CN105540935A - Method for removing fluorin ions, sulfate radical ions and iron ions from organic amine liquor - Google Patents

Method for removing fluorin ions, sulfate radical ions and iron ions from organic amine liquor Download PDF

Info

Publication number
CN105540935A
CN105540935A CN201610070401.3A CN201610070401A CN105540935A CN 105540935 A CN105540935 A CN 105540935A CN 201610070401 A CN201610070401 A CN 201610070401A CN 105540935 A CN105540935 A CN 105540935A
Authority
CN
China
Prior art keywords
organic amine
amine liquid
ion
ions
liquid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201610070401.3A
Other languages
Chinese (zh)
Inventor
左永伟
魏凤玉
罗松志
李正贤
王天保
何西民
王琪
陈亚中
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tongguan Smelting Branch Of Tongling Nonferrous Metals Group Co Ltd
Hefei University of Technology
Original Assignee
Tongguan Smelting Branch Of Tongling Nonferrous Metals Group Co Ltd
Hefei University of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tongguan Smelting Branch Of Tongling Nonferrous Metals Group Co Ltd, Hefei University of Technology filed Critical Tongguan Smelting Branch Of Tongling Nonferrous Metals Group Co Ltd
Priority to CN201610070401.3A priority Critical patent/CN105540935A/en
Publication of CN105540935A publication Critical patent/CN105540935A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • C02F2001/422—Treatment of water, waste water, or sewage by ion-exchange using anionic exchangers
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/101—Sulfur compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/12—Halogens or halogen-containing compounds
    • C02F2101/14—Fluorine or fluorine-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C02F2101/203—Iron or iron compound
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/18—Nature of the water, waste water, sewage or sludge to be treated from the purification of gaseous effluents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00—General aspects of water treatment
    • C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Treating Waste Gases (AREA)
  • Removal Of Specific Substances (AREA)

Abstract

The invention provides a method for removing fluorin ions and sulfate radical ions from organic amine liquor. The method comprises the following steps of 1, using the organic amine liquor containing the fluorin ions and the sulfate radical ions to take a reaction with a calcium carbonate suspension for producing calcium carbonate and calcium fluoride precipitates; 2, performing filtering treatment on the organic amine liquor treated in the first step, and removing the calcium carbonate and calcium fluoride precipitates in a reaction system; 3, contacting the organic amine liquor subjected to the filtering treatment with ion exchange resin, and performing ion exchange treatment. The method provided by the invention also comprises the step of removing ferrous ions and iron ions from the organic amine liquor. The organic amine liquor is pretreated by a limestone suspension; partial sulfate radical ions and fluorin ions are removed; then, filtering and ion exchange column treatment are performed; the fluorin ions and the sulfate radical ions in the organic amine liquor after the resolution treatment can be effectively removed; the operation burden of an ion exchange column can be relieved; the service life of the organic amine liquor is prolonged.

