CN106673019A - Method for producing sodium carbonate with salt-containing wastewater and CO2 - Google Patents
Method for producing sodium carbonate with salt-containing wastewater and CO2 Download PDFInfo
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- CN106673019A CN106673019A CN201510763581.9A CN201510763581A CN106673019A CN 106673019 A CN106673019 A CN 106673019A CN 201510763581 A CN201510763581 A CN 201510763581A CN 106673019 A CN106673019 A CN 106673019A
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- China
- Prior art keywords
- salt
- nacl
- salt solution
- rich
- brine waste
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 title claims abstract description 74
- 150000003839 salts Chemical class 0.000 title claims abstract description 70
- 229910000029 sodium carbonate Inorganic materials 0.000 title claims abstract description 36
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 24
- 239000002351 wastewater Substances 0.000 title abstract description 18
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 126
- 238000000034 method Methods 0.000 claims abstract description 106
- 239000011780 sodium chloride Substances 0.000 claims abstract description 50
- 238000003763 carbonization Methods 0.000 claims abstract description 32
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims abstract description 22
- 239000012452 mother liquor Substances 0.000 claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 8
- 238000001354 calcination Methods 0.000 claims abstract description 7
- 238000000926 separation method Methods 0.000 claims abstract description 4
- 239000012266 salt solution Substances 0.000 claims description 70
- 239000012267 brine Substances 0.000 claims description 55
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 55
- 239000002699 waste material Substances 0.000 claims description 55
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 37
- 235000017550 sodium carbonate Nutrition 0.000 claims description 29
- 238000010438 heat treatment Methods 0.000 claims description 28
- 238000001704 evaporation Methods 0.000 claims description 19
- 230000008020 evaporation Effects 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 18
- 239000012528 membrane Substances 0.000 claims description 18
- 238000001556 precipitation Methods 0.000 claims description 14
- 238000002425 crystallisation Methods 0.000 claims description 13
- 230000008025 crystallization Effects 0.000 claims description 13
- 238000001728 nano-filtration Methods 0.000 claims description 12
- 238000001223 reverse osmosis Methods 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000000909 electrodialysis Methods 0.000 claims description 8
- 239000007791 liquid phase Substances 0.000 claims description 8
- -1 polytetrafluoroethylene Polymers 0.000 claims description 8
- 150000001412 amines Chemical class 0.000 claims description 6
- 229920002301 cellulose acetate Polymers 0.000 claims description 6
- 239000003507 refrigerant Substances 0.000 claims description 6
- 239000004695 Polyether sulfone Substances 0.000 claims description 5
- 229920006393 polyether sulfone Polymers 0.000 claims description 5
- 230000008929 regeneration Effects 0.000 claims description 5
- 238000011069 regeneration method Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N n-propyl alcohol Natural products CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 239000004760 aramid Substances 0.000 claims description 2
- 150000004982 aromatic amines Chemical class 0.000 claims description 2
- 229920003235 aromatic polyamide Polymers 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 239000002033 PVDF binder Substances 0.000 claims 1
- 238000001764 infiltration Methods 0.000 claims 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims 1
- 238000000066 reactive distillation Methods 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 36
- 229910001868 water Inorganic materials 0.000 abstract description 36
- 239000003245 coal Substances 0.000 abstract description 20
- 239000000126 substance Substances 0.000 abstract description 20
- 230000008901 benefit Effects 0.000 abstract description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 abstract description 4
- 238000003889 chemical engineering Methods 0.000 abstract description 2
- 239000002244 precipitate Substances 0.000 abstract 2
- 235000017557 sodium bicarbonate Nutrition 0.000 abstract 2
- 238000004065 wastewater treatment Methods 0.000 abstract 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 21
- 238000005255 carburizing Methods 0.000 description 10
- 239000003153 chemical reaction reagent Substances 0.000 description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 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 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 3
- 230000008014 freezing Effects 0.000 description 3
- 238000007710 freezing Methods 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000012372 quality testing Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000013535 sea water Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 238000005057 refrigeration Methods 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 241000208340 Araliaceae Species 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229920006266 Vinyl film Polymers 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229940058401 polytetrafluoroethylene Drugs 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D7/00—Carbonates of sodium, potassium or alkali metals in general
- C01D7/16—Preparation from compounds of sodium or potassium with amines and carbon dioxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/01—Chlorine; Hydrogen chloride
- C01B7/03—Preparation from chlorides
- C01B7/035—Preparation of hydrogen chloride from chlorides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D7/00—Carbonates of sodium, potassium or alkali metals in general
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/141—Feedstock
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The invention relates to the field of coal chemical engineering wastewater treatment, and discloses a method for producing sodium carbonate with salt-containing wastewater and CO2. The method comprises the following steps: (1) performing separation treatment on the salt-containing wastewater so as to remove divalent salts in the salt-containing wastewater and obtain mono-valent salt enriched salt-containing water; (2) in the presence of an accelerant and CO2, performing carbonization treatment on the mono-valent salt enriched salt-containing water so as to obtain a sodium bicarbonate precipitate and carbonization mother liquor; (3) performing calcining treatment on the sodium bicarbonate precipitate, thereby obtaining sodium carbonate. By adopting the method disclosed by the invention, CO2 discharged from coal chemical industry production can be successfully used in the salt-containing wastewater treatment process, and besides the difficulty in treating NaCl with a low additional value in the salt-containing wastewater, and great carbon emission reduction burden can be effectively solved, certain economic benefits can be made, and effective technical methods for achieving the purpose of zero emission of the salt-containing wastewater can be provided for enterprises of coal chemical industry and the like.
