CN101787541B - Method for removing nitrates through CIM membrane method - Google Patents
Method for removing nitrates through CIM membrane method Download PDFInfo
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- CN101787541B CN101787541B CN2010101011908A CN201010101190A CN101787541B CN 101787541 B CN101787541 B CN 101787541B CN 2010101011908 A CN2010101011908 A CN 2010101011908A CN 201010101190 A CN201010101190 A CN 201010101190A CN 101787541 B CN101787541 B CN 101787541B
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Abstract
The invention discloses a method for removing nitrates through CIM membrane method, belonging to the technical field of chlor-alkali production. The method comprises the three steps of performing membrane filtration, adjusting the pH value of water containing rich nitrates, and freezing to remove nitrates. By using the invention, the pH value of water containing rich nitrates is controlled to 10-11, thus reducing the equipment corrosion caused by the water containing rich nitrates. In addition, a mother liquid storage tank is introduced in the membrane component for storing centrifugal motherliquid; a mother liquid pump is used to send centrifugal mother liquid back to the mirabilite-settling chamber, and mirabilite particles grow in the mirabilite-settling chamber and are recycled continuously. By adding the mother liquid storage tank to recycle centrifugal mother liquid, the sodium sulfate in centrifugal mother liquid can be recycled to increase the recovery of mirabilite; and as more mirabilite is precipitated and crystallized and cold energy in the mother liquid tank is recycled, the temperature system of the mirabilite-settling chamber is more stable, and the yield of mirabilite is more stable. On the other side, sodium sulfate in the water containing low nitrates is correspondingly reduced and the water pump using the water containing low nitrates is not easy to block and stop.
Description
Technical field
The invention discloses a kind of C IM embrane method and remove the method for nitre, belong to technical field of chlor-alkali production.
Background technology
At present, China's chlor-alkali production mainly contains two kinds of ionic membrane method and diaphragm processes.Because the asbestos pollution in the diaphragm process alkali-making process is more serious, is replaced by the ionic membrane method alkali-making process gradually.In ionic membrane method alkali-making process process, because can't seeing through ionic membrane in electrolytic process, sulfate radical enters the caustic soda system, therefore the phenomenon that exists sulfate radical in brine system, to accumulate.Simultaneously, in process of production, free chlorine needs to add S-WAT to the harm of device in the brine system in its system in order to eliminate, and the oxidized back of inferior sulfate radical accumulates in brine system equally with the form of sulfate radical.After these concentration that are accumulated in the sulfate radical in the brine system surpass certain value, can be in electrolytic process at anode discharge, the oxygen and the antianode that also can produce free state when having consumed electric energy produce comparatively serious destruction.So, must remove the sulfate radical that accumulates in these systems.Because sulfate radical combines the back and forms sodium sulfate (saltcake) with sodium ion, therefore remove the process of sulfate radical in the system and cry again except that nitre.
The method of removing nitre mainly contains barium chloride method, calcium method, cold method and embrane method.Because it is a physical process to the removal of sulfate radical that embrane method is removed nitre, does not need to add chemical reagent in system, technology controlling and process is fairly simple, and clean environment has replaced other gradually and removed the nitre method.So-called embrane method is removed nitre, is to utilize salt solution to reach purpose except that nitre by the selective filter film.The CIM film is a kind of pressure drive membrane, the CIM embrane method is removed nitre when fully absorbing the SRS advantage, can control rich salt made from earth containing a comparatively high percentage of sodium chloride water concentration by regulating internal circulating load, thereby solved sodium sulfate crystalline problem in film, thereby be the cleaning technique of nitrate removal of recommending encouragement in the industry.