Description

Remove the method for fluorion, sulfate ion and iron ion in organic amine liquid
Technical field
The present invention relates to organic amine liquid purification techniques in renewable organic amine liquid doctor treatment, particularly relate to a kind of method removing fluorion, sulfate ion and iron ion in organic amine liquid.Remove part fluorion and sulfate ion before energy ion exchange treatment of the present invention, improve the work-ing life of organic amine liquid, save production cost.
Background technology
Industrial smoke containing a large amount of sulfurous gas can not directly enter in air, needs just can discharge after purifying treatment.Usually, organic amine absorbent is adopted to carry out purifying treatment to described flue gas.Its principle makes sulfur-containing smoke gas and organic amine absorbent carry out reversely contacting the rich solution formed afterwards containing negatively charged ion such as nitrate radical, inferior sulfate radical, bisulfite, sulfate radical, chlorion, fluorions.The organic amine salt existed with the form such as inferior sulfate radical, bisulfite in rich solution can by carrying out heating desorption in desorption tower, discharge the acidic high-temperature mixed gas containing sulfurous gas, then the sulfur dioxide gas of high density can be reclaimed through condensation and gas-liquid separation, for Sulphuric acid or sulphur etc.The organic amine absorbent obtained after desorb is returned poor amine liquid storage tank, then organic amine absorbent is through purifying treatment simultaneously, after removing sulfate radical, fluorion etc., again loops back absorption tower and processes flue gas.
For organic amine absorbent, sulfate radical, fluorion belong to a kind of pollutent or chaff interference, when generating and running up to certain value, the sweetening effectiveness of organic amine absorbent to flue gas will be affected, and also corrosion is also existed to equipment, sulfate ion after effective removal parsing in organic amine absorbent and fluorion are one of focus technology points of operation flue gas desulfurization technique steady in a long-term.
At present, the conventional method removing sulfate ion and fluorion has electroosmose process, settling process or ion exchange method.Sulfate ion after resolving in organic amine absorbent and fluorinion concentration higher, ion-exchange column operation burden is heavier, removal effect is not good, and special iron ion of resolving in rear organic amine absorbent makes exchange resin have intoxicating phenomenon, increases the consumption of ion exchange resin.
Summary of the invention
Technical problem solved by the invention is: overcome the defect removing sulfate ion and fluorion method poor effect in organic amine liquid at present, when in organic amine liquid, nitrate radical plasma concentration is higher, direct employing ion exchange treatment, sulfate ion and fluorion decreasing ratio instability in organic amine liquid, impurity anions concentration in organic amine liquid is higher, and the removal efficiency of sulfate ion and fluorion is lower.The invention provides a kind of method removing fluorion and sulfate ion in organic amine liquid, by organic amine liquid through the pre-treatment of Wingdale suspension liquid, remove portion sulfate ion and fluorion, then after filtration, treatment on ion exchange columns, effectively can remove the fluorion in the organic amine liquid after dissection process and sulfate ion, alleviate the operation burden of ion exchange column, improve the work-ing life of organic amine liquid.
Second technical problem solved by the invention is: overcome the defect removing sulfate ion and fluorion method poor effect in organic amine liquid at present, by removing iron ion in organic amine liquid, avoid ion exchange resin poisoning, decrease the consumption of ion exchange resin.
Specifically, the present invention proposes following technical scheme.
First aspect, the invention provides a kind of method removing fluorion and sulfate ion in organic amine liquid, the method comprises the steps:
First step, makes containing fluorion (F -) and sulfate ion (SO 4 2-) organic amine liquid and calcium carbonate suspension liquid react, generate calcium carbonate and calcium fluoride precipitate;
Second step, carries out filtration treatment by the organic amine liquid after first step process, the calcium carbonate in removing reaction system and calcium fluoride precipitate; And
Third step, by the organic amine liquid after filtration treatment and contacts ionic exchange resin, carries out ion exchange treatment.
Preferably, wherein, in first step, the massfraction of described calcium carbonate suspension liquid is 5-15wt%, and described is 1:1.2-1.8 containing fluorion and the organic amine liquid of sulfate ion and the volume ratio of calcium carbonate suspension liquid, preferred 1:1.5.
Preferably, wherein, in first step, the described feed flow containing the organic amine of fluorion and sulfate ion is 25-35m 3/ h, preferred 30m 3/ h; The suspension liquid feed flow of described calcium carbonate is 40-50m 3/ h, preferred 45m 3/ h.
Preferably, wherein, in first step, described organic amine liquid containing fluorion and sulfate ion and calcium carbonate suspension liquid react under agitation, and stirring velocity is 40-60rpm, preferred 50rpm; The residence time of reaction system is 8-12min, preferred 10min.
Preferably, wherein, in first step, the pH value of reaction system is 7.0-9.0, preferred 7.0-7.8.
Preferably, wherein, first step also comprises the step removing ferrous ion in organic amine liquid and iron ion.
Preferably, wherein, air is passed in the reaction system of first step, the ferrous ions in organic amine liquid is become iron ion, and generates ferric hydroxide precipitate.
Preferably, wherein, in first step, step diatomite and/or activated carbon powder added in the reaction system of first step is also comprised.
Preferably, wherein, in third step, ion exchange resin is strong basic type anion-exchange resin.
Preferably, wherein, in ion exchange treatment, temperature is 15 ~ 45 DEG C, and pressure is 10 ~ 40KPa air speed is 0.8 ~ 1.0cm/s.
Technical scheme of the present invention is adopted at least to have following beneficial effect: the present invention adopts calcium carbonate suspension liquid to carry out reactions steps, sulfate removal rate is at 5%-30%, the decreasing ratio of fluorion is at 25%-50%, carry out ion-exchange treatment step, in organic amine liquid, sulfate removal rate is 11% ~ 25%, the decreasing ratio of fluorion 7% ~ 17%, integrated artistic sulfate removal rate and fluorion decreasing ratio high.In addition, iron ion decreasing ratio of the present invention is 5% ~ 15%.The present invention is applicable to the isoionic organic amine liquid of purification enrichment nitrate radical, improves the work-ing life of purification organic amine liquid, saves production cost.The present invention be a kind of technique simple efficient, invest little, running cost is low, fluorion, the technology that sulfate removal rate is high.
Embodiment
Content for a better understanding of the present invention, is described further technical scheme of the present invention below in conjunction with embodiment, but concrete embodiment is not the restriction done the present invention.
