystallization method can recycle water resource and crystallization
Salt, but its investment is high with operating cost and takes up an area larger.Meanwhile if the crystal salt of recycling is sodium sulphate and chlorination
The mixed salt of sodium composition, is worth lower.In addition, generally being needed in order to ensure crystallizing evaporator operates normally and guarantee crystal salt quality
Waste water is strictly pre-processed.In short, desulfurization wastewater processing technique also needs development investment operating cost lower and high attached
The technology of value added resource utilization.
Nanoscale magnesium has apparent small-size effect, skin effect, quantum size effect and macroscopical tunnel-effect,
Modified processing, soilless sticking phenomenon, optics, catalysis, magnetism, mechanics, in terms of there are many exceptional functions and important
Application value, prospect are boundless.Contain a large amount of magnesium ion in desulfurization wastewater, may be used as the raw material for preparing magnesia.
But it in existing desulfurization wastewater processing technique, typically lays stress in the softening of desulfurization wastewater, isolated pair
Product is existed in the form of mixing pug, is then uniformly processed, cannot obtain the very high magnesium oxide product of purity.Stone
Cream is a kind of application and its extensive chemical substance, that is, can be used as industrial materials and construction material, it can also be used to cement retarder,
Gypsum building products, modelling, medical food additive, gas washing in SA production, filler, paint filler etc.；Gypsum and its system
The microcellular structure and thermal dehydration of product are allowed to have excellent sound insulation, heat-insulated and fire protecting performance.And traditional desulfurization wastewater processing
It is often laid stress in technology in waste water softening, obtained byproduct is often carried out at concentration in the form of mixing pug
Reason, can not obtain the very high gypsum product of purity.
Summary of the invention
In order to solve the above technical problems, the present invention provides a kind of system for preparing magnesia as raw material using desulfurization wastewater,
A kind of method that nanoscale magnesium powder body is prepared as raw material substep softening using desulfurization wastewater is proposed, in softening desulfurization wastewater
Byproduct recycling, the especially preparation of salt magnesia are carried out in the process, and the synthesization for realizing resource utilizes.
The present invention is to reach above-mentioned technical purpose, and used technical solution is as follows:
The present invention includes:
Reaction tank 1 (5) is used to separate a part of calcium ion, the water inlet of the reaction tank 1 (5) and precipitation reaction pond
Top be connected, the water outlet of the reaction tank 1 (5) is connected by suction pump (6) with tubular membrane 1 (7).If secondary supernatant calcium
When ion concentration is higher than 1000mg/L, sodium hydroxide solution is added, pH is controlled 7.0, solid sodium sulfate is then added, adds
Amount are as follows: 3 (x-1000) mg/L；Then calcium sulfate is added, dosage is the 1% of solid sodium sulfate；The x is calcium ion concentration,
Unit mg/L；If calcium ion concentration is lower than 1000mg/L in secondary supernatant, pH is controlled 7.0 with sodium hydroxide solution
Afterwards, it is separated by solid-liquid separation by tubular membrane 1 (7), obtains mud mixture and three-level supernatant.
Reaction tank 2 (9) is used to separate remaining all calcium ions, the water inlet and tubular membrane 1 of the reaction tank 2 (9)
(7) it is connected, the water outlet of the reaction tank 2 (9) is connected by suction pump with filtering ponds (11).Sodium carbonate liquor is added, is generated
Precipitation of calcium carbonate is separated by solid-liquid separation with filtering ponds (11) after fully reacting, obtains level Four supernatant and calcium carbonate solid product.
Reaction tank 3 (12), is used to separate magnesium ion, under the water inlet of the reaction tank 3 (12) and filtering ponds (11)
Portion is connected, and the water outlet of the reaction tank 3 (12) is connected by suction pump (13) with tubular membrane 2 (14).It is molten to add sodium hydroxide
Liquid generates magnesium hydrate precipitate, to separate from system.
As a further improvement of the present invention, the pretreatment unit includes homogeneous pond (2), precipitation reaction pond (3) and plate
Frame filter press 1 (4)；The water inlet of the homogeneous pond (2) passes through desulfurization wastewater pipeline connection desulfurizing tower (1), the homogeneous pond (2)
Water outlet is connected with the precipitation reaction pond (3).The lower part in precipitation reaction pond (3) is connected with plate and frame filter press 1 (4), water outlet
It is connected with reaction tank 1 (5).Since there are many slightly solubility substances and water quality from the desulfurization wastewater that desulfurizing tower directly comes out
All there is certain fluctuation with water, it is therefore desirable to carry out homogeneous using homogeneous pond, and keep the indissoluble object in desulfurization wastewater heavy
Shallow lake obtains preliminary sedimentation, and level-one supernatant imports in next stage reaction unit, to remove influence of these substances to subsequent reactions.