Description
Technical field
The present invention relates to coal chemical industrial waste water process field, in particular it relates to it is a kind of using brine waste and
CO2The method of production soda ash.
Background technology
In recent years, by the dual restriction of water resource and water environmental problems, domestic Coal Chemical Engineering Project is proposed one after another
Wastewater zero discharge scheme.Wastewater zero discharge is on the basis of classifying rationally is carried out to water system, with reference to useless
Water feature, realizes maximum treatment for reuse, no longer in the form of the waste water outside drain into setting for natural water
Meter scheme.By water quality and the water yield, coal chemical industrial waste water is broadly divided into coal gasification organic wastewater and brine waste.
Brine waste includes biochemical treatment waste water up to standard and peace and quiet waste water, and total dissolved solidss (TDS) content is
1-3g/L.Coal Chemical Industry brine waste is constituted based on inorganic salts, slightly solubility hardly degraded organic substance.Typically
Coal Chemical Industry brine waste zero emission flow process obtains TDS by pretreatment and film concentration technology first
The high strong brine of 50-80g/L, is then tied by the further concentrate of the crystallization treatment technique such as evaporative crystallization
Brilliant salt.
However, crystal salt composition complexity, concentration of narmful substance height that crystallizer is discharged, need to be given up as dangerous
Thing is processed, it is impossible to and boiler ash, gasifier slag etc. remove slag together that field is mixed to bury.Hazardous waste is final
Dispose it is previous as pre-processed using the method such as physics, chemistry, biology, change its physics, chemistry,
The characteristics such as biology, reduce toxicity, reduce volume, it is to avoid this life environmental pollution.At present for how passing through
Crystal salt is changed into unhazardous waste and there is no feasible scheme to propose by pretreatment.
Therefore, how crystal salt is rationally utilized, realizes that real waste water near-zero release scheme is coalification industrial and commercial bank
The problem of industry urgent need to resolve.
The content of the invention
The invention aims to overcome drawbacks described above of the prior art, there is provided a kind of useless using saliferous
Water and CO2The method of production soda ash, the method can rationally utilize crystal salt, realize that real waste water is near
Zero-emission, and Coal Chemical Industry is successfully produced the CO of discharge2The disposal process of brine waste is used, together
When efficiently solve the disposal difficulties of low value-added NaCl and huge carbon emission reduction pressure in brine waste.
The present inventor has found in numerous studies, in the brine waste of current Coal Chemical Industry production discharge
The main method of disposal of NaCl is evaporative crystallization, but the added value of its NaCl for producing is relatively low, not
Have good whereabouts, and it is mishandling to be easy to be classified as danger useless, so as to greatly increase the expense of disposal；
On the contrary, at present the raw material such as industrial widely used NaCl produces soda ash (the market appearance of whole world soda ash
Amount is about ten thousand tons/year of 5000-6000), and NaCl mostlys come from seawater and the technique such as evaporates brine, however, needing
To be drawn attention, the NaCl in seawater is a kind of component of naturally occurring, be not in itself one kind
Pollution sources.Simultaneously, Coal Chemical Industry is due to its process characteristic, the height of up to millions of tonnes of annual discharge
Pure CO2Gas, is faced with huge carbon emission reduction pressure.Therefore, comprehensive preceding factors, the present invention's sends out
A person of good sense is had surprisingly found that by substantial amounts of test, by the way that brine waste to be carried out successively separating treatment and carbon
Change is processed so that brine waste removes divalent salts to obtain rich monovalent salt salt solution by the separating treatment,
In accelerator and CO2In the presence of, rich monovalent salt salt solution is obtained into sodium acid carbonate by the carbonization treatment and is sunk
Form sediment and carbonization mother liquor, in the way of sodium acid carbonate precipitation is carried out into calcination processing to obtain soda ash, can utilize
And first using the CO of Coal Chemical Industry production discharge2The substantial amounts of NaCl lifes contained in gas and brine waste
Soda ash is produced, disposal difficulties of low value-added NaCl and huge had both been efficiently solved in brine waste simultaneously
Carbon emission reduction pressure, and successfully turn waste into wealth.