Sulfur-containing oxide (SO 2and SO 3) stack gas or other industrial gaseous wastees need just can discharge after purifying treatment.In prior art, organic amine liquid is adopted to carry out purifying treatment to described flue gas in absorption tower, concrete, sulfur-containing smoke gas carries out reverse contact with organic amine liquid in absorption tower, form the rich solution containing negatively charged ion such as inferior sulfate radical, bisulfite, sulfate radical, chlorine root, fluorine root, nitrate radicals, the flue gas after process discharges air after other aftertreatments.Rich solution is added Thermal desorption in Analytic Tower, the organic amine salt existed with the form such as inferior sulfate radical, bisulfite in rich solution can by heating desorption in desorption tower, discharge the high-temperature gas mixture body containing sulfurous gas sour gas, then through condensation and gas-liquid separation, the sulfur dioxide gas of high density can be reclaimed, for Sulphuric acid or sulphur etc.Then, the organic amine liquid after Analytic Tower process is transported in poor amine liquid storage tank, and after filtration unit (such as pressure filter, filter) process, spent ion exchange resin process organic amine liquid, to remove sulfate radical in machine amine liquid and fluorine radical ion.Organic amine liquid after treatment on ion exchange columns reuses to carry out circular treatment to described flue gas.But, contain fluorion (F by ion exchange resin treatment -) and sulfate ion (SO 4 2-) organic amine liquid time, ion exchange resin consumption is many, and effectively can not remove fluorion.When being recycled by the fluorion organic amine liquid containing high density, reduce organic amine liquid to the receptivity of the sour gas such as sulfurous gas, particularly also can cause corrosion to sweetener such as absorption tower.In addition, prior art ion exchange treatment is limited in one's ability, selective to negatively charged ion, when in organic amine liquid, nitrate ion concentration is higher, the removal ability of sulfate ion is not obvious, and there is organic amine liquid entrainment loss phenomenon in regenerative process, resin regeneration process flush time is long, and a reaction time needs about 6 hours.
The present invention arranges reactive tank the physical filtering device (pressure filter, filter etc.) of traditional organic amine liquid refining plant is front, adopts the suspension liquid process of limestone powder or calcium carbonate preparation to contain fluorion (F -) and sulfate ion (SO 4 2-) organic amine liquid, reach and remove part fluorion (F -) and sulfate ion (SO 4 2-) effect, to the process of subsequent ion exchange column bring just benefit and improve overall fluorion (F -) and sulfate ion (SO 4 2-) removal effect.The present invention can also remove ferrous ion in organic amine liquid and iron ion, avoids ion exchange resin poisoning, decreases the consumption of ion exchange resin.
" sulfur-containing smoke gas " of the present invention refers to sulfur-containing oxide (SO 2and SO 3) stack gas or other industrial gaseous wastees." desulfurization " of the present invention refers to and remove oxysulfide (SO from stack gas or other industrial gaseous wastees 2)." organic amine " of the present invention refers to that routine can be applied to the organic species of organic amine wet desulphurization, include but not limited to N, N-dihydroxy ethyl piperazine, piperazine, thanomin, diethanolamine, trolamine, methyldiethanolamine, tripropanol amine, three butanolamines, triethylenediamine etc." organic amine liquid " of the present invention refers to the aqueous solution containing above-mentioned organic amine.Of the present invention " containing fluorion (F -) and sulfate ion (SO 4 2-) organic amine liquid " refer to and adopt organic amine liquid to carry out desulfurization process to containing sulfurous gas, sulphur trioxide and hydrofluoric sulfur-containing smoke gas, the liquid then obtained after Analytic Tower dissection process.
The method of fluorion, sulfate ion and iron ion in organic amine liquid is removed the following detailed description of the present invention.
Remove a method for fluorion and sulfate ion in organic amine liquid, the method comprises the steps:
First step, makes containing fluorion (F -) and sulfate ion (SO 4 2-) organic amine liquid and calcium carbonate suspension liquid react.Fluorion (F in organic amine liquid -) and calcium carbonate reaction, generate calcium fluoride precipitate, the sulfate ion (SO in organic amine liquid 4 2-) and calcium carbonate reaction, generate calcium sulfate precipitation.Reaction equation is as shown below:
CaCO 3+2H ++SO 4 2-＝CaSO 4↓+H 2O+CO 2
CaCO 3+2H ++2F -＝CaF 2↓+H 2O+CO 2
In the present invention, containing fluorion (F -) and sulfate ion (SO 4 2-) organic amine liquid in, fluorion (F -) concentration can be more than 157mg/L, sulfate ion (SO 4 2-) concentration can be more than 1g/L.
Source of calcium carbonate of the present invention can be Wingdale or calcium carbonate compound etc., by soluble in water for source of calcium carbonate powder, is mixed with the suspension liquid of 5-15wt%.Preferably, source of calcium carbonate powder is through refining, and the volume particle size distribution of more than 80% particle is between 0.074-0.147 μm (200 ~ 100 order), and its purity is not less than 85%.Described is 1:1.2-1.8 containing fluorion and the organic amine liquid of sulfate ion and the volume ratio of calcium carbonate suspension liquid, preferred 1:1.5.The described feed flow containing the organic amine of fluorion and sulfate ion is 25-35m 3/ h, preferred 30m 3/ h; The suspension liquid feed flow of described calcium carbonate is 40-50m 3/ h, preferred 45m 3/ h.The pH value controlling reaction system in reaction process is 7.0-9.0, preferred 7.0-7.8.On pH value of reaction system is greater than, adds acid solution in limited time, under pH value of reaction system is less than, adds alkali lye in limited time.Preferred acid solution is sulphuric acid soln, and preferred alkali lye is sodium hydroxide solution.PH changing conditions can be observed by online pH meter.PH value controls, when the scope of the invention is outer, can uses excessive acid solution or alkali lye, introduce new impurity, such as sodium ion, thus affect recycling of organic amine liquid.
In this step, described organic amine liquid containing fluorion and sulfate ion and calcium carbonate suspension liquid react under agitation, and stirring velocity is 40-60rpm, preferred 50rpm; The residence time of reaction system is 8-12min, preferred 10min.
In a concrete embodiment, reactive tank is set, by the calcium carbonate suspension liquid of 5-15wt%, with 45m the physical filtering device (pressure filter, filter etc.) of organic amine liquid refining plant is front 3the flow of/h is added in reactive tank.Carried by transferpump bottom poor amine liquid storage tank and be rich in F -, SO 4 2-organic amine liquid with 30m 3the flow of/h enters in reactive tank, and open whipping appts in reactive tank, stirring velocity is 40-60rpm, preferred 50rpm, and the residence time of reaction system is 8-12min, preferred 10min.Control pH value in reaction at 7.0-7.8.Through measuring, SO in organic amine liquid 4 2-decreasing ratio at about 5-30%, F -decreasing ratio at about 30-50%.The carbonic acid gas generated directly is discharged from reactive tank.