It is added in precipitation reaction pond and generates precipitating after recapturing agent, be sufficiently separated by solid-liquid separation after ageing, obtain secondary supernatant.Precipitating is anti-
Ying Chi is for heavy-metal ion removal.
As a further improvement of the present invention, the calcium ion removal unit include reaction tank 1 (5), suction pump (6,10),
Tubular membrane 1 (7) and plate and frame filter press 2 (8), reaction tank 2 (9) and filtering ponds (11).The water inlet and precipitating of reaction tank 1 (5) are anti-
The top of Ying Chi (3) is connected, and the water outlet of reaction tank 1 (5) is connected by suction pump (6) with tubular membrane 1 (7).Tubular membrane 1 (7)
Mud discharging mouth be connected with plate and frame filter press 2 (8), the water inlet of reaction tank 2 (9) is connected with tubular membrane 1 (7), reaction tank 2 (9)
Water outlet is connected by suction pump (10) with filtering ponds (11).The lower sodium sulphate of price is selected to go in reaction tank 1 (5) first
Except part calcium ion, then it is separated by solid-liquid separation by tubular membrane 1 (7), obtains mud mixture and three-level supernatant.It is reacting
Sodium carbonate liquor is added in pond 2 (9), is generated precipitation of calcium carbonate, is separated by solid-liquid separation, is obtained with filtering ponds (11) after fully reacting
Level Four supernatant and calcium carbonate solid product.
As a further improvement of the present invention, the magnesium ion removal unit include reaction tank 3 (12), tubular membrane 2 (14),
Plate and frame filter press 3 (15)；Tray drier (16), rotary calcining furnace (17) and nano-level grinder (18).The reaction tank 3 (12)
Water inlet be connected with the lower part of filtering ponds (11), sodium hydroxide solution is added in the reaction tank 3 (12) and dispersing agent generates hydrogen
The water outlet of magnesium oxide precipitation, the reaction tank 3 (12) is connected by suction pump (13) with tubular membrane 2 (14).Tubular membrane 2 (14)
Mud discharging mouth be connected with plate and frame filter press 3 (15), subsequently into tray drier (16), rotary calcining furnace (17) and nano-milled
Machine (18) carries out filters pressing, drying, calcining and grinding, obtains nano magnesia.
As a further improvement of the present invention, the desalination unit includes nanofiltration device (20), and suction pump (21) is reverse osmosis
Device (22) and high-salt wastewater evaporator (23).Nanofiltration device (20) influent side is connected with tubular membrane thickener 2 (14), receives
Filter device (20) water outlet side and reverse osmosis unit (22) influent side pass through suction pump (21) and are connected, nanofiltration device (20) and reverse osmosis
Concentrated water obtained by device (22) enters high-salt wastewater evaporator (23).Pyatyi supernatant is passed through into nanofiltration device and reverse osmosis unit
Afterwards, it produces water side and obtains the fresh water of water quality reaching standard, can be used as industrial water and carry out reflux use, concentrated water side is evaporated crystallization and obtains
Solid mixed salt is comprehensively utilized.
Compared with prior art, the present invention having the following technical effect that
The present invention carries out the softening of desulfurization wastewater by the method for step-by-step processing, during softening, to by-products at different levels
Product are recycled, and the magnesia of high-purity, gypsum and lime stone has especially been prepared, and realize the comprehensive utilization of resource,
And treated that waste water quality is completely up to standard, can be used as industrial water and carries out reflux use.
The present invention reacts calcium ion with sulfate ion and generates calcium sulfate, so by adding metabisulfite solution in early period
Calcium sulphate solid product, i.e. gypsum product are obtained by dehydration and drying afterwards.
Detailed description of the invention
Attached drawing 1 is schematic structural view of the invention；
Attached drawing 2 is process flow chart of the invention.
In attached drawing: 1- desulfurizing tower；2- homogeneous pond；3- precipitation reaction pond；4- plate and frame filter press 1；5- reaction tank 1；6,10,
13,19,21- suction pump；7- tubular membrane 1；8- plate and frame filter press 2；9- reaction tank 2；11- filtering ponds；12- reaction tank 3；14- pipe
Formula film 2；15- plate and frame filter press 3；16- tray drier；17- rotary calcining furnace；18- nano-level grinder；20- nanofiltration device；
22- reverse osmosis unit；23- high-salt wastewater evaporator；
Arrow in attached drawing indicates the inflow direction of material.
