CN105645514B - The isolation and purification method of ammonium sulfate and sodium sulphate mixed solution in a kind of fume desulfurizing agent regenerative process - Google Patents
The isolation and purification method of ammonium sulfate and sodium sulphate mixed solution in a kind of fume desulfurizing agent regenerative process Download PDFInfo
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- CN105645514B CN105645514B CN201610038209.6A CN201610038209A CN105645514B CN 105645514 B CN105645514 B CN 105645514B CN 201610038209 A CN201610038209 A CN 201610038209A CN 105645514 B CN105645514 B CN 105645514B
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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/24—Sulfates of ammonium
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- 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
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- Environmental & Geological Engineering (AREA)
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Abstract
The isolation and purification method of ammonium sulfate and sodium sulphate mixed solution in a kind of fume desulfurizing agent regenerative process, by NH4 +Type cationic ion-exchange resin is filled in cation exchange column using wet method, by ammonium sulfate and sodium sulphate mixed solution by resin bed, collects post bottom ammonium sulfate efflux;After efflux is dried, ammonium sulfate is obtained, complete to isolate and purify;The ion exchange resin failed in exchange column being filled in using deionized water, ammonium bicarbonate soln priority drip washing to be regenerated, resin being finally washed with deionized, NH can be obtained again4 +Type resin.Present invention introduces ion exchange resin, the Efficient Conversion purification ammonium salt from the double salting liquids of accessory substance after the acidifying of sodium acid carbonate regenerative process, so as to obtain high-purity sulfuric acid ammonium, and loaded resin is utilized by being repeated after regeneration, resin regeneration efflux can also continue to serve as desulfurizing agent, without waste residue and liquid discharge, the green economy and utilization rate of technique are improve, rational approach is provided to reclaim.
Description
Technical field
Technical field is utilized the invention belongs to industrial wastewater, and in particular to ammonium sulfate in a kind of fume desulfurizing agent regenerative process
With the isolation and purification method of sodium sulphate mixed solution.
Background technology
The atmosphere pollution of current China is increasingly serious, used as maximum in the world coal production state and country of consumption, sulfur dioxide
Total emission volumn is in world's umber one, and in this context, flue gas desulfurization technique has obtained fast development in recent years, but largely
Desulfurizing byproduct it is also following, for traditional limestone-gypsum method, China just produces desulfurated plaster 5230 in only 2010
Ten thousand tons, desulfurated plaster comprehensive utilization it is poor, at this stage mainly with abandon stack based on, both waste land resource, again produce ring
Pollute in border.Therefore, the accessory substance produced by desulphurization denitration process process is put in face of chemical industry and environmentalist
Very urgent task.
Sodium acid carbonate sulfur method is than traditional desulfurization method of limestone-gypsum rate (close to 100% removal efficiency) high, reaction speed
Rate is fast, alkali utilization rate is high, and can simultaneously remove the heavy metals such as nitrogen oxides and mercury, and Tongji University's Dongmei SUN exists《Sodium acid carbonate
Desulfurization and its screening of optimal conditions are inquired into》And Timothy C.Keener exist《Study of the Reaction of
SO2with NaHCO3and Na2CO3》In mention NaHCO3Typically there is preferable desulfurized effect under different shape, there is pole
Great development utilizes future.But two large problems, i.e. cost of material process problem high and accessory substance are faced, sodium acid carbonate suction is constrained
Agent is received in the industrial development of desulfurization, its advantage is not brought into play at utmost.NaHCO3Flue gas desulfurization primary chemical is anti-
Should be:2NaHCO3+SO2+1/2O2→Na2SO4+2CO2+H2O, 2NaHCO3→Na2CO3+CO2+H2O, Na2CO3+SO2+1/2O2→
Na2SO4+2CO2。
In order to reduce cost and by-product contamination, " The Airborn ProcessTM" take ten years and investigated
