CN106986356A - A kind of lime-flue gas bittern purifying method - Google Patents

A kind of lime-flue gas bittern purifying method Download PDF

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CN106986356A
CN106986356A CN201710332760.6A CN201710332760A CN106986356A CN 106986356 A CN106986356 A CN 106986356A CN 201710332760 A CN201710332760 A CN 201710332760A CN 106986356 A CN106986356 A CN 106986356A
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reaction
lime
liquid
hec
halogen
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CN106986356B (en
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林应南
方远西
周高峰
刘钰林
王乐
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JIANGXI JINGHAO SALINIZATION CO Ltd
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JIANGXI JINGHAO SALINIZATION CO Ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D3/00—Halides of sodium, potassium or alkali metals in general
    • C01D3/04—Chlorides

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  • Engineering & Computer Science (AREA)
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  • Inorganic Chemistry (AREA)
  • Separation Of Suspended Particles By Flocculating Agents (AREA)

Abstract

The invention discloses a kind of lime-flue gas bittern purifying method, comprise the steps of：1) first order reaction is clarified：Ca in the former halogen of measurement2+、Mg2+Concentration, the amount of lime and soda ash, is fed intake, soda ash is then delivered into former halogen, finally deliver remaining lime in advance with lime first needed for calculating；2) sample and do over again：The Ca in saltwater brine is mixed after test reaction2+、Mg2+Concentration value, qualified then to carry out step 3), it is not up to standard, further purified using caustic soda and soda ash；3) once flocculate：HEC maleic acid chitin composite flocculant flocculating settings are added into mixing saltwater brine；4) second order reaction is clarified：To after once settling carbon dioxide flue gas is passed through in liquid；5) secondary flocculation：HEC maleic acid chitin composite flocculant flocculating settings are added into saltwater brine；6) liquid is transferred to the smart halogen bucket in salt manufacturing workshop after settling.The present invention has huge economic benefit compared to traditional two alkaline process；Using composite flocculation agent, the clarification time is short, and the turbidity of bittern is low after purification, and flocculant is more stable.

Description

A kind of lime-flue gas bittern purifying method
Technical field
The present invention relates to salt industry technical field, more particularly to a kind of lime-flue gas bittern purifying method.
Background technology
Salt is as the necessity of human survival and one of the most basic raw material of chemical industry, in the daily life of national economy In all occupy very important status.China is production salt one of most long country, and China's salt resource is very in history of the world Abundant, Qinghai, Xinjiang, Tibet etc. are saved, autonomous region is dispersed with several thousands of salt lakes with spreading all over the place, Sichuan, Yunnan, Jiangsu, Shandong, Henan etc. save subsurface storage and abundant rock salt, and Huai'an possesses the maximum salt mine in the whole world.
China's sulfate type salt mine contains Mg mostly through the bittern after hydromining2+、Ca2+、SO4 2-Deng foreign ion, due to halogen Calcium, the magnesium addition contained in water, during salt manufacturing is produced, is separated out, influence is conducted heat and increased easily on evaporation, heat-transfer equipment Consumption, while bringing into finished product salt and finished product anhydrous sodium sulfate, influence yield and quality, therefore must be removed to it.Tradition Mg is removed using two alkaline process2+、Ca2+Ion.So-called two alkaline process, is to utilize the OH- in NaOH to remove Mg2+, Na2CO3In CO3 2- Remove Ca2+Its reaction is as follows；
2NaOH+MgSO4→Mg(OH)2↓+Na2SO4
Na2CO3+CaSO4→CaCO3↓+Na2SO4
Application and research of two alkaline process in terms of salt manufacturing bittern deionization are more ripe, but with the two alkali market prices It is constantly soaring, two alkaline process NaOH consumptions are big, and cost is high, and the corrosivity of caustic soda is strong, and the loss to equipment is larger, this also from Improve production cost on the other hand.In addition, flocculant plays a crucial role to bittern purifying, the flocculant that presently, there are is in halogen The suspended particulate of generation can not be thoroughly removed in water treatment procedure, causes partial suspended particle to enter next process with bittern, Eventually enter into salt product and nitre product so that product purity is not high, or qualification rate reduction, lose every year larger.
The content of the invention
Based on above-mentioned technical problem, the invention provides a kind of lime-flue gas bittern purifying method, following step is included Suddenly：
1) first order reaction is clarified：Ca in the former halogen of measurement2+、Mg2+Concentration, then according to first order reaction clarify former halogen amount and Ca in former halogen2+、Mg2+The amount of lime and soda ash needed for concentration value is calculated, first with calculate gained lime consumption value 60%~ 80% progress lime feeds intake in advance, is then pressed into former halogen and calculates gained soda ash volume value dispensing soda ash, the complete backward former halogen of reaction It is middle to deliver remaining lime；
2) sample and do over again：Mixed bittern sample is taken to be analyzed after first order reaction clarifying reaction, Mixed bittern after test reaction Ca in liquid2+、Mg2+Concentration value, works as Ca2+≤15mg/L、Mg2+Up to standard during≤10mg/L, mixing saltwater brine carries out next process, Work as Ca2+、Mg2+When concentration value is unsatisfactory for above-mentioned requirements, further purified using caustic soda and soda ash；
3) once flocculate：When mix saltwater brine detection it is up to standard or do over again feed intake end after, to mixing saltwater brine in add HEC- horses Come sour-chitin composite flocculant flocculating setting, sedimentation terminate after take once sedimentation after liquid observe, when once settle after liquid still When muddy, extension sedimentation time or timely do over again add flocculant again；
4) second order reaction is clarified：After the completion of flocculating setting, to once settling after liquid carry out second order reaction clarification, to once sinking Carbon dioxide flue gas is passed through after drop in liquid, reaction solution is stirred during being passed through until reaction is complete, stopped after the completion of reaction Only stir；
5) secondary flocculation：After the completion of second order reaction clarification, HEC- maleic acids-chitosan is added into secondary smoke reaction container Composite flocculation agent flocculating setting, sedimentation takes liquid test turbidity after sedimentation after terminating, liquid turbidity is unqualified after secondary settlement, Extension sedimentation time or timely do over again add flocculant again, until liquid turbidity reaches requirement after secondary settlement；
6) liquid is transferred to the smart halogen bucket in salt manufacturing workshop and carries out subsequent fine halogen after the secondary settlement after will be up to standard.