The technical process that existing CIM embrane method is removed nitre is as follows:
(1), membrane filtration:
Light salt brine after the dechlorination enters the light salt brine dashpot, is cooled to about 35 ℃ by water cooler, adopts volume pump to add 10% hydrochloric acid soln and 4%Na respectively
2SO
3Solution, regulate light salt brine pH value to 5.5～7.5, remove the free chlorine that contains in the salt solution, by the raw material salt water pump salt solution is delivered to security personnel's strainer behind ORP (redox electrode current potential)≤100mv, enter the CIM membrane module after filtering out the suspended substance in the light salt brine, in membrane module, utilize the selectivity of film that the sodium sulfate in the light salt brine is carried out enrichment, (sodium sulfate quality concentration is 20～40g/L) to enter rich salt made from earth containing a comparatively high percentage of sodium chloride tank to rich salt made from earth containing a comparatively high percentage of sodium chloride water, and (sodium sulfate quality concentration≤0.5g/L) enters the recovered brine groove to denitration salt solution;
(2), freezing denitration:
Rich salt made from earth containing a comparatively high percentage of sodium chloride water is delivered to freezing denitrating system by rich salt made from earth containing a comparatively high percentage of sodium chloride water pump, is delivered to pre-cold trap after interchanger is cooled to 16～20 ℃;
Rich salt made from earth containing a comparatively high percentage of sodium chloride water overflow in the pre-cold trap is delivered in vaporizer heat exchange cooling by the freeze cycle pump with rich salt made from earth containing a comparatively high percentage of sodium chloride water to converting the halogen groove, sends back to after rich nitre brinish temperature is reduced to-10～-12 ℃ and converts the halogen groove;
Rich salt made from earth containing a comparatively high percentage of sodium chloride water after the cooling is by converting the overflow of halogen groove to heavy nitre groove, saltcake crystallization in heavy nitre groove, grow and be enriched in the heavy nitre groove awl end, separate out salt solution overflow behind the saltcake crystal to poor salt made from earth containing a comparatively high percentage of sodium chloride tank, the heavy nitre groove awl end sodium sulfate crystal grain of growing up is sent into wet cyclone by the nitre stock pump and is carried out preliminary solid-liquid separation, separating obtained liquid phase is returned and is converted the halogen groove and carry out crystallization once more, it is centrifugal that separating obtained solid phase enters whizzer, is product saltcake (Na by the isolated solid matter of whizzer
2SO
410H
2O), centrifugal gained liquid phase (centrifuge mother liquor) enters poor salt made from earth containing a comparatively high percentage of sodium chloride tank, and the poor salt made from earth containing a comparatively high percentage of sodium chloride water in the poor salt made from earth containing a comparatively high percentage of sodium chloride tank is sent into interchanger by poor salt made from earth containing a comparatively high percentage of sodium chloride water pump, mixes the back with membrane module denitration salt solution and pumps out the battery limit (BL) by recovered brine.
Existing CIM embrane method is removed in the nitre, because the CIM film shrinks under weakly acidic condition, expands under weakly alkaline condition, thereby more helps the enrichment of sodium sulfate under the weakly acidic condition, Gu rich salt made from earth containing a comparatively high percentage of sodium chloride water slant acidity often.Rich salt made from earth containing a comparatively high percentage of sodium chloride water is directly sent into refrigeration system through rich salt made from earth containing a comparatively high percentage of sodium chloride water pump and is lowered the temperature, and the rich salt made from earth containing a comparatively high percentage of sodium chloride water after the cooling reclaims saltcake in heavy nitre groove.Because rich salt made from earth containing a comparatively high percentage of sodium chloride water slant acidity, to the corrosion that the equipment of refrigeration system (comprise pre-cold trap, convert the halogen groove, heavy nitre groove, vaporizer and each pipeline, pump) causes comparatively serious (generally use 3 months then tangible pipe perforation phenomenon can occur), if send the battery limit (BL) then can cause the waste of resource at this point.And because though centrifuge drum can be classified the above material of diameter 10 μ m, the material of diameter＜10 μ m then can enter the whizzer mother liquor by centrifuge drum, thereby contain small part sodium sulfate in the centrifuge mother liquor inevitably, the crystallization in poor salt made from earth containing a comparatively high percentage of sodium chloride tank of this part sodium sulfate causes the obstruction and the parking (generally using the obstruction that can cause poor salt made from earth containing a comparatively high percentage of sodium chloride water pump in 48 hours) of poor salt made from earth containing a comparatively high percentage of sodium chloride water pump easily.