A whole set of sodium acid carbonate removes SO2(US 005980848A, US 7393378B2), sodium acid carbonate regeneration (B of US 6475458)
And regeneration accessory substance fertilizer purifies technology and the SEPARATE APPLICATION of (US 006106796A) patent, and in the willing tower of U.S.'s Gent
Ji Zhou (Airborn companies 5MW power plants demonstration project), the Wyoming State (Jim Bridger power plants) and Haier of West Germany cloth are grand
The input application such as (Solvary power plants) ground.Sodium acid carbonate regenerative process main chemical reactions equation is:NH4HCO3+
Na2SO4→(NH4)2SO4+NaHCO3↓, i.e., more expensive sodium acid carbonate is regenerated come NaHCO with cheap ammonium hydrogen carbonate3Crystallization
Contain Na in residual solution afterwards2SO4、(NH4)2SO4、NH4HCO3With a small amount of NaHCO3, then the double salt of gained are molten after persulfuric acid acidifying
Na in liquid2SO4:(NH4)2SO4=1:2 (mol ratios), if directly discharge will cause serious water pollution to this waste water,
Airborn considers that the economic worth of sodium sulphate in this waste water is limited, so this waste water is carried out into separating-purifying, obtains high-purity
Ammonium sulfate, ammonium sulfate can be used as nitrogenous fertilizer, ore floatation, metal recovery, production refractory material etc., so as to larger economy can be obtained
Benefit, by 6 years (1990~1996) time process optimizations, it used Steppecd crystallization that the purity of ammonium sulfate is improved from 60%
To 99%, the sodium sulphate separated again returns to sodium acid carbonate regeneration stage.The method is high to Control system resolution requirement, consuming
Heat energy, crystallization and sweating speed are difficult effectively control, and recyclability is not strong.Therefore purification ammonium sulfate is converted from regenerative wastewater is
Significantly problem.
Also have to the method that this pair of salting liquid carries out trans-utilization a lot, such as sublimed method, cave ether organic solvent liquid-liquid extraction
Method etc..The product purity of sublimed method production is at a relatively high, and Na can not be detected substantially+Etc. any impurity, but the technical process is not easily-controllable
System, it is difficult to find suitable mode of heating and collect the method for product, and production process energy consumption is too high, raw materials consumption is very big,
It is difficult to produce economic benefit.Therefore consider from economic benefit angle and engineering reliability angle, should not use.Cave ether is organic
The mechanism of solvent liquid-liquid extraction method is alkali metal to be mutually complexed in water with not being complexed crown compound (such as 18- crown-s 6), is complexed sun
Ion and anion mutually form ion pair in water, complex ion to mutually entering organic phase by water, so as to reach deimpurity purpose,
Method selectivity is very strong, and extraction efficiency is also high, and major defect is cave ether expensive, and manufacturer is few, is difficult buying.Therefore should
Method is also uneconomical, should not use.
The content of the invention
To overcome the problems of the prior art, it is an object of the invention to provide a kind of selectivity it is good, can be recycled, environment
Pollute less, be suitable to gained ammonium sulfate and sulfuric acid after the fume desulfurizing agent regenerative process accessory substance acidifying of industrialized production, low cost
The isolation and purification method of the double salting liquids of sodium.
To achieve these goals, the present invention is adopted the following technical scheme that:
The isolation and purification method of ammonium sulfate and sodium sulphate mixed solution in a kind of fume desulfurizing agent regenerative process, by NH4 +Type
Cationic ion-exchange resin is filled in cation exchange column using wet method, at room temperature, by pH value in fume desulfurizing agent regenerative process
Ammonium sulfate for 4~8 passes through resin bed, Na with sodium sulphate mixed solution+With the NH on resin4 +Generation exchange reaction, collects
Post bottom ammonium sulfate efflux, with the Na in ammonium sulfate efflux+Concentration reaches 5mg/L to collect terminal;The ammonium sulfate that will be collected
After efflux is dried, ammonium sulfate is obtained, complete to isolate and purify.