Further, the step is specially：
1) first order reaction is clarified：The Ca in analysis, the former halogen of measurement is sampled to former halogen2+、Mg2+Concentration, it is anti-according to one-level Answer the Ca in the amount of former halogen and former halogen in bucket2+、Mg2+The amount of lime and soda ash needed for concentration value is calculated, first to first order reaction bucket Former halogen is inside pumped into, is fed intake in advance while carrying out lime into first order reaction bucket with calculate gained lime consumption value 60%~80%, The agitator started during feeding intake in advance in first order reaction bucket is stirred to former halogen, so that former halogen and lime mixing are more equal It is even, stop when the liquid level of former halogen is to specified fluid level scale into former halogen；Then thrown into former halogen by calculating gained soda ash volume value Put time interval >=1 hour of soda ash, the release time of soda ash and the end that feeds intake in advance；Delivered in most backward former halogen and calculate gained stone The remainder of grey volume value, delivers the time of remaining lime and delivers time interval >=40min that soda ash terminates, dispensing terminates 1~3h is reacted afterwards, and reaction stops stirring after terminating；
2) sample and do over again：Mixed bittern sample is taken to be analyzed after first order reaction clarifying reaction, Mixed bittern after test reaction Ca in liquid2+、Mg2+Concentration value, works as Ca2+≤15mg/L、Mg2+Up to standard during≤10mg/L, mixing saltwater brine carries out next process, Work as Ca2+、Mg2+When concentration value is unsatisfactory for above-mentioned requirements, further purified using caustic soda and soda ash, according to measurement result meter The injected volume for calculating caustic soda or soda ash is done over again, and it is specifically calculated as follows：
A. calcium ion is exceeded, and magnesium ion is up to standard,
Soda ash amount (kg)=(CCa2+× 2.65 ÷ 1000+0.1) × 5500 ÷ 0.988,
Caustic soda without,
B. calcium ion is exceeded, and magnesium ion is exceeded,
Soda ash amount (kg)=(CCa2+× 2.65 ÷ 1000+0.1) × 5500 ÷ 0.988,
Caustic soda amount (kg)=(CMg2+× 3.33 ÷ 1000) × 5500 ÷ 0.3,
C. calcium ion is up to standard, and magnesium ion is exceeded,
Caustic soda amount (kg)=CMg2+(mg/l) × 3.33 ÷ 0.3 of ÷ 1000 × 5500,
Soda ash is without adding；
Wherein CCa2+And CMg2+The Ca in mixing saltwater brine after reaction is represented respectively2+、Mg2+Concentration measurement, in above-mentioned formula Middle CCa2+And CMg2+Unit be mg/L；
3) once flocculate：When mix saltwater brine detection it is up to standard or do over again feed intake end 20min after, to first order reaction bucket in add HEC- maleic acids-chitin composite flocculant, the volume of addition/saltwater brine of shown flocculant is 1~2mg/L, flocculating setting Time be more than 0.5h, settling temperature be 40~50 DEG C, sedimentation terminate after take once sedimentation after observe, when once settle after liquid according to When so muddy, extension 1~2h sedimentation times or timely do over again add flocculant again；
4) second order reaction is clarified：After the completion of flocculating setting, liquid pump enters in secondary smoke reaction container after once settling, and opens Agitator is stirred to the saltwater brine in secondary smoke reaction container, and titanium dioxide soot is then passed through into secondary smoke reaction container Gas, is passed through time >=2h, and flow of carbon dioxide gas amount is 10~20L/min, continues to stir 10~30min progress after the completion of being passed through Reaction, stops stirring after the completion of reaction；
5) secondary flocculation：After the completion of second order reaction clarification, HEC- maleic acids-chitosan is added into secondary smoke reaction container Composite flocculation agent, the volume of addition/saltwater brine of shown flocculant is 1~2mg/L, and the flocculating setting time is more than 0.5h, is sunk Cooling degree is 40~50 DEG C, and sedimentation takes liquid test turbidity after sedimentation after terminating, the turbidity of liquid is unqualified after secondary settlement, Extension 1~2h sedimentation times or timely do over again add flocculant again, until liquid turbidity reaches requirement after secondary settlement；
6) liquid is transferred to the smart halogen bucket in salt manufacturing workshop and carries out subsequent fine halogen after the secondary settlement after will be up to standard.
Further, in order to prevent line clogging, original halogen amount and former halogen are delivered and must managed immediately to delivering after terminating every time Road is rinsed, and flushing liquor flows into first order reaction bucket and participates in reaction.
Further, it is described once sedimentation or the secondary settlement it is up to standard after, first open slush pump, reaction will be deposited on Flocculant and reaction precipitation the discharge reaction container of bottom of the barrel, leave the supernatant liquor after standing and carry out subsequent technique.
Further, liquid turbidity acceptance value is≤3 degree after the secondary settlement.
Further, the HEC- maleic acids-chitin composite flocculant uses HEC (hydroxyethyl cellulose), maleic acid It is composited with chitosan, is the step of its specific preparation method：
(1) aqueous solution of maleic acid is configured, the wherein mass fraction of maleic acid is 5%~10%；
(2) aqueous maleic acid is heated to 70~80 DEG C, then HEC is dissolved in the aqueous solution of maleic acid, dissolved During be sufficiently stirred for solution, be configured to HEC mass fractions be 20%~30% mixed solution, wherein mixing time >=1h；
(3) continue the temperature of holding mixed solution, dissolve chitosan in mixed solution, add the molal quantity of chitosan Equal to the molal quantity of HEC in mixed solution, solution is sufficiently stirred in course of dissolution, wherein mixing time >=1h；
(4) temperature of above-mentioned solution is kept, glacial acetic acid is added into solution, 1h is sufficiently stirred for, is then added into solution Mass fraction carries out recombination reaction for 10% watery hydrochloric acid, constantly solution is stirred in course of reaction, the reaction time for 2~ 4h, room temperature is air-cooled to after the completion of reaction by solution, stands more than 30h；
(5) liquid dries evaporation below 70 DEG C after reacting, and after having a large amount of floccules to separate out in solution, filtering is wadded a quilt with cotton Shape filtrate, filtrate is dried under≤50 DEG C of environment, that is, obtains the HEC- maleic acids-chitin composite flocculant.
Further, 1~1.5 times of the molal quantity that the molal quantity of addition glacial acetic acid is HEC in mixed solution.
As the optimal preferred of above range, the molal quantity of addition glacial acetic acid is the molal quantity 1.2 of HEC in mixed solution Times.