Summary of the invention
The objective of the invention is to overcome existing above-mentioned deficiency in the prior art, provide a kind of improved CIM embrane method to remove the nitre method.
Technical scheme of the present invention is as follows:
A kind of CIM embrane method is removed the nitre method, comprises following processing step:
(1), membrane filtration:
Light salt brine after the dechlorination enters the light salt brine dashpot, is cooled to 30～35 ℃ by water cooler, adopts volume pump to add 10% hydrochloric acid soln and 4%Na respectively
2SO
3Solution, regulate light salt brine pH value to 5.5～7.5, remove the free chlorine in the salt solution, by the raw material salt water pump salt solution is delivered to security personnel's strainer behind ORP≤100mv, enter the CIM membrane module after filtering out the suspended substance in the light salt brine, utilize the selectivity of film that the sodium sulfate in the light salt brine is carried out enrichment in membrane module, rich salt made from earth containing a comparatively high percentage of sodium chloride water enters rich salt made from earth containing a comparatively high percentage of sodium chloride tank, and denitration salt solution enters the recovered brine groove;
(2), regulate rich nitre brinish pH value:
In rich salt made from earth containing a comparatively high percentage of sodium chloride tank, drip the electrolytic solution that contains 10%NaOH, regulate rich nitre brinish pH value to 10～11;
(3), freezing denitration:
Rich salt made from earth containing a comparatively high percentage of sodium chloride water is delivered to freezing denitrating system by rich salt made from earth containing a comparatively high percentage of sodium chloride water pump, after interchanger is cooled to 16～20 ℃, be delivered to and convert the halogen groove, by the freeze cycle pump rich salt made from earth containing a comparatively high percentage of sodium chloride water is delivered in the vaporizer heat exchange cooling, send back to after rich nitre brinish temperature is reduced to-10～-12 ℃ and convert the halogen groove;
Rich salt made from earth containing a comparatively high percentage of sodium chloride water after the cooling is by converting the overflow of halogen groove to heavy nitre groove, saltcake crystallization in heavy nitre groove, grows and is enriched at the heavy nitre groove awl end, separates out the salt solution overflow poor salt made from earth containing a comparatively high percentage of sodium chloride tank extremely behind the saltcake crystal;
The heavy nitre groove awl end sodium sulfate crystal grain of growing up is sent into wet cyclone by the nitre stock pump and is carried out preliminary solid-liquid separation, separating obtained liquid phase is returned and is converted the halogen groove and carry out crystallization once more, it is centrifugal that separating obtained solid phase enters whizzer, is product saltcake (Na by the isolated solid matter of whizzer
2SO
410H
2O), centrifugal gained liquid phase (centrifuge mother liquor) is sent into the mother liquor storage tank, is pumped to heavy nitre groove through mother liquor;
Poor salt made from earth containing a comparatively high percentage of sodium chloride water in the poor salt made from earth containing a comparatively high percentage of sodium chloride tank is sent into interchanger by poor salt made from earth containing a comparatively high percentage of sodium chloride water pump, mixes the back with membrane module denitration salt solution and pumps out the battery limit (BL) by recovered brine.