The NH4 +Type cationic ion-exchange resin is containing sulfonic resin.
Described is gel-network precipitation method Seplite LSI-010, macroporous type cation containing sulfonic resin
Exchanger resin Amberlite 252Na or Amberlite FPC 22Na.
The pH value is that the flow velocity that 4~8 ammonium sulfate and sodium sulphate mixed solution pass through resin bed is 2~8BV/h.
By the NH after failure4 +It is 7~9 that type cationic ion-exchange resin is first washed with deionized to efflux pH value, then is used
Ammonium bicarbonate soln, ammonium chloride solution or ammonium sulfate drip washing resin, it is 7 to be finally washed with deionized to efflux pH value
~9, obtain NH4 +Type cationic ion-exchange resin, NH4 +Type cationic ion-exchange resin can be reused.
The molar concentration of the ammonium bicarbonate soln, ammonium chloride solution or ammonium sulfate is 1~2mol/L, and volume is 3
~5BV.
The flow velocity of the deionized water is 6~8BV/h.
The flow velocity of the ammonium bicarbonate soln, ammonium chloride solution or ammonium sulfate is 1.5~2BV/h.
Compared with prior art, the device have the advantages that being:The present invention at room temperature, uses NH4 +Type cation is handed over
Changing gained sodium sulphate and ammonium sulfate pair salting liquids after resin is acidified to sodium acid carbonate regenerative process accessory substance, to carry out ion exchange anti-
Answer and eluent dried, obtain high-purity sulphuric acid ammonium, with simplicity, purification efficiency advantage high, resin repeats regeneration,
And resin regeneration process efflux can also continue to serve as desulfurizing agent, the ammonium sulfate purity obtained by the method reach 95% with
On, commercial value is created, solve sodium acid carbonate in the prior art and exist in being processed as desulfurizer regeneration process byproduct
Difficult manipulation, the too big problem of energy consumption, greatly reduce production cost, compensate for sodium acid carbonate method desulphurization cost shortcoming high.
Other foreign ions will not be introduced again, reduce water pollution, without waste residue and liquid discharge, comprehensive resource utilization rate it is high, selectivity
Good, the green economy of whole method is good, and rational approach, more carbonic acid are provided to reclaim valuable industry and product for agriculture
Large-scale use of the hydrogen sodium method in flue gas desulfurization field is provided may.And with larger practicality and popularity, it is applicable
Ammonium sulfate is purified in being converted from various ammonium sulfate and the double salting liquid industrial wastewaters of sodium sulphate.
Further, the resin after ion exchange can carry out regeneration cycle with ammonium bicarbonate soln or other ammonium salt solutions
Utilize, regenerative process efflux can continue to serve as desulfurizing agent or recycling, and resin repeat usage is high.
Further, if using ammonium sulfate regenerating resin, efflux is double salt sodium sulphate and ammonium sulfate mixed solution, is somebody's turn to do
Mixed solution can return to deionization exchange and obtains ammonium sulfate again, and the ammonium sulfate of regeneration comes to double salting liquid ion exchanges
The ammonium sulfate for obtaining afterwards.This is also a circulation.
Brief description of the drawings
Fig. 1 is the schematic diagram that exchange adsorption is carried out on ion exchange resin.
Specific embodiment
The present invention is explained in detail in by the way of specific embodiment below, but the present invention is not limited to embodiment.
The present invention is comprised the following steps:
1) by NH4 +Type cationic ion-exchange resin is filled in cation exchange column using wet method, is 4 by pH value at room temperature
After~8 sodium acid carbonate desulfurization regeneration accessory substance acidifying the double salting liquids of gained (i.e. ammonium sulfate and sodium sulphate mixed solution) with 2~
The flow velocity of 8BV/h is by resin bed, Na+With the NH combined on resin4 +Generation exchange reaction, collects the ammonium sulfate outflow of post bottom
Liquid, with the Na in efflux+Concentration reaches 5mg/L for terminal, stops collecting.
