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 PDF

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Publication number
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
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salt
nacl
salt solution
rich
brine waste
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Inventor
赵兴雷
李国涛
马瑞
张桐
霍卫东
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Shenhua Group Corp Ltd
National Institute of Clean and Low Carbon Energy
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Shenhua Group Corp Ltd
National Institute of Clean and Low Carbon Energy
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Priority to CN201510763581.9A priority Critical patent/CN106673019A/en
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01DCOMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D7/00Carbonates of sodium, potassium or alkali metals in general
    • C01D7/16Preparation from compounds of sodium or potassium with amines and carbon dioxide
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B7/00Halogens; Halogen acids
    • C01B7/01Chlorine; Hydrogen chloride
    • C01B7/03Preparation from chlorides
    • C01B7/035Preparation of hydrogen chloride from chlorides
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01DCOMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D7/00Carbonates of sodium, potassium or alkali metals in general
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/10Process efficiency
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/141Feedstock

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

One kind is using brine waste and CO2The method of production soda ash
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。
CN201510763581.9A 2015-11-11 2015-11-11 Method for producing sodium carbonate with salt-containing wastewater and CO2 Pending CN106673019A (en)

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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
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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TW201408598A (en) * 2012-08-16 2014-03-01 Ahilan Raman Process and system for producing sodium chloride brine

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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
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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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