The present invention slowly drips 10%NaOH solution in rich salt made from earth containing a comparatively high percentage of sodium chloride water, rich nitre brinish pH value is controlled between 10～11, to reduce the corrosion of rich salt made from earth containing a comparatively high percentage of sodium chloride water to equipment.And in membrane module, introduced a mother liquor storage tank and stored centrifuge mother liquor, and sent centrifuge mother liquor back to heavy nitre groove, continued to reclaim saltcake particle wherein, made it in heavy nitre groove, continue to grow up with the mother liquor pump.Increase the mother liquor storage tank and reclaim centrifuge mother liquor, not only can reclaim the yield of the contained sodium sulfate of centrifuge mother liquor, and, reclaim the cold in the mother liquor tank simultaneously owing to there is more saltcake to separate out crystallization with the increase saltcake, the temperature hierarchy of stable more heavy nitre groove makes saltcake output more stable.On the other hand, the corresponding minimizing of institute's contains sodium sulfate in the poor salt made from earth containing a comparatively high percentage of sodium chloride water, the difficult obstruction and the parking of poor salt made from earth containing a comparatively high percentage of sodium chloride water pump.
Description of drawings:
Fig. 1 is a membrane filtration process schematic flow sheet of the present invention.
Fig. 2 is a freezing denitrating technique schematic flow sheet of the present invention.
Mark among the figure:
V-001: the light salt brine dashpot,
V-201: the raw material salt tank,
V-202: rich salt made from earth containing a comparatively high percentage of sodium chloride tank,
V-203: the recovered brine groove,
The V-204:CIM membrane module,
V-205: cell liquor head tank,
V-301: convert the halogen groove,
V-302: heavy nitre groove,
V-303: poor salt made from earth containing a comparatively high percentage of sodium chloride tank,
V-304: wet cyclone,
V-305: the mother liquor storage tank,
E-101/102: the light salt brine water cooler,
E-301: interchanger,
F-201A/B: security personnel's strainer,
E-302A/B/C: vaporizer,
P-301A/B/C freeze cycle pump,
S-301: whizzer.
Embodiment
The present invention is described in further detail below in conjunction with embodiment.But this should be interpreted as that the scope of the above-mentioned theme of the present invention only limits to following embodiment, allly all belong to scope of the present invention based on the technology that content of the present invention realized.
Embodiment 1
The CIM embrane method that present embodiment is enumerated is removed the nitre method, comprises following processing step:
(1), membrane filtration:
From the pH value of ionic membrane operation be 10.2, temperature is that 80 ℃ dechlorination light salt brine enters light salt brine dashpot V-001, elder generation after E102 (cold fluid is a recirculated water) is cooled to 33 ℃, adopts volume pump respectively with 10% hydrochloric acid soln and 4%Na through light salt brine water cooler E101 (cold fluid is a recovered brine)
2SO
3Solution is delivered to static mixer and mixes, regulate light salt brine pH value to 6.8, and the free chlorine that may contain in the salt solution further removed, ORP enters raw material salt tank V-201 behind the 34mv, by the raw material salt water pump salt solution is delivered to security personnel filter F-201A/B then, enter CIM membrane module V-204 after filtering out the suspended substance in the light salt brine, in membrane module, utilize the selectivity of film that the sodium sulfate in the light salt brine is carried out enrichment, rich salt made from earth containing a comparatively high percentage of sodium chloride water enters rich salt made from earth containing a comparatively high percentage of sodium chloride tank V-202, denitration salt solution enters recovered brine groove V-203, and recovered brine goes out system after recovered brine is pumped to water cooler E-101 recovered energy;
In the said process in the dechlorination light salt brine concentration of sodium sulfate be that the concentration of sodium sulfate in 14.8g/L, the out of stock salt solution is that the concentration of sodium sulfate in 1.3g/L, the rich salt made from earth containing a comparatively high percentage of sodium chloride water is 35.6g/L.