2) after the ammonium sulfate efflux that will be collected is dried, ammonium sulfate is obtained, completes to isolate and purify;Wherein, BV is resinite
Product.
3) cationic ion-exchange resin after failure is filled in exchange column using wet method, adopts be washed with deionized first
It is 7~9 to pH value, then with the ammonium bicarbonate soln, ammonium chloride solution or ammonium sulfate that 3~5BV, molar concentration are 1~2mol/L
With the speed drip washing resin of 1.5~2BV/h, it is 7~9 to be finally washed with deionized to efflux pH value to solution, obtains NH4 +Type
Cationic ion-exchange resin;The NH4 +Cation exchange groups contained by type cationic ion-exchange resin are containing sulfonic resin, containing benzene sulfonic acid base
Resin can equally use.
The use ammonium bicarbonate soln drip washing resin, efflux is that sodium acid carbonate and ammonium hydrogen carbonate mixed solution can continue to use
Make fume desulfurizing agent.Ammonium bicarbonate soln can also use the ammonium salts such as ammonium chloride solution, ammonium sulfate to replace, but now, efflux
It is exactly villaumite or sulfate liquor, also recyclable conversion is recycled.
The present invention is described in detail below:
The first step, the type selecting of resin:According to the characteristic of ion exchange resin, in conjunction be currently needed for the sodium sulphate of purifying with
The property and feature of the double salting liquids of ammonium sulfate, from storng-acid cation exchange resin, with reference to making for itself system and resin
With parameter and performance, the NH of final choice4 +Type cationic ion-exchange resin is containing the tree that cation exchange groups are sulfonic group or benzene sulfonic acid base
Fat.
Second step, conversion purification ammonium sulfate:Using NH4 +Type cationic ion-exchange resin and Na in solution+Swap reaction,
And efflux is dried so as to obtain the ammonium sulfate of high-purity, specifically, by NH4 +Type cationic ion-exchange resin wet method
It is filled in cation exchange column, at room temperature, the double salting liquids of gained (rub after sodium acid carbonate desulfurization regeneration process byproduct is acidified
You are concentration ratio Na2SO4:(NH4)2SO4=1:2;PH value is 4~8) with the flow velocity of 2~8BV/h by resin bed, use 1mol/L
Sulfuric acid solution and the sodium hydroxide solution of 1mol/L adjust the pH value of ammonium sulfate and sodium sulphate mixed solution so that in liquid phase
Na+From liquid phase bulk motion to resin particle surfaces, and with the NH that combines on resin4 +Generation exchange reaction, is got off by exchange
NH4 +It is diffused into liquid phase main body so that there was only NH in solution4 +.Whole exchange process had both occurred to also occur in tree in resin surface
Inside fat, and equivalent exchange principle is followed, reaction equation is 2R-NH4+Na2SO4→2R-Na+(NH4)2SO4, exchange adsorption shows
Intention is shown in Fig. 1, in ion exchange process, is connected to the function base dissociation on the changeless skeleton in ion exchange resin
The ammonium ion for going out is swapped with the sodium ion dissociated in solution, and whole exchange process follows equivalent and exchanges principle, Er Qie
Resin particle surfaces and inside all there occurs ion exchange process, so that the amount of ammonium ion increases in solution, collect post bottom sulfuric acid
Ammonium efflux.Under normal circumstances, the speed of Liquid film diffusion or particles diffusion determines the general speed of ion exchange.
Finally press formula Q=(C-C0) V/W calculates the ion exchange capacity of ion exchange resin under fixed mass.