Further, it is that the guarantee composite flocculation agent is free of small molecular weight impurity particle, drying obtains HEC- maleic acids-shell After glycan composite flocculation agent, the composite flocculation agent is immersed in redistilled water, then repeat step (5) 1~2 times.
Further, the chitosan is water-soluble carboxymethyl chitosan.
As can be seen from the above technical solutions, it is an advantage of the invention that：
1. bittern can be greatly lowered than two traditional alkaline process in the lime that the present invention is used-flue gas bittern purifying method Cost is purified, while when former halogen sodium sulphate is unstable, when sometimes relatively low, supplement caustic soda also ensures that flue gas purifying technique and whole The normal production of sal prunella system, the present invention is cost-effective to be calculated as follows compared to two alkaline process：
Liquid level 18m after the clear halogen production of first order reaction bucket, using rear liquid level 4m, the volume of every meter of reaction container is 314m3, then The total utilization of clear halogen is (18-4) × 314=4396m3.OH needed for the clear halogen of one-level-The content of ion is 0.53g/L, then conversion Amount into caustic soda is caustic soda that the ÷ 31%=17684kg concentration of 0.53 × 40 ÷ 17 × 4396 is 31%.The clear halogen calcium ion of one-level For 500mg/L or so, and calcium ion content is about 380mg/L in former halogen, then increase soda ash injected volume is (500-380) ÷ The ÷ 98.8%=1415kg of 1000 × 106 ÷ 40 × 4396.It is 5500kg to make lime used in the clear halogen of one-level.The present invention is used 5500kg lime instead of the caustic soda 17684kg that two alkaline process concentration are 31% plus 1415kg soda ash.By market price quick lime About 600 yuan/ton, the market price of soda ash is about 1500 yuan/ton, and the market price of caustic soda is about 700 yuan/ton.Phase so of the present invention Than in traditional two alkaline process, the clear halogen of an one-level reacts the expense saved and is：(17.684×700-1.415×1500-5.5× 520) ÷ 5=11479.26 members, can add up to save more than 550 ten thousand yuan over a year, with huge economic benefit.
2. traditional flocculant clean-up effect is not good, often there is the still muddy situation of bittern after purification, therefore usually Need sedimentation of doing over again, labor intensive material resources；The present invention substitutes the salt manufacturing flocculant used in tradition using composite flocculation agent, after purification The turbidity of bittern is low, using almost not occurred the phenomenon for needing to do over again since 3 years, and flocculant is relatively stable, normal temperature storage The term of validity apparently higher than tradition use salt manufacturing flocculant.
Embodiment
A kind of lime-flue gas bittern purifying method, is comprised the steps of：
1) first order reaction is clarified：Ca in the former halogen of measurement2+、Mg2+Concentration, then according to first order reaction clarify former halogen amount and Ca in former halogen2+、Mg2+The amount of lime and soda ash needed for concentration value is calculated, first with calculate gained lime consumption value 60%~ 80% progress lime feeds intake in advance, is then pressed into former halogen and calculates gained soda ash volume value dispensing soda ash, the complete backward former halogen of reaction It is middle to deliver remaining lime；
2) sample and do over again：Mixed bittern sample is taken to be analyzed after first order reaction clarifying reaction, Mixed bittern after test reaction Ca in liquid2+、Mg2+Concentration value, works as Ca2+≤15mg/L、Mg2+It is up to standard during≤10mg/L that (generally situation not up to standard is very Rare, situation not up to standard is mainly due to lime used in previous step technique or soda ash low quality or expired rotten), Mixed bittern Liquid carries out next process, works as Ca2+、Mg2+When concentration value is unsatisfactory for above-mentioned requirements, carried out using caustic soda and soda ash further net Change；
3) once flocculate：When mix saltwater brine detection it is up to standard or do over again feed intake end after, to mixing saltwater brine in add HEC- horses Come sour-chitin composite flocculant flocculating setting, sedimentation terminate after take once sedimentation after liquid observe, when once settle after liquid still When muddy, extension sedimentation time or timely do over again add flocculant again；
4) second order reaction is clarified：After the completion of flocculating setting, to once settling after liquid carry out second order reaction clarification, to once sinking Carbon dioxide flue gas is passed through after drop in liquid, reaction solution is stirred during being passed through until reaction is complete, stopped after the completion of reaction Only stir；
5) secondary flocculation：After the completion of second order reaction clarification, HEC- maleic acids-chitosan is added into secondary smoke reaction container Composite flocculation agent flocculating setting, sedimentation takes liquid test turbidity after sedimentation after terminating, liquid turbidity is unqualified after secondary settlement, Extension sedimentation time or timely do over again add flocculant again, until liquid turbidity reaches requirement after secondary settlement；
6) liquid is transferred to the smart halogen bucket in salt manufacturing workshop and carries out subsequent fine halogen after the secondary settlement after will be up to standard.
Embodiment 1
A kind of lime-flue gas bittern purifying method, is comprised the steps of：
1) first order reaction is clarified：The Ca in analysis, the former halogen of measurement is sampled to former halogen2+、Mg2+Concentration, it is anti-according to one-level Answer the Ca in the amount of former halogen and former halogen in bucket2+、Mg2+The amount of lime and soda ash needed for concentration value is calculated, calculates reaction response used Equation is as follows：
CaO+H2O→Ca(OH)2
Ca(OH)2+Mg2+→Ca2++Mg(OH)2↓
Ca2++Na2CO3→CaCO3↓+2Na+
Former halogen is pumped into first order reaction bucket first, while with calculating the 60% of gained lime consumption value to first order reaction barrel Interior progress lime is fed intake in advance, and the agitator started during feeding intake in advance in first order reaction bucket is stirred to former halogen, so as to original Halogen and lime mixing evenly, stop into former halogen when the liquid level of former halogen is to specified fluid level scale；Then into former halogen by calculating Gained soda ash volume value delivers time interval >=1 hour of soda ash, the release time of soda ash and the end that feeds intake in advance；Most backward former halogen It is middle to deliver the remainder for calculating gained lime consumption value, deliver the time of remaining lime and deliver the time interval that soda ash terminates 1h is reacted in >=40min, dispensing after terminating, reaction stops stirring after terminating；
2) sample and do over again：Mixed bittern sample is taken to be analyzed after first order reaction clarifying reaction, Mixed bittern after test reaction Ca in liquid2+、Mg2+Concentration value, Ca2+Concentration be 4.5mg/L, Mg2+Concentration 2.8mg/L meet the requirements, mixing saltwater brine carry out Next process；
3) once flocculate：Mix saltwater brine to detect after 20min up to standard, adding HEC- maleic acids-shell into first order reaction bucket gathers Sugared composite flocculation agent, the volume of addition/saltwater brine of flocculant is 1mg/L, and the flocculating setting time is 0.5h, and settling temperature is 40 DEG C, sedimentation takes liquid after once sedimentation to observe after terminating, the clarification of saltwater brine supernatant liquor opens slush pump, will be deposited on reaction container bottom Flocculant and reaction precipitation the discharge reaction container in portion, leave the supernatant liquor after standing and carry out subsequent technique；
4) second order reaction is clarified：After the completion of flocculating setting, liquid pump enters in secondary smoke reaction container after once settling, and opens Agitator is stirred to the saltwater brine in secondary smoke reaction container, and titanium dioxide soot is then passed through into secondary smoke reaction container Gas, is passed through the time for 2h, flow of carbon dioxide gas amount is 10L/min, continues stirring 10min after the completion of being passed through and is reacted, instead Stop stirring after the completion of answering；
5) secondary flocculation：After the completion of second order reaction clarification, HEC- maleic acids-chitosan is added into secondary smoke reaction container Composite flocculation agent, the volume of addition/saltwater brine of flocculant is 1mg/L, and the flocculating setting time is 0.5h, and settling temperature is 40 DEG C, sedimentation takes liquid after sedimentation to test turbidity using WGZ-200 types photoelectric turbidimeter after terminating, turbidity is 1.1 degree, and meeting will Evaluation, is then turned on slush pump, and the flocculant and reaction precipitation of being deposited on reaction bottom of the barrel are discharged into reaction container, left after standing Supernatant liquor carry out subsequent technique；
6) liquid is transferred to the smart halogen bucket in salt manufacturing workshop and carries out subsequent fine halogen after the secondary settlement after will be up to standard.