In this step, the preferred technical scheme of the present invention also comprises the step removing ferrous ion in organic amine liquid and iron ion.Concrete, passed into by air in the reaction system of first step, the ferrous ions in organic amine liquid becomes iron ion, and generates ferric hydroxide precipitate further, to remove ferrous ion in organic amine liquid and iron ion.The intake of air is the reacting weight according to pending organic amine liquid ferrous ions, when the opportunity of air can be reaction beginning, also can be after reaction terminates.Due to the existence of nitrate ion, ferrous ion is easy to be oxidized to iron ion, and therefore the speed that passes into of air does not have special requirement, can complete speed of the present invention, can the phase passes into air after the reaction.The decreasing ratio of ferrous ion and iron ion is 5% ~ 15%.
In this step, diatomite and/or activated carbon powder can also be added in the reaction system of first step.The present invention's diatomite used, activated carbon powder are conventional commercial diatomite and activated carbon powder.Diatomite, activity charcoal powder are sorbing materials, the fine dusts in absorption organic amine liquid and particulate matter.Add diatomite and/or activated carbon in the first step reaction later stage, add-on is determined by according to organic amine liquid purity.
In this step, sulfate removal rate is at 5%-30%, and the decreasing ratio of fluorion is at 25%-50%.
Second step, carries out filtration treatment by the organic amine liquid after first step process.
In the present invention, described filter method can adopt conventional method to implement, to remove calcium fluoride precipitate and the calcium sulfate precipitation of first step generation, and other solids suspensions in organic amine liquid.The preferred filter type of the present invention carries out press filtration for adopting plate-and-frame filter press.Described plate-and-frame filter press is conventional equipment.
Third step, by the organic amine liquid after filtration treatment and contacts ionic exchange resin, carries out ion exchange treatment.
The mode of the present invention to organic amine liquid and contacts ionic exchange resin does not have special stipulation, and such as, organic amine liquid after can making filtration treatment crosses ion exchange resin column, or makes contacts ionic exchange resin impregnated in organic amine liquid.In this step, ion exchange resin column is the strong basic type anion-exchange resin of strong basic type anion-exchange resin post, optimization styrene system, such as D201 macroporous resin, 201*4 strongly basic anion exchange resin or 201*7 strongly basic anionic resin.In ion exchange treatment, temperature is 15 ~ 45 DEG C, and pressure is 10 ~ 40KPa, and air speed is 0.8 ~ 1.0cm/h.
After ion exchange treatment, in organic amine liquid, sulfate removal rate is 11% ~ 25%, and the decreasing ratio of fluorion is 7% ~ 17%.Organic amine liquid after ion exchange treatment reuses to carry out circular treatment to flue gas.
Below by embodiment, the invention will be further described.
In the following Examples and Comparative Examples, containing fluorion (F -) and sulfate ion (SO 4 2-) organic amine liquid be following method obtain.Sulfur-containing smoke gas consists of: SO 2: 6000 ~ 10000mg/Nm 3, SO 3: 190 ~ 260mg/Nm 3; O 2: 18% ~ 19%wt; H 2o:90 ~ 120g/Nm 3; N xo:150 ~ 250mg/Nm 3, all the other are nitrogen.F ion content is lower, but accumulative harm is comparatively large, and HF has severe corrosive in acid condition
Sulfur-containing smoke gas desulfurization: adopt organic amine liquid to process sulfur-containing smoke gas.By organic amine liquid from top, absorption tower spray, sulfur-containing smoke gas passes into from bottom, absorption tower, and control liquid-gas ratio is 6.75 ~ 7.71kg/m 3, fume desulfurizing agent contacts with sulfur-containing smoke gas is reverse, and the gas be cleaned enters air through tower top, absorbs SO 2organic amine liquid be called rich solution, by entering rich solution groove at the bottom of tower.
Desorb: by the rich solution that obtains from the rich solution groove on absorption tower by interchanger preheating, then from desorption tower top spray, rich solution partial solution in desorption tower is inhaled.At the bottom of desorption tower, there is reboiler, about 115 DEG C are heated to and desorb again in reboiler, liquid after desorb flows into bottom desorption apparatus, the desorption gas of high temperature and water vapour are discharged from the top of desorption tower, then condenser and vapour liquid separator is entered, in stripping gas, the cooled water of condensation with separating returns desorption tower, the purer high temperature SO obtained 2gas, sends into next procedure.Be called lean solution after rich solution desorb, discharge from the bottom of desorption tower and enter poor amine liquid storage tank through conveyer trough, and recycle as organic amine liquid.
Above-mentioned sulfur-containing smoke gas desulfurization and after resolving step cycle 3 times, get organic amine liquid in the lean solution groove raw material as following embodiment and comparative example, in this organic amine liquid, the concentration of organic amine is 18wt% ~ 20wt%, and the density of organic amine liquid is 1050kg/m 3, organic amine liquid temp about 80 DEG C, fluorion (F -) concentration is 157g/L, sulfate ion (SO 4 2-) concentration be 98.88g/L, Fe ionic concn is 32.02mg/L, nitrate ion concentration is 65 ~ 75mg/L.Fluorinion concentration adopts PXSJ-226 ion meter method to record, Fe ionic concn adopts adjacent phenanthroline spectrophotometry, sulfate ion adopts barium sulfate precipitate volumetry to record, and sulfite ion adopts iodimetry,iodometry to record, and nitrate ion adopts PXSJ-226 type ionometer method of masurement to record.
Embodiment 1
Limestone powder is added to the water and is mixed with the suspension liquid of 5wt%, with 45m 3/ h flow is added in reactive tank.Carried by transferpump bottom poor amine liquid storage tank and be rich in F -, SO 4 2-organic amine liquid with 25m 3/ h flow enters in reactive tank, and open whipping appts in reactive tank, rotating speed is 40rpm.Add sulphuric acid soln or sodium hydroxide solution by added automatically system, control pH value in reaction at 7.0-8.0, the reaction system residence time is 8min.Through measuring, in organic amine liquid, fluorinion concentration is 115mg/L, and sulfate ion concentration is 79.87g/L, SO 4 2-decreasing ratio at 19.23%, F -decreasing ratio 27%.
By organic amine liquid reacted in reactive tank again by being pumped to plate-and-frame filter press (Hangzhou Xing Yuan, F-40m 2, filtration area is 40 square metres) and carry out press filtration.Organic amine liquid after filtration delivers to system reuse again by being pumped to after D201 macroporous strong-base type anion-exchange column carries out deep purifying.
From the organic amine liquid that ion exchange column is discharged, fluorinion concentration is 103mg/L, and sulfate ion concentration is 69.30g/L, and fluorion decreasing ratio is 10.43%, and sulfate removal rate is 13.23%.
Embodiment 2
Limestone powder is added to the water and is mixed with the suspension liquid of 15wt%, with 50m 3/ h flow is added in reactive tank.Carried by transferpump bottom poor amine liquid storage tank and be rich in F -, SO 4 2-organic amine liquid with 35m 3/ h flow enters in reactive tank, and open whipping appts in reactive tank, rotating speed is 60rpm.Add sulphuric acid soln or sodium hydroxide solution by added automatically system, control pH value in reaction at 8.0-9.0, the reaction system residence time is 12min.Through measuring, in organic amine liquid, fluorinion concentration is 96mg/L, and sulfate ion concentration is 71.44g/L, SO 4 2-decreasing ratio at 27.75%, F -decreasing ratio 38.85%.