Therefore, to achieve these goals, the invention provides a kind of utilize brine waste and CO2Production
The method of soda ash, methods described includes：
(1) brine waste is carried out into separating treatment, removes the divalent salts in the brine waste, with
To rich monovalent salt salt solution；
(2) in accelerator and CO2In the presence of, the rich monovalent salt salt solution is carried out into carbonization treatment, obtain
To sodium acid carbonate precipitation and carbonization mother liquor；
(3) the sodium acid carbonate precipitation for obtaining step (2) carries out calcination processing, to obtain soda ash.
The utilization brine waste and CO of the present invention2The method of production soda ash, can not only effectively solving saliferous
The disposal difficulties of low value-added NaCl in waste water, additionally it is possible to produce certain economic benefit, are Coal Chemical Industry
Realize that the near-zero release target of brine waste provides effective technological means Deng enterprise.Meanwhile, using rich one
Valency salt salt solution or richness NaCl salt solution, accelerator and CO2Between carburizing reagent production sodium carbonate, success
Coal Chemical Industry is produced the CO of discharge on ground2The disposal process of brine waste is used, brine waste is being solved
In low value-added NaCl disposal difficulties while, also efficiently solve huge carbon emission reduction pressure.Separately
Outward, it is of the invention it is a kind of preferred embodiment, by being heated to carbonization mother liquor or electricity
Dialysis is processed, can not only regeneration accelerator so that accelerator can recycle, but also can obtain
To hydrochloric acid, i.e., only need to consume value relatively low NaCl and CO2, it becomes possible to production is pure compared with high added value
Alkali and hydrochloric acid, can greatly improve the economy of process.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Description of the drawings
Fig. 1 is the utilization brine waste and CO of one embodiment of the present invention2Joint-producing anhydrous sodium carbonate and hydrochloric acid
Process chart.
Fig. 2 is a kind of utilization brine waste and CO of preferred embodiment of the present invention2Joint-producing anhydrous sodium carbonate and salt
The process chart of acid.
Fig. 3 is the utilization brine waste and CO of another kind of preferred embodiment of the present invention2Joint-producing anhydrous sodium carbonate and
The process chart of hydrochloric acid.
Specific embodiment
The specific embodiment of the present invention is described in detail below in conjunction with Fig. 1-Fig. 3.It should be understood that
It is that specific embodiment described herein is merely to illustrate and explains the present invention, is not limited to this
Invention.
The invention provides a kind of utilize brine waste and CO2The method of production soda ash, the method includes：
(1) brine waste is carried out into separating treatment, removes the divalent salts in the brine waste, with
To rich monovalent salt salt solution；
(2) in accelerator and CO2In the presence of, the rich monovalent salt salt solution is carried out into carbonization treatment, obtain
To sodium acid carbonate precipitation and carbonization mother liquor；
(3) the sodium acid carbonate precipitation for obtaining step (2) carries out calcination processing, to obtain soda ash.
The method according to the invention, in order to ensure that carbonization treatment has preferable effect, under preferable case,
In step (1), it is 50-360g/L that the condition of separating treatment causes the concentration of NaCl in rich monovalent salt salt solution,
More preferably 90-300g/L.
For the specific embodiment of separating treatment, there is no particular limitation, can be commonly used in the art each
Method for separating and processing is planted, as long as the condition that can control separating treatment causes NaCl in rich monovalent salt salt solution
Concentration be 50-360g/L.It is not more than the brine waste of 10g/L preferably for NaCl concentration,
Separating treatment includes that carrying out reverse-osmosis treated and nanofiltration successively to brine waste is processed；For NaCl concentration
Brine waste more than 10g/L, separating treatment includes carrying out nanofiltration process to brine waste.It is further excellent
Selection of land, the condition of reverse-osmosis treated includes：Pressure is 0-10MPa, and temperature is 10-50 DEG C, membrane aperture
For 0.3-1nm, membrane material is selected from cellulose acetate, aromatic polyamides, poly tetrafluoroethylene, poly- inclined fluorine
One or more in vinyl film and polypropylene screen；Preferably, the condition that nanofiltration is processed includes：Pressure is
0.5-3MPa, temperature is 10-50 DEG C, and membrane aperture is 1-2nm, and membrane material is selected from cellulose acetate, sulphur
Change one or more in polysulfones, sulfonated polyether sulfone, polyamide and polyvinyl alcohol.