HEC- maleic acids-chitin composite flocculant uses HEC (hydroxyethyl cellulose), maleic acid and water in above-mentioned steps Dissolubility carboxymethyl chitosan is composited, and is the step of its specific preparation method：
(1) aqueous solution of maleic acid is configured, the wherein mass fraction of maleic acid is 5%；
(2) aqueous maleic acid is heated to 70 DEG C, then HEC is dissolved in the aqueous solution of maleic acid, course of dissolution In be sufficiently stirred for solution, be configured to HEC mass fractions be 20% mixed solution, wherein mixing time be 1h；
(3) continue the temperature of holding mixed solution, water-soluble carboxymethyl chitosan is dissolved in mixed solution, add shell The molal quantity of glycan, which is equal in the molal quantity of HEC in mixed solution, course of dissolution, is sufficiently stirred for solution, and wherein mixing time is 1h；
(4) temperature of above-mentioned solution is kept, glacial acetic acid is added into solution, 1h is sufficiently stirred for, mole of glacial acetic acid is added 1 times of the molal quantity that number is HEC in mixed solution, then adds mass fraction compound anti-for 10% watery hydrochloric acid progress into solution Should, constantly solution is stirred in course of reaction, the reaction time is 2h, solution is air-cooled to room temperature after the completion of reaction, stood 30h；
(5) liquid dries evaporation at 70 DEG C after reacting, after having a large amount of floccules to separate out in solution, the cotton-shaped mistake of filtering acquisition Screening, filtrate is dried under 50 DEG C of environment, that is, obtains the HEC- maleic acids-chitin composite flocculant.
Embodiment 2
A kind of lime-flue gas bittern purifying method, is comprised the steps of：
1) first order reaction is clarified：The Ca in analysis, the former halogen of measurement is sampled to former halogen2+、Mg2+Concentration, it is anti-according to one-level Answer the Ca in the amount of former halogen and former halogen in bucket2+、Mg2+The amount of lime and soda ash needed for concentration value is calculated, first to first order reaction bucket Former halogen is inside pumped into, feeds intake, is fed intake in advance in advance while carrying out lime into first order reaction bucket with calculate gained lime consumption value 70% During start first order reaction bucket in agitator former halogen is stirred, so as to former halogen and lime mixing evenly, work as original Stop when the liquid level of halogen is to specified fluid level scale into former halogen；Then soda ash is delivered by calculating gained soda ash volume value into former halogen, The time interval of the release time of soda ash and the end that feeds intake in advance is 1 hour；Delivered in most backward former halogen and calculate gained lime consumption The remainder of value, delivers the time of remaining lime and delivers the time interval 50min that soda ash terminates, dispensing is reacted after terminating 2h, reaction stops stirring after terminating；
2) sample and do over again：Mixed bittern sample is taken to be analyzed after first order reaction clarifying reaction, Mixed bittern after test reaction Ca in liquid2+、Mg2+Concentration value, Ca2+Concentration be 2.8mg/L, Mg2+Concentration be 2.2mg/L, it is as a result up to standard, mix saltwater brine Carry out next process；
3) once flocculate：Saltwater brine is mixed to detect after ends 20min up to standard, into first order reaction bucket addition HEC- maleic acids- Chitin composite flocculant, the volume of addition/saltwater brine of flocculant is 1.5mg/L, and the flocculating setting time is 0.5h, sedimentation temperature Spend for 40 DEG C, sedimentation takes liquid after once sedimentation to observe after terminating, liquid is clarified after once settling, and opens slush pump, will be deposited on anti- The flocculant and reaction precipitation discharge reaction container of bottom of the barrel are answered, the supernatant liquor after standing is left and carries out subsequent technique；
4) second order reaction is clarified：After the completion of flocculating setting, liquid pump enters in secondary smoke reaction container after once settling, and opens Agitator is stirred to the saltwater brine in secondary smoke reaction container, and titanium dioxide soot is then passed through into secondary smoke reaction container Gas, is passed through the time for 3h, flow of carbon dioxide gas amount is 10L/min, continues stirring 10min after the completion of being passed through and is reacted, instead Stop stirring after the completion of answering；
5) secondary flocculation：After the completion of second order reaction clarification, HEC- maleic acids-chitosan is added into secondary smoke reaction container Composite flocculation agent, the volume of addition/saltwater brine of flocculant is 1.5mg/L, and the flocculating setting time is 0.5h, and settling temperature is 50 DEG C, sedimentation takes liquid after sedimentation to test turbidity using WGZ-200 types photoelectric turbidimeter after terminating, turbidity is 0.7 degree, is first opened Slush pump, discharges reaction container by the flocculant and reaction precipitation of being deposited on reaction bottom of the barrel, leaves the supernatant liquor after standing and enter Row subsequent technique；
6) liquid is transferred to the smart halogen bucket in salt manufacturing workshop and carries out subsequent fine halogen after the secondary settlement after will be up to standard.