Organic amine liquid reacted in reactive tank is carried out press filtration by being pumped to plate-and-frame filter press (with embodiment 1) again.Organic amine liquid after filtration delivers to system reuse again by being pumped to after D201 macroporous strong-base type anion-exchange column carries out deep purifying.
From the organic amine liquid that ion exchange column is discharged, fluorinion concentration is 85mg/L, and sulfate ion concentration is 59.98g/L, and fluorion decreasing ratio is 11.46%, and sulfate removal rate is 16.04%.
Embodiment 3
Limestone powder is added to the water and is mixed with the suspension liquid of 10wt%, with 45m 3/ h flow is added in reactive tank.Carried by transferpump bottom poor amine liquid storage tank and be rich in F -, SO 4 2-organic amine liquid with 30m 3/ h flow enters in reactive tank, and open whipping appts in reactive tank, rotating speed is 50rpm.Add sulphuric acid soln or sodium hydroxide solution by added automatically system, control pH value in reaction 7.0 ~ 7.8, the reaction system residence time is 10min.Through measuring, in organic amine liquid, fluorinion concentration is 98g/L, and sulfate ion concentration is 71.84g/L, SO 4 2-decreasing ratio at 27.35%, F -decreasing ratio 37.58%.
Organic amine liquid reacted in reactive tank is carried out press filtration by being pumped to plate-and-frame filter press (with embodiment 1) again.Organic amine liquid after filtration delivers to system reuse again by being pumped to after D201 macroporous strong-base type anion-exchange column carries out deep purifying.
From the organic amine liquid that ion exchange column is discharged, fluorinion concentration is 86mg/L, and sulfate ion concentration is 63.46g/L, and fluorion decreasing ratio is 12.74%, and sulfate removal rate is 11.66%.
Embodiment 4
Limestone powder is added to the water and is mixed with the suspension liquid of 10wt%, with 45m 3/ h flow is added in reactive tank.Carried by transferpump bottom poor amine liquid storage tank and be rich in F -, SO 4 2-organic amine liquid with 30m 3/ h flow enters in reactive tank., air is passed in reactive tank, to remove the iron ion in organic amine liquid meanwhile.
Open whipping appts in reactive tank, rotating speed is 50rpm.Add sulphuric acid soln or sodium hydroxide solution by added automatically system, control pH value in reaction 7.0 ~ 7.8, the reaction system residence time is 10min.
Through measuring, in organic amine liquid, fluorinion concentration is 96mg/L, and sulfate ion concentration is 72.20g/L, and iron concentration is 27.95mg/L, SO 4 2-decreasing ratio at about 26.98%, F -decreasing ratio about 38.85%, iron ion decreasing ratio is 12.71%.
Organic amine liquid reacted in reactive tank is carried out press filtration by being pumped to plate-and-frame filter press (with embodiment 1) again.Organic amine liquid after filtration delivers to system reuse again by being pumped to after D201 macroporous strong-base type anion-exchange column carries out deep purifying.
From the organic amine liquid that ion exchange column is discharged, fluorinion concentration is 87mg/L, and sulfate ion concentration is 62.66g/L, and fluorion decreasing ratio is 9.38%, and sulfate removal rate is 13.21%.
Comparative example 1
Carried by transferpump bottom poor amine liquid storage tank and be rich in F -, SO 4 2-organic amine liquid with 30m 3/ h flow is delivered to plate-and-frame filter press and is carried out press filtration.Organic amine liquid after filtration delivers to system reuse again by being pumped to after D201 macroporous strong-base type anion-exchange column carries out deep purifying.
From the organic amine liquid that ion exchange column is discharged, fluorinion concentration is 134mg/L, and sulfate ion concentration is 87.57g/L, and fluorion decreasing ratio is 14.65%, and sulfate removal rate is 11.44%.
Comparative example 2
Limestone powder is added to the water and is mixed with the suspension liquid of 10wt%, with 45m 3/ h flow is added in reactive tank.Carried by transferpump bottom poor amine liquid storage tank and be rich in F -, SO 4 2-organic amine liquid with 30m 3/ h flow enters in reactive tank., air is passed in reactive tank, to remove the iron ion in organic amine liquid meanwhile.
Whipping appts is opened in reactive tank.Add sulphuric acid soln or sodium hydroxide solution by added automatically system, control pH value in reaction more than 6.0, and be less than 7.0, the reaction system residence time is 10min.
Through measuring, in organic amine liquid, fluorinion concentration is 121mg/L, sulfate ion concentration is 82.34g/L, and iron concentration is that the decreasing ratio of 30.05mg/L, SO42-is about 16.73%, the decreasing ratio of F-is about 22.03%, and iron ion decreasing ratio is 6.09%.
Organic amine liquid reacted in reactive tank is carried out press filtration by being pumped to plate-and-frame filter press (with embodiment 1) again.Organic amine liquid after filtration delivers to system reuse again by being pumped to after D201 macropore ion exchange column carries out deep purifying.
From the organic amine liquid that ion exchange column is discharged, fluorinion concentration is 107mg/L, and sulfate ion concentration is 73.95g/L, and fluorion decreasing ratio is 11.57%, and sulfate removal rate is 10.19%.
As can be seen here, when pH value is less than 7.0, be unfavorable for removing of relevant ions.
Comparative example 3
Limestone powder is added to the water and is mixed with the suspension liquid of 10wt%, with 45m 3/ h flow is added in reactive tank.Carried by transferpump bottom poor amine liquid storage tank and be rich in F -, SO 4 2-organic amine liquid with 30m 3/ h flow enters in reactive tank., air is passed in reactive tank, to remove the iron ion in organic amine liquid meanwhile.
Whipping appts is opened in reactive tank.Add sulphuric acid soln or sodium hydroxide solution by added automatically system, control pH value in reaction at 9.0-10.0.
Through measuring, in organic amine liquid, fluorinion concentration is 107mg/L, and sulfate ion concentration is 71.54g/L, and iron concentration is 27.53mg/L, SO 4 2-decreasing ratio at about 27.65%, F -decreasing ratio about 31.85%, iron ion decreasing ratio is 13.97%.But detect that foreign ion sodium ion increases, be unfavorable for that amine liquid recycles.
Organic amine liquid reacted in reactive tank is carried out press filtration by being pumped to plate-and-frame filter press (with embodiment 1) again.Organic amine liquid after filtration delivers to system reuse again by being pumped to after D201 macropore ion exchange column carries out deep purifying.
From the organic amine liquid that ion exchange column is discharged, fluorinion concentration is 97mg/L, and sulfate ion concentration is 64.42g/L, and fluorion decreasing ratio is 9.35%, and sulfate removal rate is 9.95%.But detect that foreign ion sodium ion increases.
PH value is selected at 7.0-9.0 by the present invention, and especially 7.0 ~ 7.8, the efficiency comparison that sulfate ion and fluorion remove is high, and the foreign ion introduced is less.Although alkalescence strengthens be conducive to removing of ion, reinforced effects is not obvious, can introduce more foreign ion sodium ion etc. simultaneously.