Specific embodiment
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation
Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common
Technical staff's every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
The present invention includes:
Reaction tank 1 (5) is used to separate a part of calcium ion, the water inlet of the reaction tank 1 (5) and precipitation reaction pond
Top be connected, the water outlet of the reaction tank 1 (5) is connected by suction pump (6) with tubular membrane 1 (7).If secondary supernatant calcium
When ion concentration is higher than 1000mg/L, sodium hydroxide solution is added, pH is controlled 7.0, solid sodium sulfate is then added, adds
Amount are as follows: 3 (x-1000) mg/L；Then calcium sulfate is added, dosage is the 1% of solid sodium sulfate；The x is calcium ion concentration,
Unit mg/L；If calcium ion concentration is lower than 1000mg/L in secondary supernatant, pH is controlled 7.0 with sodium hydroxide solution
Afterwards, it is separated by solid-liquid separation by tubular membrane 1 (7), obtains mud mixture and three-level supernatant.
Reaction tank 2 (9) is used to separate remaining all calcium ions, the water inlet and tubular membrane 1 of the reaction tank 2 (9)
(7) it is connected, the water outlet of the reaction tank 2 (9) is connected by suction pump with filtering ponds (11).Sodium carbonate liquor is added, is generated
Precipitation of calcium carbonate is separated by solid-liquid separation with filtering ponds (11) after fully reacting, obtains level Four supernatant and calcium carbonate solid product.
Reaction tank 3 (12), is used to separate magnesium ion, under the water inlet of the reaction tank 3 (12) and filtering ponds (11)
Portion is connected, and the water outlet of the reaction tank 3 (12) is connected by suction pump (13) with tubular membrane 2 (14).It is molten to add sodium hydroxide
Liquid generates magnesium hydrate precipitate, to separate from system.
The pretreatment unit includes homogeneous pond (2), precipitation reaction pond (3) and plate and frame filter press 1 (4)；The homogeneous pond
(2) water inlet passes through desulfurization wastewater pipeline connection desulfurizing tower (1), homogeneous pond (2) water outlet and the precipitation reaction pond
(3) it is connected.The lower part in precipitation reaction pond (3) is connected with plate and frame filter press 1 (4), and water outlet is connected with reaction tank 1 (5).Due to from
There are many slightly solubility substances in the desulfurization wastewater that desulfurizing tower directly comes out, and the ion of slightly solubility substance can be generated, only
It is these ions due to being dispersed in different positions, can not contacts, it can not be in conjunction with generation slightly solubility substance, it is therefore desirable to using
Matter pond carries out homogeneous, is combined the ion that indissoluble object can be generated and generates indissoluble object, then precipitate indissoluble object, in level-one
Clear liquid imports in next stage reaction unit, to remove influence of these substances to subsequent reactions.It adds and recaptures in precipitation reaction pond
Precipitating is generated after agent, is sufficiently separated by solid-liquid separation after ageing, obtains secondary supernatant.Precipitation reaction pond is for removing removing heavy metals
Ion.
The calcium ion removal unit includes reaction tank 1 (5), suction pump (6,10), tubular membrane 1 (7) and plate and frame filter press 2
(8), reaction tank 2 (9) and filtering ponds (11).The water inlet of reaction tank 1 (5) is connected with the top of precipitation reaction pond (3), reaction tank
The water outlet of 1 (5) is connected by suction pump (6) with tubular membrane 1 (7).The mud discharging mouth and plate and frame filter press 2 (8) of tubular membrane 1 (7)
It is connected, the water inlet of reaction tank 2 (9) is connected with tubular membrane 1 (7), and the water outlet of reaction tank 2 (9) passes through suction pump (10) and mistake
Filter tank (11) is connected.It selects the lower sodium sulphate of price to remove part calcium ion in reaction tank 1 (5) first, then passes through pipe
Formula film 1 (7) is separated by solid-liquid separation, and mud mixture and three-level supernatant are obtained.Sodium carbonate liquor is added in reaction tank 2 (9),
Precipitation of calcium carbonate is generated, is separated by solid-liquid separation after fully reacting with filtering ponds (11), obtains level Four supernatant and calcium carbonate solid
Product.