As shown in figure 1, the method according to the invention, excellent in order to further improve the effect of carbonization treatment
In the case of choosing, the method also includes：In step (2), before carbonization treatment, to rich monovalent salt salt
Water carries out concentration, improves the concentration of NaCl in rich monovalent salt salt solution to obtain rich NaCl salt solution.Enter
One step is preferably so that the concentration of NaCl is 150-360g/L in rich NaCl salt solution, still more preferably
For 200-350g/L, then still more preferably it is saturation NaCl salt solution.
For concentration, with the specific embodiment that obtains rich NaCl salt solution, there is no particular limitation, can
Various methods commonly used in the art are thought, as long as so that the concentration of NaCl is in richness NaCl salt solution
150-360g/L.Under preferable case, in step (2), the mode of concentration is freezing and crystallizing
Process or heating evaporation is processed, the embodiment of Freeze crystallization includes：In the presence of refrigerant,
Rich monovalent salt salt solution is freezed 10-300min at 0～-25 DEG C, ice and richness NaCl salt solution is obtained, enters one
Preferably, the ice that Freeze crystallization is obtained is reclaimed and return after cold production system recycling step.It is right
In refrigerant, there is no particular limitation, can be various refrigerants commonly used in the art, for example can be with
For liquefied ammonia, propylene or fluorinated hydrocarbon.
Under preferable case, the embodiment of heating evaporation process includes：By rich monovalent salt salt solution in 80-120
10-300min is heated at DEG C, rich NaCl salt solution is obtained.
With the method for the invention it is preferred in the case of, in step (2), the embodiment of carbonization treatment
Including：By rich monovalent salt salt solution or richness NaCl salt solution and accelerator and CO2Carry out carburizing reagent, Fu Yi
NaCl, CO in valency salt salt solution or richness NaCl salt solution2It is 1-3 with the mol ratio of accelerator：1-4：1,
Reaction temperature is 25-50 DEG C, and the reaction time is 10-300min.
The method according to the invention, rich monovalent salt salt solution or richness NaCl salt solution (are used with accelerator in following formula
A is represented) and CO2Carry out carburizing reagent and generate sodium acid carbonate (NaHCO3) precipitation, key reaction formula
As shown in formula (1)：
NaCl+CO2+A+H2O->NaHCO3↓+A·H++Cl- (1)
The method according to the invention, it will be understood by those skilled in the art that of the present invention " promote
Enter agent " reaction of carbon dioxide, sodium chloride and water can not only be promoted to generate sodium acid carbonate, and can carry
High reaction speed.
With the method for the invention it is preferred in the case of, accelerator is organic amine, more preferably tertiary amine
There is the organic amine of sterically hindered structure with other, be still more preferably fatty amines, alcamines, acyl
One or more in amine, ester cyclammonium class and aromatic amine, then be still more preferably N- methyl two
One or more in monoethanolamine, triethanolamine and 2- methyl-2-amino -1- propyl alcohol.
Sodium acid carbonate precipitation and carbonization mother liquor can be obtained in carbonization treatment by way of separation of solid and liquid, it is right
It is not particularly limited in the mode of separation of solid and liquid, can is various methods commonly used in the art, for example can be with
For filtration or centrifugation.
With the method for the invention it is preferred in the case of, in step (3), the temperature of calcination processing is 150-250
DEG C, the time is 10-150min.
Method according to the invention it is possible to the carbonization mother liquor that step (2) is obtained is directly entered into downstream work
Used as materials such as reactant, additives in skill or other processing steps, in order to further reduce into
Originally, increase economic efficiency, under preferable case, the method also includes that the carbonization for obtaining step (2) is female
Liquid is heated or electrodialysis process, with regeneration accelerator and obtains hydrochloric acid.
The method according to the invention, for the condition of electrodialysis process, there is no particular limitation, as long as can
Accelerator is regenerated and is obtained hydrochloric acid, this is known to those skilled in the art, will not be described here.
In step (4), under preferable case, the mode of heating is that heating flash evaporation is processed, reacts essence
Evaporate process, rectification under vacuum process or extracting rectifying to process, more preferably heating flash evaporation is processed.More enter
Preferably, the condition of heating flash evaporation process includes one step：Temperature is 80-300 DEG C, and the time is 20-300min,
Pressure is 0.05-0.15MPa.By temperature rise to 80-300 DEG C speed can in wider scope ripple
Dynamic, under preferable case, heating rate is 1-10 DEG C/min.
The method according to the invention, it will be understood by those skilled in the art that carbonization mother liquor is through heating
Process or electrodialysis process can realize the regeneration of accelerator, at the same can obtain hydrogen chloride gas and/or
Water.By the ratio for controlling hydrogen chloride gas and water mixing, the hydrochloric acid of variable concentrations, such as work can be obtained
Widely used concentration is the technical hydrochloric acid of 31wt% in industry.Wherein, accelerator regenerates and obtains chlorination
Shown in the main reaction equation such as formula (2) of the process of hydrogen：
A·H++Cl-->A+HCl↑ (2)
With the method for the invention it is preferred in the case of, the method also include will heat or electrodialysis at
The liquid phase material that reason is obtained is back to carbonization treatment.