Claims (10)

1. remove a method for fluorion and sulfate ion in organic amine liquid, the method comprises the steps:
First step, makes the organic amine liquid containing fluorion and sulfate ion and calcium carbonate suspension liquid react, generates calcium carbonate and calcium fluoride precipitate;
Second step, carries out filtration treatment by the organic amine liquid after first step process, the calcium carbonate in removing reaction system and calcium fluoride precipitate; And
Third step, by the organic amine liquid after filtration treatment and contacts ionic exchange resin, carries out ion exchange treatment.
2. method according to claim 1, it is characterized in that, in first step, the massfraction of described calcium carbonate suspension liquid is 5-15wt%, described is 1:1.2-1.8 containing fluorion and the organic amine liquid of sulfate ion and the volume ratio of calcium carbonate suspension liquid, preferred 1:1.5.
3. method according to claim 2, is characterized in that, in first step, the described feed flow containing the organic amine of fluorion and sulfate ion is 25-35m 3/ h, preferred 30m 3/ h; The suspension liquid feed flow of described calcium carbonate is 40-50m 3/ h, preferred 45m 3/ h.
4. the method according to any one of claim 1-3, is characterized in that, in first step, described organic amine liquid containing fluorion and sulfate ion and calcium carbonate suspension liquid react under agitation, and stirring velocity is 40-60rpm, preferred 50rpm; The residence time of reaction system is 8-12min, preferred 10min.
5. the method according to any one of claim 1-4, is characterized in that, in first step, the pH value of reaction system is 7.0-9.0, preferred 7.0-7.8.
6. the method according to any one of claim 1-5, is characterized in that, first step also comprises the step removing ferrous ion in organic amine liquid and iron ion.
7. method according to claim 6, is characterized in that, is passed into by air in the reaction system of first step, the ferrous ions in organic amine liquid is become iron ion, and generates ferric hydroxide precipitate.
8. the method according to any one of claim 1-7, is characterized in that, in first step, also comprises step diatomite and/or activated carbon powder added in the reaction system of first step.
9. the method according to any one of claim 1-8, is characterized in that, in third step, ion exchange resin is strong basic type anion-exchange resin.
10. method according to claim 9, is characterized in that, in ion exchange treatment, temperature is 15 ~ 45 DEG C, and pressure is 10 ~ 40KPa, and air speed is 0.8 ~ 1.0cm/s.
CN201610070401.3A 2016-01-29 2016-01-29 Method for removing fluorin ions, sulfate radical ions and iron ions from organic amine liquor Pending CN105540935A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610070401.3A CN105540935A (en) 2016-01-29 2016-01-29 Method for removing fluorin ions, sulfate radical ions and iron ions from organic amine liquor