HEC- maleic acids-chitin composite flocculant uses HEC (hydroxyethyl cellulose), maleic acid and water in above-mentioned steps Dissolubility carboxymethyl chitosan is composited, and is the step of its specific preparation method：
(1) aqueous solution of maleic acid is configured, the wherein mass fraction of maleic acid is 8%；
(2) aqueous maleic acid is heated to 70 DEG C, then HEC is dissolved in the aqueous solution of maleic acid, course of dissolution In be sufficiently stirred for solution, be configured to HEC mass fractions be 30% mixed solution, wherein mixing time be 1h；
(3) continue the temperature of holding mixed solution, water-soluble carboxymethyl chitosan is dissolved in mixed solution, add shell The molal quantity of glycan, which is equal in the molal quantity of HEC in mixed solution, course of dissolution, is sufficiently stirred for solution, and wherein mixing time is 2h；
(4) temperature of above-mentioned solution is kept, glacial acetic acid is added into solution, 1h is sufficiently stirred for, mole of glacial acetic acid is added 1.2 times of the molal quantity that number is HEC in mixed solution, then adds mass fraction into solution and is combined for 10% watery hydrochloric acid Constantly solution is stirred in reaction, course of reaction, the reaction time is 4h, and solution is air-cooled into room temperature after the completion of reaction, quiet Put 30h；
(5) liquid dries evaporation at 60 DEG C after reacting, after having a large amount of floccules to separate out in solution, the cotton-shaped mistake of filtering acquisition Screening, filtrate is dried under 50 DEG C of environment, that is, obtains the HEC- maleic acids-chitin composite flocculant.
Embodiment 3
A kind of lime-flue gas bittern purifying method, is comprised the steps of：
1) first order reaction is clarified：The Ca in analysis, the former halogen of measurement is sampled to former halogen2+、Mg2+Concentration, it is anti-according to one-level Answer the Ca in the amount of former halogen and former halogen in bucket2+、Mg2+The amount of lime and soda ash needed for concentration value is calculated, first to first order reaction bucket Former halogen is inside pumped into, feeds intake, is fed intake in advance in advance while carrying out lime into first order reaction bucket with calculate gained lime consumption value 80% During start first order reaction bucket in agitator former halogen is stirred, so as to former halogen and lime mixing evenly, work as original Stop when the liquid level of halogen is to specified fluid level scale into former halogen；Then soda ash is delivered by calculating gained soda ash volume value into former halogen, The time interval of the release time of soda ash and the end that feeds intake in advance 1 hour；Delivered in most backward former halogen and calculate gained lime consumption value Remainder, deliver the time of remaining lime and deliver the time interval 60min that soda ash terminates, dispensing reacts 3h after terminating, Reaction stops stirring after terminating；
2) sample and do over again：Mixed bittern sample is taken to be analyzed after first order reaction clarifying reaction, Mixed bittern after test reaction Ca in liquid2+、Mg2+Concentration value, wherein Ca2+Concentration be 4.8mg/L, Mg2+Concentration be 3.1mg/L, it is as a result up to standard, mixing Saltwater brine carries out next process；
3) once flocculate：When mix saltwater brine detection it is up to standard or do over again feed intake end 20min after, to first order reaction bucket in add HEC- maleic acids-chitin composite flocculant, the volume of addition/saltwater brine of flocculant is 2mg/L, and the flocculating setting time is 0.5h, settling temperature is 50 DEG C, and sedimentation takes liquid after once sedimentation to observe after terminating, liquid is limpid up to standard after sedimentation.Once sedimentation reaches After mark, slush pump is first opened, the flocculant and reaction precipitation of being deposited on reaction bottom of the barrel are discharged into reaction container, left after standing Supernatant liquor carries out subsequent technique；
4) second order reaction is clarified：After the completion of flocculating setting, liquid pump enters in secondary smoke reaction container after once settling, and opens Agitator is stirred to the saltwater brine in secondary smoke reaction container, and titanium dioxide soot is then passed through into secondary smoke reaction container Gas, is passed through time 2h, and flow of carbon dioxide gas amount is 20L/min, continues stirring 30min after the completion of being passed through and is reacted, is reacted After the completion of stop stirring；
5) secondary flocculation：After the completion of second order reaction clarification, HEC- maleic acids-chitosan is added into secondary smoke reaction container Composite flocculation agent, the volume of addition/saltwater brine of flocculant is 2mg/L, and the flocculating setting time is 0.5h, and settling temperature is 50 DEG C, sedimentation takes the turbidity of liquid after liquid test turbidity after sedimentation, test gained secondary deposition to be 1.3 degree after terminating, up to standard.Then Slush pump is first opened, the flocculant and reaction precipitation of being deposited on reaction bottom of the barrel are discharged into reaction container, the upper strata after standing is left Clear liquid carries out subsequent technique；
6) liquid is transferred to the smart halogen bucket in salt manufacturing workshop and carries out subsequent fine halogen after the secondary settlement after will be up to standard.
HEC- maleic acids-chitin composite flocculant uses HEC (hydroxyethyl cellulose), maleic acid and water in above-mentioned steps Dissolubility carboxymethyl chitosan is composited, and is the step of its specific preparation method：
(1) aqueous solution of maleic acid is configured, the wherein mass fraction of maleic acid is 10%；
(2) aqueous maleic acid is heated to 80 DEG C, then HEC is dissolved in the aqueous solution of maleic acid, course of dissolution In be sufficiently stirred for solution, be configured to HEC mass fractions be 20% mixed solution, wherein mixing time be 1h；
(3) continue the temperature of holding mixed solution, water-soluble carboxymethyl chitosan is dissolved in mixed solution, add shell The molal quantity of glycan, which is equal in the molal quantity of HEC in mixed solution, course of dissolution, is sufficiently stirred for solution, and wherein mixing time is 1h；
(4) temperature of above-mentioned solution is kept, glacial acetic acid is added into solution, 1h is sufficiently stirred for, mole of glacial acetic acid is added 1.5 times of the molal quantity that number is HEC in mixed solution, then adds mass fraction into solution and is combined for 10% watery hydrochloric acid Constantly solution is stirred in reaction, course of reaction, the reaction time is 3h, and solution is air-cooled into room temperature after the completion of reaction, quiet Put 30h；
(5) liquid dries evaporation at 70 DEG C after reacting, after having a large amount of floccules to separate out in solution, the cotton-shaped mistake of filtering acquisition Screening, filtrate is dried under 50 DEG C of environment, that is, obtains the HEC- maleic acids-chitin composite flocculant.