The method according to the invention, the method also includes：Will be at separating treatment, concentration and heating
The water obtained during reason or electrodialysis process returns production system and recycles.
The method according to the invention, for brine waste, there is no particular limitation, can lead for petrochemical industry
The brine waste that domain, coal chemical technology and power domain, iron and steel domain, field of seawater desalination are produced,
Under preferable case, NaCl contents are 2-400g/L, Ca in brine waste2+With Mg2+Total content be
0-200mg/L, COD value is 0-1000mg/L.
The method according to the invention, the soda ash that step (3) is obtained at least conforms to the class of technical grade sodium carbonate II
The quality standard of certified products, i.e. Na2CO3Content >=98 mass %, NaCl content≤1.2 mass %, water
Insolubles content≤0.15 mass % etc..
Embodiment
Hereinafter will be described the present invention by embodiment, but and be not so limited the present invention model
Enclose.In following examples, if no special instructions, the method for being used is method commonly used in the art.
The each component and its content in water is determined using inductively coupled plasma (ICP) method.
Aluminium polychloride is purchased from Hebei Shen Mei chemical building materials Co., Ltd, and the trade mark is SM-103.
Embodiment 1
The present embodiment is used for explanation using method shown in Fig. 2, using brine waste and CO2Joint-producing anhydrous sodium carbonate and
The method of hydrochloric acid.
The waste water discharged from coal chemical industry enterprises is simulated as raw water using synthesis brine waste, its water quality ginseng
Number is as shown in table 1.
(1) it is 10m by flow3The above-mentioned synthesis brine waste of/h carries out reverse-osmosis treated, obtains flow
For 6.6m3The product water and flow of/h is 3.4m3The NaCl concentration of/h is the reverse osmosis concentrated water of 100g/L,
Product water is returned into production system to recycle, wherein, the condition of reverse-osmosis treated includes：Pressure is
5MPa, temperature is 30 DEG C, and membrane aperture is 0.5nm, and membrane material is cellulose acetate.
(2) it is 3.4m by flow3The reverse osmosis concentrated water of/h carries out nanofiltration process, obtains flow for 0.85m3/h
Rich divalent salts salt solution and flow be 2.55m3The NaCl concentration of/h is (rich for the rich monovalent salt salt solution of 90g/L
The water quality parameter of monovalent salt salt solution is as shown in table 1).0.0002wt% waddings are added in rich divalent salts salt solution
Solidifying agent aluminium polychloride, separates out divalent salts precipitation.Wherein, the condition that nanofiltration is processed includes：Pressure is
2MPa, temperature is 25 DEG C, and membrane aperture is 1.5nm, and membrane material is sulfonated polyether sulfone.
(3) it is 2.55m by flow3The rich monovalent salt salt solution of/h carries out Freeze crystallization, wherein, it is cold
Freezing the method for crystallization treatment includes：In the presence of freon refrigerant, by rich monovalent salt salt solution at -25 DEG C
Lower refrigeration 180min, it is 0.8m to obtain ice and flow3The NaCl concentration of/h is the NaCl salt of 285g/L
Water, the ice that Freeze crystallization is obtained is reclaimed and return after cold production system recycling.
(4) it is 0.8m by flow3The NaCl concentration of/h is the NaCl salt solution and 156kg N- of 285g/L
Methyl diethanolamine and 116L/h CO2Carry out carburizing reagent, reaction temperature is 30 DEG C, the reaction time is
60min, is centrifugally separating to obtain 100kg sodium acid carbonates precipitation and 512kg carbonization mother liquors.
(5) 60min is calcined at sodium acid carbonate being deposited in into 200 DEG C, 63kg soda ash products are obtained.
(6) carbonization mother liquor is carried out into heating flash evaporation process, obtains hydrochloric acid, vapor and remaining liquid phase thing
Material, and remaining liquid phase material is back into step (4) carries out carburizing reagent, wherein, at heating flash evaporation
The condition of reason includes：Temperature is risen into 250 DEG C with the heating rate of 4 DEG C/min, 250 DEG C of temperature is kept
The pressure 30min of degree and 0.08MPa.
Quality testing is carried out to the soda ash that step (5) is obtained, testing result shows：Na2CO3Content is
98.4 mass %, NaCl contents are 1.0 mass %, and water insoluble matter content is 0.09 mass %, meets work
The quality standard of the class certified products of industry level sodium carbonate II.