The magnesium ion removal unit includes reaction tank 3 (12), tubular membrane 2 (14), plate and frame filter press 3 (15)；Disc type is dry
Dry machine (16), rotary calcining furnace (17) and nano-level grinder (18).The water inlet of the reaction tank 3 (12) and filtering ponds (11)
Lower part is connected, and sodium hydroxide solution is added in reaction tank 3 (12) and dispersing agent generates magnesium hydrate precipitate, the reaction tank 3
(12) water outlet is connected by suction pump (13) with tubular membrane 2 (14).The mud discharging mouth and plate and frame filter press 3 of tubular membrane 2 (14)
(15) be connected, subsequently into tray drier (16), rotary calcining furnace (17) and nano-level grinder (18) progress filters pressing, drying,
Calcining and grinding, obtain nano magnesia.
The desalination unit includes nanofiltration device (20), suction pump (21), reverse osmosis unit (22) and high-salt wastewater evaporation
Device (23).Nanofiltration device (20) influent side is connected with tubular membrane 2 (14), nanofiltration device (20) water outlet side and reverse osmosis unit
(22) influent side is connected by suction pump (21), and concentrated water obtained by nanofiltration device (20) and reverse osmosis unit (22) enters high-salt wastewater
Evaporator (23).By Pyatyi supernatant after nanofiltration device and reverse osmosis unit, produces water side and obtain purity fresh water up to standard, it can
It carries out reflux as industrial water to use, concentrated water side, which is evaporated crystallization and obtains solid mixed salt, to be comprehensively utilized.
The technical process for carrying out the separating calcium and magnesium of desulfurization wastewater using system of the present invention is as follows:
(1) by desulfurization wastewater in homogeneous pond abundant homogeneous, precipitate indissoluble object completely, obtain level-one supernatant；Sampling
Level-one supernatant water quality is chemically examined, each ion concentration is detected；
(2) level-one supernatant is imported into precipitation reaction pond, adds generate precipitating after recapturing agent thereto；It is sufficiently aged laggard
Row is separated by solid-liquid separation, and obtains secondary supernatant；The reaction occurred during this is as follows:
M2++S2-=MS ↓
Wherein: M2+For heavy metal ion；
(3) secondary supernatant is imported into reaction tank 1, if secondary supernatant calcium ion concentration is higher than 1000mg/L, added
Concentration is 15wt% sodium hydroxide solution, and pH is controlled 7.0, then adds solid sodium sulfate, dosage are as follows: 3 (x-1000)
mg/L；Then calcium sulfate is added, dosage is the 1% of solid sodium sulfate；The x is calcium ion concentration, unit mg/L；If second level
When calcium ion concentration is lower than 1000mg/L in supernatant, pH is controlled after 7.0 with sodium hydroxide solution, passes through tubular type film device
It is separated by solid-liquid separation, obtains mud mixture and three-level supernatant；It is CaSO after mud mixture dehydration4·2H2O, wherein containing
There is a small amount of Mg (OH)2；Gypsum product is obtained after mud mixture is dehydrated, the water sloughed, which is passed through in homogeneous pond, to be continued to join
With circulation；
The reaction occurred during this is as follows:
Ca2++SO4 2-=CaSO4↓
Mg2++2OH-=Mg (OH)2↓
(4) three-level supernatant is imported in reaction tank 2, adds sodium carbonate liquor, dosage is according to following ratio: carbonate
The molar ratio of ion and calcium ion is 1.1-1.3；Generation precipitation of calcium carbonate, 30 DEG C of reaction temperature, time 40min；Fully reacting
It is separated by solid-liquid separation afterwards with filtering ponds 1, obtains level Four supernatant and calcium carbonate pug, after calcium carbonate pug is dehydrated
Calcium carbonate solid product is obtained, is back to use in the desulfurization workshop section of desulfurizing tower；The reaction occurred during this is as follows:
Ca2++CO3 2-=CaCO3↓
Mg2++CO3 2-=MgCO3↓
(5) level Four supernatant is imported in reaction tank 3, adds sodium hydroxide solution and PEG-6000 dispersing agent, generate hydrogen
Magnesium oxide precipitation；It is separated by solid-liquid separation with tubular type film device, obtains Pyatyi supernatant；It is obtained after precipitating filtering means dehydration is dry high-purity
Spend magnesium hydroxide solid product；To guarantee magnesium ion precipitating completely, dispersing agent additional amount is 2.5mL/100mL waste water, hydroxide
Sodium should be added slowly, and the liquid inlet volume of sodium hydroxide is 6mL/min, and pH control blender in 11.0~11.5, reaction process turns
Fast 600r/min, mixing time 30min, temperature 60 C are aged 60min after stirring, and 60 DEG C of Aging Temperature；
The reaction occurred during this is as follows:
Mg2++2OH-=Mg (OH)2↓
(6) calcining is dried in magnesium hydroxide solid product, and obtains nano magnesia after being ground with nano-level grinder；
1600 DEG C of calcination temperature, time 1.5h；The reaction occurred during this is as follows:
(7) it by Pyatyi supernatant after nanofiltration device and reverse osmosis unit, produces water side and obtains purity fresh water up to standard, it can
It carries out reflux as industrial water to use, concentrated water side, which is evaporated crystallization and obtains solid mixed salt, to be comprehensively utilized.