Comparative example 1
A kind of lime-flue gas bittern purifying method, as described in Example 2, its difference is for its operating procedure and parameter： The step 1) in first order reaction clarification, bittern is carried out using storage soda ash for a long time and normal lime is placed in on-site First order reaction.Other techniques and parameter and embodiment 2 are just the same.
As a result in step 2) sampling and to do over again, detection finds Ca2+Concentration be 22.4mg/L, Mg2+Concentration be 3.7mg/L, Ca2+Concentration value is unsatisfactory for requiring, further purified using caustic soda and soda ash, and caustic soda is calculated according to measurement result Or the injected volume of soda ash is done over again, it is specifically calculated as follows：
Calcium ion is exceeded, and magnesium ion is up to standard,
Soda ash amount (kg)=(CCa2+× 2.65 ÷ 1000+0.1) × 5500 ÷ 0.988,
Caustic soda without,
Wherein CCa2+And CMg2+The Ca in mixing saltwater brine after reaction is represented respectively2+、Mg2+Concentration measurement, in above-mentioned formula Middle CCa2+And CMg2+Unit be mg/L；
Therefore reopen agitator to be stirred mixing saltwater brine, the above-mentioned placements of 887kg are added into first order reaction bucket The soda ash (certainly, better with qualified soda ash) of storage for a long time carries out purification of doing over again, and 3h, reaction knot are reacted in dispensing after terminating Stop stirring after beam.C in subsequent sampling and testing bitternCa2+And CMg2+Value, wherein Ca2+Concentration drop to 10.6mg/L, it is full Foot is required.
Comparative example 2
A kind of lime-flue gas bittern purifying method, as described in Example 2, its difference is for its operating procedure and parameter： The step 1) in first order reaction clarification, first order reaction is carried out to bittern using underproof lime and normal soda ash.Other Technique and parameter and embodiment 2 are just the same.
As a result in step 2) sampling and to do over again, detection finds Ca2+Concentration be 6.9mg/L, Mg2+Concentration be 21.1mg/L, Mg2+Concentration value is unsatisfactory for requiring, further purified using caustic soda and soda ash, is calculated and burnt according to measurement result The injected volume of alkali or soda ash is done over again, and it is specifically calculated as follows：
Calcium ion is up to standard, and magnesium ion is exceeded,
Caustic soda amount (kg)=CMg2+(mg/l) × 3.33 ÷ 0.3 of ÷ 1000 × 5500,
Soda ash is without adding
Wherein CCa2+And CMg2+The Ca in mixing saltwater brine after reaction is represented respectively2+、Mg2+Concentration measurement, in above-mentioned formula Middle CCa2+And CMg2+Unit be mg/L；
Therefore reopen agitator to be stirred mixing saltwater brine, into first order reaction bucket, addition 1288kg caustic soda is carried out Do over again purification, 3h is reacted in dispensing after terminating, reaction stops stirring after terminating.C in subsequent sampling and testing bitternCa2+And CMg2+Value, Wherein Mg2+Concentration drop to 2.6mg/L, meet and require.
Comparative example 3
A kind of lime-flue gas bittern purifying method, as described in Example 2, its difference is for its operating procedure and parameter： The step 1) in first order reaction clarification, first order reaction is carried out to bittern using underproof lime and underproof soda ash.Its His technique and parameter and embodiment 2 are just the same.
As a result in step 2) sampling and to do over again, detection finds Ca2+Concentration be 25.4mg/L, Mg2+Concentration be 24.7mg/L, Ca2+And Mg2+It is unsatisfactory for requiring with concentration value, is further purified using caustic soda and soda ash, according to measurement As a result calculate caustic soda or the injected volume of soda ash is done over again, it is specifically calculated as follows：
Calcium ion is exceeded, and magnesium ion is exceeded,
Soda ash amount (kg)=(CCa2+× 2.65 ÷ 1000+0.1) × 5500 ÷ 0.988,
Caustic soda amount (kg)=(CMg2+× 3.33 ÷ 1000) × 5500 ÷ 0.3,
Wherein CCa2+And CMg2+The Ca in mixing saltwater brine after reaction is represented respectively2+、Mg2+Concentration measurement, in above-mentioned formula Middle CCa2+And CMg2+Unit be mg/L；
Therefore reopen agitator to be stirred mixing saltwater brine, into first order reaction bucket, addition 931.4kg is qualified 3h is reacted in soda ash and 1507.9kg caustic soda, dispensing after terminating, reaction stops stirring after terminating.In subsequent sampling and testing bittern CCa2+And CMg2+Value, wherein Ca2+Concentration drop to 9.6mg/L；Mg2+Concentration drop to 4.4mg/L, meet and require.
Comparative example 4
A kind of lime-flue gas bittern purifying method, as described in Example 2, its difference is for its operating procedure and parameter： The step 3) once flocculate and step 5) the secondary polyacrylamide flocculant or poly- for using and often having in salt industry that flocculates Aluminum chloride flocculant is closed, is tested as a comparison.Other techniques and parameter and embodiment 2 are just the same.
5 experiments are carried out as flocculant with polyacrylamide flocculant and flocculant of polymeric aluminium chloride respectively, it is real every time The processing step tested is with parameter as embodiment 2.Sedimentation takes liquid after sedimentation to use WGZ-200 type photoelectricity turbidity respectively after terminating Measurement examination turbidity, as a result as shown in table 1：
Table 1
Many experiments show that polyacrylamide flocculant and flocculant of polymeric aluminium chloride are generally the time required to effectively settling 1h or so, under process conditions described in embodiment 2 (sedimentation time only has 30min), it is difficult to meet settlement request, as shown in table 1.
Comparative example 5
A kind of lime-flue gas bittern purifying method, as described in Example 2, its difference is for its operating procedure and parameter： HEC- maleic acids-the chitin composite flocculant is poly- using HEC (hydroxyethyl cellulose), maleic acid and water-soluble carboxymethyl shell Sugar is composited, and is the step of its specific preparation method：By the HEC, maleic acid and water-soluble carboxymethyl shell with the equivalent of embodiment 2 Glycan add simultaneously with the acetate and hydrochloride mixed solution of the equivalent of embodiment 2, without using the addition manner described in embodiment 2 and Sequentially.Other techniques and parameter and embodiment 2 are just the same.