Table 1
The water of rich monovalent salt salt solution, the NaCl salt solution that step (3) is obtained and ice that step (2) is obtained
Matter parameter is as shown in table 2.
Table 2
| COD(mg/L) | TDS(mg/L) | NaCl concentration (g/L) | |
| Rich monovalent salt salt solution | 230 | 9510 | 90 |
| NaCl salt solution | 241 | 12315 | 285 |
| Ice | 153 | 7206 | 1 |
Embodiment 2
The present embodiment is used for explanation using method shown in Fig. 3, using brine waste and CO2Joint-producing anhydrous sodium carbonate and
The method of hydrochloric acid.
(1) it is 11m by flow3Synthesizing brine waste described in the table 1 of/h carries out reverse-osmosis treated, obtains
Flow is 7m3The product water and flow of/h is 4m3The NaCl concentration of/h is the reverse osmosis concentrated water of 110g/L,
Product water is returned into production system to recycle, wherein, the condition of reverse-osmosis treated includes：Pressure is
5.2MPa, temperature is 28 DEG C, and membrane aperture is 0.5nm, and membrane material is cellulose acetate.
(2) it is 4m by flow3The reverse osmosis concentrated water of/h carries out nanofiltration process, obtains flow for 1.1m3/h
Rich divalent salts salt solution and flow be 2.9m3The NaCl concentration of/h is the rich monovalent salt salt solution of 105g/L.
0.0005wt% flocculant poly aluminium chloride is added in rich divalent salts salt solution, divalent salts precipitation is separated out.Its
In, the condition that nanofiltration is processed includes：Pressure is 2.1MPa, and temperature is 28 DEG C, and membrane aperture is 1.5nm,
Membrane material is sulfonated polyether sulfone.
(3) it is 2.9m by flow3The rich monovalent salt salt solution of/h carries out heating evaporation process, wherein, heating
The method of evaporation process includes：Rich monovalent salt salt solution is heated into 50min at 110 DEG C, obtaining flow is
0.77m3The NaCl concentration of/h is the NaCl salt solution of 326g/L, and the water that heating evaporation process is obtained is returned
Return production system circulation to use.
(4) it is 0.77m by flow3The NaCl concentration of/h is the NaCl salt solution and 214.5kg tri- of 326g/L
Monoethanolamine and 128.1L/h CO2Carburizing reagent is carried out, reaction temperature is 50 DEG C, and the reaction time is 50min,
It is filtrated to get 110kg sodium acid carbonates precipitation and 606kg carbonization mother liquors.
(5) 55min is calcined at sodium acid carbonate being deposited in into 150 DEG C, 69kg soda ash products are obtained.
(6) carbonization mother liquor is carried out into heating flash evaporation process, obtains hydrochloric acid, vapor and remaining liquid phase thing
Material, and remaining liquid phase material is back into step (4) carries out carburizing reagent, wherein, at heating flash evaporation
The condition of reason includes：Temperature is risen into 280 DEG C with the heating rate of 2 DEG C/min, 280 DEG C of temperature is kept
The pressure 25min of degree and 0.05MPa.
Quality testing is carried out to the soda ash that step (5) is obtained, testing result shows：Na2CO3Content is
99.1 mass %, NaCl contents are 0.6 mass %, and water insoluble matter content is 0.1 mass %, meets work
The quality standard of the class certified products of industry level sodium carbonate II.
The NaCl salt solution and heating that rich monovalent salt salt solution that step (2) is obtained, step (3) are obtained steams
The water quality parameter for sending out the water that process is obtained is as shown in table 3.
Table 3
Embodiment 3
The present embodiment is used to illustrate the utilization brine waste and CO of the present invention2The side of joint-producing anhydrous sodium carbonate and hydrochloric acid
Method.
Waste water from coal chemical industry enterprises discharge, its water quality parameter such as table 4 are simulated using synthesis brine waste
It is shown.
Table 4
(1) it is 10m by flow3The above-mentioned synthesis brine waste of/h carries out nanofiltration process, and obtaining flow is
2.5m3The rich divalent salts salt solution of/h and flow are 7.5m3The NaCl concentration of/h is the rich monovalent salt of 90g/L
Salt solution.0.0003wt% flocculant poly aluminium chloride is added in rich divalent salts salt solution, divalent salts is separated out and is sunk
Form sediment.Wherein, the condition that nanofiltration is processed includes：Pressure is 1.9MPa, and temperature is 28 DEG C, and membrane aperture is
1.5nm, membrane material is sulfonated polyether sulfone.
(2) it is 7.5m by flow3The rich monovalent salt salt solution of/h carries out Freeze crystallization, wherein, freezing
The method of crystallization treatment includes：In the presence of freon refrigerant, by rich monovalent salt salt solution at -25 DEG C
Refrigeration 200min, it is 2.35m to obtain ice and flow3The NaCl concentration of/h is the NaCl salt solution of 298g/L,
The ice that Freeze crystallization is obtained is reclaimed and return after cold production system recycling.