(2), regulate rich nitre brinish pH value:
The electrolytic solution that contains NaOH 10% from electrolysis workshop section is stored among the cell liquor head tank V-205, adopts the mode that drips to join among the rich salt made from earth containing a comparatively high percentage of sodium chloride tank V-202 then, makes rich nitre brinish pH be controlled at the state of weakly alkaline (pH=10.5);
(3), freezing denitration:
The rich salt made from earth containing a comparatively high percentage of sodium chloride water of weakly alkaline is delivered to freezing denitrating system by rich salt made from earth containing a comparatively high percentage of sodium chloride water pump, after interchanger E301 (cold fluid is poor salt made from earth containing a comparatively high percentage of sodium chloride water) is cooled to 19.5 ℃, be delivered to and convert halogen groove V-301, by freeze cycle pump P-301A/B/C rich salt made from earth containing a comparatively high percentage of sodium chloride water is delivered to heat exchange cooling among the vaporizer E-301A/B/C, the heat-eliminating medium of vaporizer E-302A/B/C is a freonll-11, sends back to after rich nitre brinish temperature is reduced to-10～-12 ℃ and converts the halogen groove; Under this temperature, sodium sulfate solubleness reduces, and separates out a part of crystal grain;
Overflow was to heavy nitre groove V-302 after rich salt made from earth containing a comparatively high percentage of sodium chloride water after the cooling arrived overflow port, crystal grain sluggish flow and growing up in heavy nitre groove, separate out salt solution overflow behind the saltcake crystal in the heavy nitre groove to poor salt made from earth containing a comparatively high percentage of sodium chloride tank V-303, the sodium sulfate crystal grain of growing up is deposited on the bottom of nitre groove, send into wet cyclone V-304 by the nitre stock pump and carry out preliminary solid-liquid separation, the few liquid phase of saltcake particle that contains after the separation enters and converts the halogen groove and carry out crystallization once more, to enter whizzer S-301 centrifugal for the many solid phases of saltcake particle that contain after the separation, and is product saltcake (Na by the isolated solid matter of whizzer
2SO
410H
2O), centrifugal gained liquid phase (centrifuge mother liquor) is sent into mother liquor storage tank V-305, is pumped to heavy nitre groove V-302 through mother liquor, makes saltcake particle tiny in centrifuge mother liquor crystal growth once more in heavy nitre groove, with the output of increase saltcake.
Poor salt made from earth containing a comparatively high percentage of sodium chloride water in the poor salt made from earth containing a comparatively high percentage of sodium chloride tank is sent into interchanger E-301 by poor salt made from earth containing a comparatively high percentage of sodium chloride water pump, mixes the back with membrane module denitration salt solution and pumps out the battery limit (BL) by recovered brine.
Present embodiment per tour saltcake output is 6 tons, does not improve one ton when more using the mother liquor storage tank.Drive so far from March, 2009, corrosion phenomenon does not appear in refrigerating apparatus, and latch up phenomenon does not appear in poor salt made from earth containing a comparatively high percentage of sodium chloride water pump yet.
Embodiment 2
The CIM embrane method that present embodiment is enumerated is removed the nitre method, comprises following processing step:
(1), membrane filtration:
From the pH value of ionic membrane operation be 10.2, temperature is that 82 ℃ dechlorination light salt brine enters light salt brine dashpot V-001, is cooled to 35 ℃ through light salt brine water cooler E101, E102, adopts volume pump respectively with 10% hydrochloric acid soln and 4%Na
2SO
3Solution is delivered to static mixer and mixes, regulate light salt brine pH value to 6.9, the free chlorine that may contain in the salt solution is further removed, ORP enters raw material salt tank V-201 behind the 60mv, by the raw material salt water pump salt solution is delivered to security personnel filter F-201A/B then, enter the CIM membrane module after filtering out the suspended substance in the light salt brine, in membrane module, utilize the selectivity of film that the sodium sulfate in the light salt brine is carried out enrichment, rich salt made from earth containing a comparatively high percentage of sodium chloride water enters rich salt made from earth containing a comparatively high percentage of sodium chloride tank V-202, denitration salt solution enters recovered brine groove V-203, and recovered brine goes out system after recovered brine is pumped to water cooler E-101 recovered energy;
In the said process in the dechlorination light salt brine concentration of sodium sulfate be that the concentration of sodium sulfate in 10.35g/L, the out of stock salt solution is that the concentration of sodium sulfate in 1.5g/L, the rich salt made from earth containing a comparatively high percentage of sodium chloride water is 33.4g/L.