Experiment finds that using above-mentioned synthetic method, solution is in the pasty state, it is impossible to form fluidic structures, and mixing time reaches 10h Afterwards, solution is still without too big change, and stands the above-mentioned state of solution holding after 30h.Embodiment institute is used to above-mentioned paste like structure The method for stating step (5)：Liquid dries evaporation at 60 DEG C after reacting, and then filters, and filtrate is dried under 50 DEG C of environment, Composition is obtained, the composition is then being used for a flocculating setting, knot as flocculant by the methods described of embodiment 2 Fruit finds that saltwater brine is still muddy after doing over again 3 times, does not reach the effect of flocculating setting.
Technical scheme provided by the present invention is described in detail above, for those of ordinary skill in the art, According to the thought of the embodiment of the present invention, it will change in specific embodiments and applications, in summary, this theory Bright book content should not be construed as limiting the invention.

Claims (10)

1. a kind of lime-flue gas bittern purifying method, it is characterised in that comprise the steps of：
1) first order reaction is clarified：Ca in the former halogen of measurement2+、Mg2+Concentration, is then clarified in former halogen amount and former halogen according to first order reaction Ca2+、Mg2+The amount of lime and soda ash needed for concentration value is calculated, is entered with calculate gained lime consumption value 60%~80% first Row lime feeds intake in advance, then reacts dispensing in completely backward former halogen by gained soda ash volume value dispensing soda ash is calculated into former halogen Remaining lime；
2) sample and do over again：Take Mixed bittern sample to be analyzed after first order reaction clarifying reaction, mixed after test reaction in saltwater brine Ca2+、Mg2+Concentration value, works as Ca2+≤15mg/L、Mg2+Up to standard during≤10mg/L, mixing saltwater brine carries out next process, works as Ca2 +、Mg2+When concentration value is unsatisfactory for above-mentioned requirements, further purified using caustic soda and soda ash；
3) once flocculate：When mix saltwater brine detection it is up to standard or do over again feed intake end after, added into mixing saltwater brine HEC- maleic acids- Chitin composite flocculant flocculating setting, sedimentation takes liquid after once sedimentation to observe after terminating, liquid is still muddy after once settling When, extension sedimentation time or timely do over again add flocculant again；
4) second order reaction is clarified：After the completion of flocculating setting, to once settling after liquid carry out second order reaction clarification, to once settle after Carbon dioxide flue gas is passed through in liquid, reaction solution is stirred during being passed through until reaction is complete, stops stirring after the completion of reaction Mix；
5) secondary flocculation：After the completion of second order reaction clarification, HEC- maleic acids-chitosan is added into secondary smoke reaction container compound Flocculant flocculating setting, sedimentation takes liquid test turbidity after sedimentation after terminating, when liquid turbidity is unqualified after secondary settlement, prolong Long sedimentation time or timely do over again add flocculant again, until liquid turbidity reaches requirement after secondary settlement；
6) liquid is transferred to the smart halogen bucket in salt manufacturing workshop and carries out subsequent fine halogen after the secondary settlement after will be up to standard.
2. a kind of lime according to claim 1-flue gas bittern purifying method, it is characterised in that the step is specific For：
1) first order reaction is clarified：The Ca in analysis, the former halogen of measurement is sampled to former halogen2+、Mg2+Concentration, according to first order reaction bucket Ca in the amount of interior former halogen and former halogen2+、Mg2+The amount of lime and soda ash needed for concentration value is calculated, the pump first into first order reaction bucket Enter former halogen, fed intake in advance while carrying out lime into first order reaction bucket with calculate gained lime consumption value 60%~80%, pre-cast During material start first order reaction bucket in agitator former halogen is stirred, so as to former halogen and lime mixing evenly, when Stop when the liquid level of former halogen is to specified fluid level scale into former halogen；Then it is pure by the volume value dispensing of gained soda ash is calculated into former halogen Time interval >=1 hour of alkali, the release time of soda ash and the end that feeds intake in advance；Lime obtained by calculating is delivered in most backward former halogen to use The remainder of value, delivers the time of remaining lime and delivers time interval >=40min that soda ash terminates, dispensing is anti-after terminating 1~3h, reaction is answered to stop stirring after terminating；
2) sample and do over again：Take Mixed bittern sample to be analyzed after first order reaction clarifying reaction, mixed after test reaction in saltwater brine Ca2+、Mg2+Concentration value, works as Ca2+≤15mg/L、Mg2+Up to standard during≤10mg/L, mixing saltwater brine carries out next process, works as Ca2 +、Mg2+When concentration value is unsatisfactory for above-mentioned requirements, further purified using caustic soda and soda ash, caustic soda is calculated according to measurement result Or the injected volume of soda ash is done over again, it is specifically calculated as follows：
A. calcium ion is exceeded, and magnesium ion is up to standard,
Soda ash amount (kg)=(CCa2+× 2.65 ÷ 1000+0.1) × 5500 ÷ 0.988,
Caustic soda without,
B. calcium ion is exceeded, and magnesium ion is exceeded,
Soda ash amount (kg)=(CCa2+× 2.65 ÷ 1000+0.1) × 5500 ÷ 0.988,
Caustic soda amount (kg)=(CMg2+× 3.33 ÷ 1000) × 5500 ÷ 0.3,
C. calcium ion is exceeded, and magnesium ion is exceeded,
Caustic soda amount (kg)=CMg2+(mg/l) × 3.33 ÷ 0.3 of ÷ 1000 × 5500,
Soda ash without adding,
Wherein CCa2+And CMg2+The Ca in mixing saltwater brine after reaction is represented respectively2+、Mg2+Concentration measurement, the C in above-mentioned formulaCa2+ And CMg2+Unit be mg/L；
3) once flocculate：When mix saltwater brine detection it is up to standard or do over again feed intake end 20min after, to first order reaction bucket in add HEC- Maleic acid-chitin composite flocculant, the volume of addition/saltwater brine of shown flocculant is 1~2mg/L, flocculating setting time For more than 0.5h, settling temperature is 40~50 DEG C, and sedimentation takes liquid after once sedimentation to observe after terminating, and liquid is still after once settling When muddy, extension 1~2h sedimentation times or timely do over again add flocculant again；
4) second order reaction is clarified：After the completion of flocculating setting, liquid pump enters in secondary smoke reaction container after once settling, and opens stirring Device is stirred to the saltwater brine in secondary smoke reaction container, and carbon dioxide flue gas is then passed through into secondary smoke reaction container, is led to The angle of incidence >=2h, flow of carbon dioxide gas amount is 10~20L/min, continues 10~30min of stirring after the completion of being passed through and is reacted, Stop stirring after the completion of reaction；
5) secondary flocculation：After the completion of second order reaction clarification, HEC- maleic acids-chitosan is added into secondary smoke reaction container compound Flocculant, the volume of addition/saltwater brine of shown flocculant is 1~2mg/L, and the flocculating setting time is more than 0.5h, sedimentation temperature Spend for 40~50 DEG C, sedimentation takes liquid test turbidity after sedimentation after terminating, liquid turbidity is unqualified after secondary settlement, extension 1 ~2h sedimentation times or timely do over again add flocculant again, until liquid turbidity reaches requirement after secondary settlement；
6) liquid is transferred to the smart halogen bucket in salt manufacturing workshop and carries out subsequent fine halogen after the secondary settlement after will be up to standard.