(3) it is 2.35m by flow3The NaCl concentration of/h is the NaCl salt solution and 357kg 2- of 298g/L
Methyl-2-amino -1- propyl alcohol and 358L/h CO2Carburizing reagent is carried out, reaction temperature is 25 DEG C, during reaction
Between be 60min, be centrifugally separating to obtain 320kg sodium acid carbonates precipitation and 1774kg carbonization mother liquors.
(4) 70min is calcined at sodium acid carbonate being deposited in into 250 DEG C, 201.9kg soda ash products are obtained.
(5) carbonization mother liquor is carried out into heating flash evaporation process, obtains hydrochloric acid, vapor and remaining liquid phase thing
Material, and remaining liquid phase material is back into step (3) carries out carburizing reagent, wherein, at heating flash evaporation
The condition of reason includes：Temperature is risen into 230 DEG C with the heating rate of 8 DEG C/min, 230 DEG C of temperature is kept
The pressure 40min of degree and 0.09MPa.
Quality testing is carried out to the soda ash that step (4) is obtained, testing result shows：Na2CO3Content is
99.1 mass %, NaCl contents are 0.5 mass %, and water insoluble matter content is 0.13 mass %, meets work
The quality standard of the class certified products of industry level sodium carbonate II.
The utilization brine waste and CO of the present invention2The method of production soda ash, can not only effectively solving saliferous
The disposal difficulties of low value-added NaCl in waste water, additionally it is possible to produce certain economic benefit, are Coal Chemical Industry
Realize that the near-zero release target of brine waste provides effective technological means Deng enterprise.Meanwhile, using rich one
Valency salt salt solution or richness NaCl salt solution, accelerator and CO2Between carburizing reagent production sodium carbonate, success
Coal Chemical Industry is produced the CO of discharge on ground2The disposal process of brine waste is used, brine waste is being solved
In low value-added NaCl disposal difficulties while, also efficiently solve huge carbon emission reduction pressure.Separately
Outward, the method for the present invention, can not only also by being heated to carbonization mother liquor or electrodialysis process
Regeneration accelerator so that accelerator can recycle, but also hydrochloric acid can be obtained, i.e., only need to consume
Value relatively low NaCl and CO2, it becomes possible to production, can be significantly compared with the soda ash and hydrochloric acid of high added value
The economy of raising process.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned reality
The detail in mode is applied, in the range of the technology design of the present invention, can be to the technical side of the present invention
Case carries out various simple variants, and these simple variants belong to protection scope of the present invention.
It is further to note that each particular technique described in above-mentioned specific embodiment is special
Levy, in the case of reconcilable, can be combined by any suitable means, in order to avoid need not
The repetition wanted, the present invention is no longer separately illustrated to various possible combinations.
Additionally, can also be combined between a variety of embodiments of the present invention, as long as its
Without prejudice to the thought of the present invention, it should equally be considered as content disclosed in this invention.
Claims (11)
1. it is a kind of to utilize brine waste and CO2The method of production soda ash, it is characterised in that the method bag
Include：
(1) brine waste is carried out into separating treatment, removes the divalent salts in the brine waste, with
To rich monovalent salt salt solution；
(2) in accelerator and CO2In the presence of, the rich monovalent salt salt solution is carried out into carbonization treatment, obtain
To sodium acid carbonate precipitation and carbonization mother liquor；
(3) the sodium acid carbonate precipitation for obtaining step (2) carries out calcination processing, obtains soda ash.
2. method according to claim 1, wherein, the method also includes：Step (2) is obtained
To carbonization mother liquor heated or electrodialysis process, with regeneration accelerator and obtain hydrochloric acid.
3. method according to claim 1 and 2, wherein, in step (1), at the separation
It is 50-360g/L that the condition of reason causes the concentration of NaCl in the rich monovalent salt salt solution, preferably
90-300g/L。
4. method according to claim 3, wherein, in step (1), for NaCl concentration
The no more than brine waste of 10g/L, the separating treatment includes carrying out at counter-infiltration brine waste successively
Reason and nanofiltration are processed；For brine waste of the NaCl concentration more than 10g/L, the separating treatment includes
Nanofiltration process is carried out to brine waste；
Preferably, the condition of the reverse-osmosis treated includes：Pressure is 0-10MPa, and temperature is 10-50
DEG C, membrane aperture is 0.3-1nm, and membrane material is selected from cellulose acetate, aromatic polyamides, polytetrafluoroethylene (PTFE)
One or more in film, polyvinylidene fluoride film and polypropylene screen；
Preferably, the condition that the nanofiltration is processed includes：Pressure is 0.5-3MPa, and temperature is 10-50 DEG C,
Membrane aperture is 1-2nm, and membrane material is selected from cellulose acetate, SPSF, sulfonated polyether sulfone, polyamide
With one or more of polyvinyl alcohol.