(2), regulate rich nitre brinish pH value:
The electrolytic solution that contains NaOH 10% from electrolysis workshop section is stored among the cell liquor head tank V-205, adopts the mode that drips to join among the rich salt made from earth containing a comparatively high percentage of sodium chloride tank V-202 then, makes rich nitre brinish pH be controlled at the state of weakly alkaline (pH=10);
(3), freezing denitration:
The rich salt made from earth containing a comparatively high percentage of sodium chloride water of weakly alkaline is delivered to freezing denitrating system by rich salt made from earth containing a comparatively high percentage of sodium chloride water pump, after interchanger E301 (cold fluid is poor salt made from earth containing a comparatively high percentage of sodium chloride water) is cooled to 20.2 ℃, be delivered to and convert the halogen groove, by the freeze cycle pump rich salt made from earth containing a comparatively high percentage of sodium chloride water is delivered among the vaporizer E-301A/B/C heat exchange cooling, send back to after rich nitre brinish temperature is reduced to-10～-12 ℃ and convert the halogen groove; Under this temperature, sodium sulfate solubleness reduces, and separates out a part of crystal grain;
Overflow was to heavy nitre groove V-302 after rich salt made from earth containing a comparatively high percentage of sodium chloride water after the cooling arrived overflow port, crystal grain sluggish flow and growing up in heavy nitre groove, separate out salt solution overflow behind the saltcake crystal in the heavy nitre groove to poor salt made from earth containing a comparatively high percentage of sodium chloride tank V303, the sodium sulfate crystal grain of growing up is deposited on the bottom of nitre groove, send into wet cyclone V304 by the nitre stock pump and carry out preliminary solid-liquid separation, the few liquid phase of saltcake particle that contains after the separation enters and converts the halogen groove and carry out crystallization once more, to enter whizzer S-301 centrifugal for the many solid phases of saltcake particle that contain after the separation, and is product saltcake (Na by the isolated solid matter of whizzer
2SO
410H
2O), centrifugal gained liquid phase (centrifuge mother liquor) is sent into mother liquor storage tank V306, is pumped to heavy nitre groove through mother liquor, makes saltcake particle tiny in centrifuge mother liquor crystal growth once more in heavy nitre groove, with the output of increase saltcake.
Poor salt made from earth containing a comparatively high percentage of sodium chloride water in the poor salt made from earth containing a comparatively high percentage of sodium chloride tank is sent into interchanger by poor salt made from earth containing a comparatively high percentage of sodium chloride water pump, mixes the back with membrane module denitration salt solution and pumps out the battery limit (BL) by recovered brine.
Present embodiment per tour saltcake output is 6 tons, does not improve 1 ton when more using the mother liquor storage tank.Drive so far from March, 2009, corrosion phenomenon does not appear in refrigerating apparatus, and latch up phenomenon does not appear in poor salt made from earth containing a comparatively high percentage of sodium chloride water pump yet.