Embodiment described above is only that preferred embodiment of the invention is described, and is not carried out to the scope of the present invention
It limits, without departing from the spirit of the design of the present invention, those of ordinary skill in the art make technical solution of the present invention
Various changes and improvements, should all fall into claims of the present invention determine protection scope in.
Claims (5)
1. a kind of system for preparing nanometer magnesia powder as raw material using desulfurization wastewater characterized by comprising reaction tank 1
(5), it is used to separate a part of calcium ion, the water inlet of the reaction tank 1 (5) is connected with the top in precipitation reaction pond, described
The water outlet of reaction tank 1 (5) is connected by suction pump (6) with tubular membrane 1 (7)；Reaction tank 2 (9) is used to separate remaining all
The water inlet of calcium ion, the reaction tank 2 (9) is connected with tubular membrane 1 (7), and the water outlet of the reaction tank 2 (9) is by drawing water
Pump is connected with filtering ponds (11).Reaction tank 3 (12) is used to separate magnesium ion, the water inlet of the reaction tank 3 (12) and filtering
The lower part in pond (11) is connected, and the water outlet of the reaction tank 3 (12) is connected by suction pump (13) with tubular membrane 2 (14).
2. a kind of system for preparing nano magnesia as raw material using desulfurization wastewater according to claim 1, which is characterized in that
The pretreatment unit includes homogeneous pond (2), precipitation reaction pond (3) and plate and frame filter press 1 (4)；The homogeneous pond (2) enters water
Mouth is connected by desulfurization wastewater pipeline connection desulfurizing tower (1), homogeneous pond (2) water outlet with the precipitation reaction pond (3).It is heavy
The lower part of shallow lake reaction tank (3) is connected with plate and frame filter press 1 (4), and water outlet is connected with reaction tank 1 (5).
3. a kind of system for preparing nano magnesia as raw material using desulfurization wastewater according to claim 1, which is characterized in that
The calcium ion removal unit includes reaction tank 1 (5), suction pump (6,10), tubular membrane 1 (7) and plate and frame filter press 2 (8), reaction
Pond 2 (9) and filtering ponds (11).The water inlet of reaction tank 1 (5) is connected with the top of precipitation reaction pond (3), and reaction tank 1 (5) goes out
The mouth of a river is connected by suction pump (6) with tubular membrane 1 (7).The mud discharging mouth of tubular membrane 1 (7) is connected with plate and frame filter press 2 (8), reaction
The water inlet in pond 2 (9) is connected with tubular membrane 1 (7), and the water outlet of reaction tank 2 (9) passes through suction pump (10) and filtering ponds (11) phase
Even.
4. a kind of system using desulfurization wastewater preparing magnesium hydroxide according to claim 1, which is characterized in that the magnesium
Ion remaval unit includes reaction tank 3 (12), tubular membrane 2 (14), plate and frame filter press 3 (15)；Tray drier (16), revolution are forged
Burn furnace (17) and nano-level grinder (18).The water inlet of the reaction tank 3 (12) is connected with the lower part of filtering ponds (11), is reacting
Sodium hydroxide solution is added in pond 3 (12) and dispersing agent generates magnesium hydrate precipitate, the water outlet of the reaction tank 3 (12) passes through
Suction pump (13) is connected with tubular membrane 2 (14).The mud discharging mouth of tubular membrane 2 (14) is connected with plate and frame filter press 3 (15), subsequently into
Tray drier (16), rotary calcining furnace (17) and nano-level grinder (18) carry out filters pressing, drying, calcining and grinding, are received
Rice magnesia.
5. a kind of system using desulfurization wastewater preparing magnesium hydroxide according to claim 1, which is characterized in that described to remove
Salt unit includes nanofiltration device (20), suction pump (21), reverse osmosis unit (22) and high-salt wastewater evaporator (23).The nanofiltration
Device (20) influent side is connected with tubular membrane 2 (14), and nanofiltration device (20) water outlet side passes through with reverse osmosis unit (22) influent side
Suction pump (21) is connected, and concentrated water obtained by nanofiltration device (20) and reverse osmosis unit (22) enters high-salt wastewater evaporator (23).
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