5. the method according to any one in claim 1-4, wherein, methods described also includes：
In step (2), before carbonization treatment, concentration is carried out to rich monovalent salt salt solution, improve described
The concentration of NaCl is obtaining rich NaCl salt solution in rich monovalent salt salt solution；Preferably so that the rich NaCl
The concentration of NaCl is 150-360g/L, more preferably 200-350g/L in salt solution.
6. method according to claim 5, wherein, in step (2), the concentration
Mode is that Freeze crystallization or heating evaporation are processed,
Preferably, the embodiment of the Freeze crystallization includes：In the presence of refrigerant, by richness
Monovalent salt salt solution freezes 10-300min at 0～-25 DEG C, obtains ice and richness NaCl salt solution；
Preferably, the embodiment that the heating evaporation is processed includes：By rich monovalent salt salt solution in 80-120
10-300min is heated at DEG C, rich NaCl salt solution is obtained.
7. method according to claim 1 or 5, wherein, in step (2), at the carbonization
The embodiment of reason includes：By rich monovalent salt salt solution or richness NaCl salt solution and accelerator and CO2Carry out carbon
Change reaction, NaCl, the CO in rich monovalent salt salt solution or richness NaCl salt solution2It is with the mol ratio of accelerator
1-3：1-4：1, reaction temperature is 25-50 DEG C, and the reaction time is 10-300min.
8. the method according to any one in claim 1-7, wherein, the accelerator is to have
One kind in machine amine, preferably fatty amines, alcamines, amide-type, ester cyclammonium class and aromatic amine or
It is various, more preferably in N methyldiethanol amine, triethanolamine and 2- methyl-2-amino -1- propyl alcohol
One or more.
9. method according to claim 1 and 2, wherein, in step (3), at the calcining
The temperature of reason is 150-250 DEG C, and the time is 10-150min.
10. method according to claim 2, wherein, the mode of heating is at heating flash evaporation
Reason, reactive distillation process, rectification under vacuum process or extracting rectifying are processed, and preferably heating flash evaporation is processed；
It is further preferred that the condition that heating flash evaporation is processed includes：Temperature is 80-300 DEG C, and the time is
20-300min, pressure is 0.05-0.15MPa；
It is further preferred that the method also includes the liquid phase thing that will heat or electrodialysis process is obtained
Material is back to carbonization treatment.
11. methods according to any one in claim 1-10, wherein, the brine waste
Middle NaCl contents are 2-400g/L, Ca2+With Mg2+Total content be 0-200mg/L, COD value is
0-1000mg/L。
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108409050A (en) * | 2018-04-17 | 2018-08-17 | 杭州碟滤膜技术有限公司 | A kind of Zero-discharge treating process of high-salt wastewater |
| CN110201976A (en) * | 2019-05-30 | 2019-09-06 | 北京航天环境工程有限公司 | A kind of abraum salt recycling treatment processing system and application |
| CN110201975A (en) * | 2019-05-30 | 2019-09-06 | 北京航天环境工程有限公司 | A kind of abraum salt recycling treatment disposal system and application |
| WO2020035854A1 (en) * | 2018-08-17 | 2020-02-20 | Asher Vitner | Separation of a strong acid from its salts |
| WO2021053669A1 (en) * | 2019-09-16 | 2021-03-25 | Asher Vitner | Separation of a strong acid from its salts |
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| CN202016881U (en) * | 2011-04-07 | 2011-10-26 | 四川金圣赛瑞化工有限责任公司 | System for producing soda ash and ammonium sulfate |
| TW201408598A (en) * | 2012-08-16 | 2014-03-01 | Ahilan Raman | Process and system for producing sodium chloride brine |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108409050A (en) * | 2018-04-17 | 2018-08-17 | 杭州碟滤膜技术有限公司 | A kind of Zero-discharge treating process of high-salt wastewater |
| CN108409050B (en) * | 2018-04-17 | 2020-12-25 | 杭州碟滤膜技术有限公司 | Zero-emission treatment process for high-salinity wastewater |
| WO2020035854A1 (en) * | 2018-08-17 | 2020-02-20 | Asher Vitner | Separation of a strong acid from its salts |
| CN110201976A (en) * | 2019-05-30 | 2019-09-06 | 北京航天环境工程有限公司 | A kind of abraum salt recycling treatment processing system and application |
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| WO2021053669A1 (en) * | 2019-09-16 | 2021-03-25 | Asher Vitner | Separation of a strong acid from its salts |
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