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610070401.3A CN105540935A (en) 2016-01-29 2016-01-29 Method for removing fluorin ions, sulfate radical ions and iron ions from organic amine liquor

Publications (1)

Publication Number Publication Date
CN105540935A true CN105540935A (en) 2016-05-04

Family

ID=55820565

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610070401.3A Pending CN105540935A (en) 2016-01-29 2016-01-29 Method for removing fluorin ions, sulfate radical ions and iron ions from organic amine liquor

Country Status (1)

Country Link
CN (1) CN105540935A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108940385A (en) * 2018-07-25 2018-12-07 南开大学 A kind of preparation method of efficient defluorinate modified resin
CN111278578A (en) * 2017-11-10 2020-06-12 日本瑞翁株式会社 Method and apparatus for regenerating cleaning solvent composition, and method and system for cleaning object to be cleaned
CN111760456A (en) * 2020-06-30 2020-10-13 双盾环境科技有限公司 Organic amine desulfurizer solution purification, desalination and impurity removal process for removing sulfur dioxide
CN114195756A (en) * 2021-12-02 2022-03-18 泰兴华盛精细化工有限公司 Method for removing anionic impurities and moisture in methylene methanedisulfonate

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5265970A (en) * 1975-11-27 1977-05-31 Chiyoda Chem Eng & Constr Co Ltd Process for treating waste water containing sulfate ions
JPH04371292A (en) * 1991-06-19 1992-12-24 Electric Power Dev Co Ltd Treatment of water containing fluoride
JPH05253575A (en) * 1992-03-11 1993-10-05 Kurita Water Ind Ltd Treatment of fluorine-containing water
CN1163864A (en) * 1997-02-20 1997-11-05 广州天河腾图实业公司 Precipitant for removing sulfate radical in water by precipitation method
JP2002079268A (en) * 2000-09-04 2002-03-19 Toray Ind Inc Method and device for producing recycled water
JP2003071470A (en) * 2001-08-30 2003-03-11 Kurita Water Ind Ltd Method and apparatus for treating fluorine-containing water
CN1923345A (en) * 2006-08-25 2007-03-07 中国石油化工集团公司 Process for removal of sulfate ions from organic amine absorbent
CN101874982A (en) * 2009-12-10 2010-11-03 攀钢集团攀枝花钢铁钒钛股份有限公司 Method for recycling desulfurizer
CN101966424A (en) * 2010-09-09 2011-02-09 攀钢集团钢铁钒钛股份有限公司 Method for removing sulfate ions and chloride ions in organic amine absorbent
CN202161906U (en) * 2011-07-15 2012-03-14 攀钢集团攀枝花钢钒有限公司 Lateral-line desulfurization liquor purifying treatment equipment
CN102586804A (en) * 2012-03-27 2012-07-18 广西靖西县一洲锰业有限公司 Method for removing fluorine ion from manganese sulfate solution for producing electrolytic manganese metal
CN103933753A (en) * 2014-05-06 2014-07-23 云南锡业股份有限公司 Method for removing fluorine ion from organic amine absorbent