3. a kind of lime according to claim 1 or 2-flue gas bittern purifying method, it is characterised in that in order to prevent pipe Road is blocked, and original halogen amount and former halogen are delivered and must be rinsed immediately to delivering pipeline after terminating every time, and it is anti-that flushing liquor flows into one-level Answer and reaction is participated in bucket.
4. a kind of lime according to claim 2-flue gas bittern purifying method, it is characterised in that described once to settle Or after the secondary settlement is up to standard, slush pump is first opened, flocculant and the reaction precipitation discharge of reaction bottom of the barrel will be deposited on Reaction container, leaves the supernatant liquor after standing and carries out subsequent technique.
5. a kind of lime according to claim 1 or 2-flue gas bittern purifying method, it is characterised in that described secondary heavy Liquid turbidity acceptance value is≤3 degree after drop.
6. a kind of lime according to claim 1 or 2-flue gas bittern purifying method, it is characterised in that the HEC- horses Carry out sour-chitin composite flocculant to be composited using HEC (hydroxyethyl cellulose), maleic acid and chitosan, its specific preparation The step of method is：
(1) aqueous solution of maleic acid is configured, the wherein mass fraction of maleic acid is 5%~10%；
(2) aqueous maleic acid is heated to 70~80 DEG C, then HEC is dissolved in the aqueous solution of maleic acid, course of dissolution In be sufficiently stirred for solution, be configured to HEC mass fractions be 20%~30% mixed solution, wherein mixing time >=1h；
(3) continue the temperature of holding mixed solution, dissolve chitosan in mixed solution, the molal quantity of addition chitosan is equal to Solution is sufficiently stirred in mixed solution in HEC molal quantity, course of dissolution, wherein mixing time >=1h；
(4) temperature of above-mentioned solution is kept, glacial acetic acid is added into solution, 1h is sufficiently stirred for, quality is then added into solution Fraction for 10% watery hydrochloric acid be constantly stirred solution in recombination reaction, course of reaction, and the reaction time is 2~4h, Solution is air-cooled to room temperature after the completion of reaction, more than 30h is stood；
(5) liquid dries evaporation below 70 DEG C after reacting, after having a large amount of floccules to separate out in solution, the cotton-shaped mistake of filtering acquisition Screening, filtrate is dried under≤50 DEG C of environment, that is, obtains the HEC- maleic acids-chitin composite flocculant.
7. a kind of lime according to claim 6-flue gas bittern purifying method, it is characterised in that addition glacial acetic acid 1~1.5 times of the molal quantity that molal quantity is HEC in mixed solution.
8. a kind of lime according to claim 7-flue gas bittern purifying method, it is characterised in that addition glacial acetic acid 1.2 times of the molal quantity that molal quantity is HEC in mixed solution.
9. a kind of lime according to claim 6-flue gas bittern purifying method, it is characterised in that ensure multiple to be described Close flocculant and be free of small molecular weight impurity particle, drying is obtained after HEC- maleic acids-chitin composite flocculant, by the compound wadding In solidifying agent immersion redistilled water, then repeating said steps (5) 1~2 times.
10. a kind of lime according to claim 6-flue gas bittern purifying method, it is characterised in that the chitosan is Water-soluble carboxymethyl chitosan.
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CN107540072A (en) * 2017-09-18 2018-01-05 湖南省湘衡盐化有限责任公司 A kind of flocculant solution preparation method and bittern purifying method
CN109574041A (en) * 2018-12-28 2019-04-05 中盐淮安鸿运盐化有限公司 A kind of lime-flue gas bittern purifying method
CN109626688A (en) * 2018-12-10 2019-04-16 中盐枣阳盐化有限公司 It is a kind of do not purify under the conditions of middle less salt nitre compare brine concentration method
CN109867297A (en) * 2017-12-05 2019-06-11 南风化工集团股份有限公司 A method of with calcium and magnesium in phosphate removal sodium sulphate type bittern
CN115970482A (en) * 2022-12-23 2023-04-18 中盐金坛盐化有限责任公司 Method for purifying flue gas and brine to refine disinfection salt

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CN1910232A (en) * 2004-01-20 2007-02-07 东亚合成株式会社 Composition containing amphoteric water-soluble polymer
CN103319024A (en) * 2013-06-06 2013-09-25 中国轻工业长沙工程有限公司 Lime-carbon dioxide method nitrate water purification process

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CN1107121A (en) * 1993-12-08 1995-08-23 山东潍坊纯碱厂 Method of preparing refined brine by using bittern
CN1910232A (en) * 2004-01-20 2007-02-07 东亚合成株式会社 Composition containing amphoteric water-soluble polymer
CN103319024A (en) * 2013-06-06 2013-09-25 中国轻工业长沙工程有限公司 Lime-carbon dioxide method nitrate water purification process

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Publication number Priority date Publication date Assignee Title
CN107540072A (en) * 2017-09-18 2018-01-05 湖南省湘衡盐化有限责任公司 A kind of flocculant solution preparation method and bittern purifying method
CN109867297A (en) * 2017-12-05 2019-06-11 南风化工集团股份有限公司 A method of with calcium and magnesium in phosphate removal sodium sulphate type bittern
CN109626688A (en) * 2018-12-10 2019-04-16 中盐枣阳盐化有限公司 It is a kind of do not purify under the conditions of middle less salt nitre compare brine concentration method
CN109574041A (en) * 2018-12-28 2019-04-05 中盐淮安鸿运盐化有限公司 A kind of lime-flue gas bittern purifying method
CN115970482A (en) * 2022-12-23 2023-04-18 中盐金坛盐化有限责任公司 Method for purifying flue gas and brine to refine disinfection salt

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