Claims (1)
1. a CIM embrane method is removed the nitre method, it is characterized in that comprising following processing step:
(1), membrane filtration:
Light salt brine after the dechlorination enters the light salt brine dashpot, is cooled to 30～35 ℃ by water cooler, adopts volume pump to add 10% hydrochloric acid soln and 4%Na respectively
2SO
3Solution, regulate light salt brine pH value to 5.5～7.5, remove the free chlorine in the light salt brine, by the raw material salt water pump light salt brine is delivered to security personnel's strainer behind ORP≤100mV, enter the CIM membrane module after filtering out the suspended substance in the light salt brine, utilize the selectivity of film that the sodium sulfate in the light salt brine is carried out enrichment in membrane module, rich salt made from earth containing a comparatively high percentage of sodium chloride water enters rich salt made from earth containing a comparatively high percentage of sodium chloride tank, and denitration salt solution enters the recovered brine groove;
(2), regulate rich nitre brinish pH value:
In rich salt made from earth containing a comparatively high percentage of sodium chloride tank, drip the electrolytic solution that contains 10%NaOH, regulate rich nitre brinish pH value to 10～11;
(3), freezing denitration:
Rich salt made from earth containing a comparatively high percentage of sodium chloride water is delivered to freezing denitrating system by rich salt made from earth containing a comparatively high percentage of sodium chloride water pump, after interchanger is cooled to 16～20 ℃, be delivered to and convert the halogen groove, by the freeze cycle pump rich salt made from earth containing a comparatively high percentage of sodium chloride water is delivered in the vaporizer heat exchange cooling, send back to after rich nitre brinish temperature is reduced to-10～-12 ℃ and convert the halogen groove;
Rich salt made from earth containing a comparatively high percentage of sodium chloride water after the cooling is by converting the overflow of halogen groove to heavy nitre groove, saltcake crystallization in heavy nitre groove, grows and is enriched at the heavy nitre groove awl end, separates out the salt solution overflow poor salt made from earth containing a comparatively high percentage of sodium chloride tank extremely behind the saltcake crystal;
The heavy nitre groove awl end sodium sulfate crystal grain of growing up is sent into wet cyclone by the nitre stock pump and is carried out preliminary solid-liquid separation, separating obtained liquid phase is returned and is converted the halogen groove and carry out crystallization once more, it is centrifugal that separating obtained solid phase enters whizzer, be the product saltcake by the isolated solid matter of whizzer, centrifugal gained liquid phase is sent into the mother liquor storage tank, is pumped to heavy nitre groove through mother liquor;
Poor salt made from earth containing a comparatively high percentage of sodium chloride water in the poor salt made from earth containing a comparatively high percentage of sodium chloride tank is sent into interchanger by poor salt made from earth containing a comparatively high percentage of sodium chloride water pump, mixes the back with membrane module denitration salt solution and pumps out the battery limit (BL) by recovered brine.
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| CN102417193B (en) * | 2011-10-11 | 2013-06-26 | 山东东岳氟硅材料有限公司 | Production method for increasing nitrate removal capacity by membrane method |
| CN102502986B (en) * | 2011-10-26 | 2013-10-16 | 中国石化江汉油田分公司盐化工总厂 | Comprehensive utilization method of ionic membrane electrolytic saline solution waste liquid |
| CN102745720A (en) * | 2012-06-20 | 2012-10-24 | 青海宜化化工有限责任公司 | Denitration method in caustic soda technology |
| CN102774981A (en) * | 2012-07-06 | 2012-11-14 | 广州昌硕环保设备有限公司 | Membrane process denitrification process of light salt brine and denitrification device |
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| CN87102396A (en) * | 1986-03-27 | 1987-10-07 | C-I-L公司 | The production of sodium chlorate |
| CN1107903A (en) * | 1994-03-03 | 1995-09-06 | 湖南化学工业设计院 | Method for preparing sodium hydroxide by brine electrolysis |
| DE19626270A1 (en) * | 1996-06-29 | 1998-01-02 | Eilenburger Elektrolyse & Umwelttechnik Gmbh | Production/regeneration of per:oxo:di:sulphate(s) in alkaline solutions |
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2010
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87102396A (en) * | 1986-03-27 | 1987-10-07 | C-I-L公司 | The production of sodium chlorate |
| CN1107903A (en) * | 1994-03-03 | 1995-09-06 | 湖南化学工业设计院 | Method for preparing sodium hydroxide by brine electrolysis |
| DE19626270A1 (en) * | 1996-06-29 | 1998-01-02 | Eilenburger Elektrolyse & Umwelttechnik Gmbh | Production/regeneration of per:oxo:di:sulphate(s) in alkaline solutions |
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| 朱大春等.钡法和膜法除硝的技术经济对比.《中国氯碱》.2008,(第7期),12-16. * |
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