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5265970A (en) * 1975-11-27 1977-05-31 Chiyoda Chem Eng & Constr Co Ltd Process for treating waste water containing sulfate ions
JPH04371292A (en) * 1991-06-19 1992-12-24 Electric Power Dev Co Ltd Treatment of water containing fluoride
JPH05253575A (en) * 1992-03-11 1993-10-05 Kurita Water Ind Ltd Treatment of fluorine-containing water
CN1163864A (en) * 1997-02-20 1997-11-05 广州天河腾图实业公司 Precipitant for removing sulfate radical in water by precipitation method
JP2002079268A (en) * 2000-09-04 2002-03-19 Toray Ind Inc Method and device for producing recycled water
JP2003071470A (en) * 2001-08-30 2003-03-11 Kurita Water Ind Ltd Method and apparatus for treating fluorine-containing water
CN1923345A (en) * 2006-08-25 2007-03-07 中国石油化工集团公司 Process for removal of sulfate ions from organic amine absorbent
CN101874982A (en) * 2009-12-10 2010-11-03 攀钢集团攀枝花钢铁钒钛股份有限公司 Method for recycling desulfurizer
CN101966424A (en) * 2010-09-09 2011-02-09 攀钢集团钢铁钒钛股份有限公司 Method for removing sulfate ions and chloride ions in organic amine absorbent
CN202161906U (en) * 2011-07-15 2012-03-14 攀钢集团攀枝花钢钒有限公司 Lateral-line desulfurization liquor purifying treatment equipment
CN102586804A (en) * 2012-03-27 2012-07-18 广西靖西县一洲锰业有限公司 Method for removing fluorine ion from manganese sulfate solution for producing electrolytic manganese metal
CN103933753A (en) * 2014-05-06 2014-07-23 云南锡业股份有限公司 Method for removing fluorine ion from organic amine absorbent

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
全国勘察设计注册工程师环保专业管理委员会等: "《注册环保工程师专业考试复习教材》", 31 May 2008, 中国环境科学出版社 *
胡岳华: "《矿物浮选》", 31 March 2014, 中南大学出版社 *
陈景德等: "《爱国卫生运动工作手册》", 31 July 1986, 湖南人民出版社 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111278578A (en) * 2017-11-10 2020-06-12 日本瑞翁株式会社 Method and apparatus for regenerating cleaning solvent composition, and method and system for cleaning object to be cleaned
CN108940385A (en) * 2018-07-25 2018-12-07 南开大学 A kind of preparation method of efficient defluorinate modified resin
CN111760456A (en) * 2020-06-30 2020-10-13 双盾环境科技有限公司 Organic amine desulfurizer solution purification, desalination and impurity removal process for removing sulfur dioxide
CN114195756A (en) * 2021-12-02 2022-03-18 泰兴华盛精细化工有限公司 Method for removing anionic impurities and moisture in methylene methanedisulfonate

Similar Documents

Publication Publication Date Title
AU2018328418B2 (en) Method for controlling aerosol production during absorption in ammonia desulfurization
CN104923044B (en) Smoke gas treatment system and method based on ozone
CN102755823B (en) Method for desulfurizing high-sulphur boiler flue gas to prepare high-purity ammonium bisulfite
IL293785A (en) Controlling aerosol production during absorption in ammonia-based desulfurization
CN105540935A (en) Method for removing fluorin ions, sulfate radical ions and iron ions from organic amine liquor
CN102282106A (en) Utilisation of desalination waste
CN102745726B (en) Method for producing magnesium sulfate heptahydrate by using desulfurization wastewater
CN101444699A (en) Technical method for removing sulfur dioxide in flue gas by using sodium sulfite and equipment thereof
CN105233647B (en) A kind of method of ammonium sulfide solution desulphurization denitration
CN110272144A (en) A kind of processing method of ferric phosphate production waste water
CN105833678A (en) Method for desulfurization of coal-fired boiler flue gas with assistance of desorption waste liquid
CN112354332B (en) Method for applying membrane separation device to ammonia desulphurization
CN109879343A (en) A kind of processing system and processing method of catalytic cracking and desulfurizing waste water
CN105013317A (en) Process flow for recovering high-purity magnesium sulfite by magnesium oxide flue gas desulphurization
US3879521A (en) Removal of SO{HD 2 {B from flue gas
CN109200627A (en) A kind of purification method of alkanolamine solution
CN104740987B (en) A kind of resource ammonia desulfurizing process
CN116445198A (en) Efficient desulfurizing agent and preparation method thereof
CN105771594A (en) Zinc oxide desulfurization process
CN111392754B (en) Method and equipment for purifying calcium chloride from fluorine-containing solid waste
CN108726541B (en) Method for preparing sodium bisulfate by resource utilization of coal chemical industry waste gas and waste water
CN111701397B (en) Process for removing sulfate ions and chloride ions in organic amine desulfurization solution and reducing loss of organic amine solution
CN111137964A (en) Coal-fired boiler ammonia desulfurization slurry dechlorination treatment process
CN110787602A (en) Method for removing thiosulfate radicals by purifying amine liquid
CN204395762U (en) A kind of waste gas treatment equipment

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20160504