In formula:Q—Na+Exchange capacity;
C0NH in-solution4 +Initial concentration (mg/L);
NH in C-exchange efflux4 +Concentration (mg/L);
V-effluent volume (L);
The quality (g) of W-isolate and purify institute's spent ion exchange resin;
3rd step, the transition of resin:The resin of gained after step 2 conversion purification is filled in exchange column using wet method,
Use first deionized water with the flow velocity washing resin of 6~8BV/h to efflux pH value be 7~9, then using 3~5BV's of volume
Molar concentration be the ammonium bicarbonate soln of 1~2mol/L with the flow velocity drip washing resin of 1.5~2BV/h, sodium form resin is converted into
NH4 +Type cationic ion-exchange resin, then with deionized water with the flow velocity washing resin of 6~8BV/h to efflux pH value be 7~9, will
Obtain NH4 +Type storng-acid cation exchange resin is put into standby in closed vessel.
4th step:It is dried to obtain ammonium sulfate:After ammonium sulfate efflux obtained by step 2 is dried, ammonium sulfate is obtained,
Completion is isolated and purified.And according to《The measure (formaldehyde method) of nitrogen content in ammonium sulfate fertilizer》To detect the purity of ammonium sulfate.Gained
The ammonium sulfate purity for arriving is higher than 95%.
It is described in detail below by specific embodiment.Double salting liquids in embodiment 1~5 are sodium acid carbonate regeneration
Gained sodium sulphate and the double salting liquids of ammonium sulfate after process byproduct acidifying, it is 2% that mass concentration is used in embodiments of the invention,
Sodium sulphate is 1 with ammonium sulfate molar concentration rate:2 double salting liquids, ion exchange column volume is 120mL.
Embodiment 1:
1) gel-network precipitation method Seplite LSI-010 are filled in exchange column using wet method, are adopted first
With the flow velocity washing resin of 6BV/h to efflux pH value it is 7~9 with deionized water, then is 1mol/ with volume 4BV, molar concentration
The ammonium bicarbonate soln of L with 1.5BV/h flow velocity drip washing resins, finally again with deionized water with the flow velocity washing resin of 6BV/h extremely
Efflux pH value is 7~9, obtains NH4 +Type cationic ion-exchange resin.
2) by NH4 +Type cationic ion-exchange resin is filled in cation exchange column using wet method, is 5 by pH value at room temperature
The regeneration double salting liquids of accessory substance with the flow velocity of 3BV/h by resin bed, Na+With the NH combined on resin4 +Generation exchanges anti-
Should, post bottom ammonium sulfate efflux is collected, with the Na in ammonium sulfate efflux+Concentration reaches 5mg/L for terminal, stops collecting, and surveys
The ion exchange capacity Q of Seplite LSI-010 resins is made for 17.5mg/g, in the ammonium sulfate vacuum drying chamber that will be collected
After being dried at 55 DEG C, it is 96.9% to measure ammonium sulfate purity.
Embodiment 2:Amplification test
1) large pores cation exchange resin Amberlite FPC22Na are filled in exchange column using wet method, first
It is 7~9 with the flow velocity washing resin of 8BV/h to efflux pH value to use deionized water, is then with 5BV, molar concentration
The ammonium bicarbonate soln of 1.5mol/L with 1.5BV/h flow velocity drip washing resins, then deionized water with the flow velocity washing resin of 8BV/h extremely
Efflux pH value is 7~9, obtains NH4 +Type cationic ion-exchange resin.
2) respectively to wet resin (the i.e. NH of each filling 120mL in two exchange columns4 +Type cationic ion-exchange resin), then by two
Individual exchange column is together in series, and double salting liquids that pH value is 6 is passed through into resin bed with the flow velocity of 2BV/h, when second exchange column
Na in efflux+When concentration reaches 5mg/L, stop operation, the resin in two pillars is regenerated, start the pure of second batch
Change experiment, single batch can reach 20BV or so to the treating capacity of the double salting liquids of regeneration accessory substance.Determine first batch
The ion exchange capacity Q of Amberlite FPC22Na resins is 20.7mg/g, after the high-concentration sulfuric acid ammonium salt solution that will be collected is dried,
It is 98.5% to measure the ammonium sulfate purity of first batch, and the exchange capacity of second lot is 18.5mg/g, and ammonium sulfate purity is
96.7%, the exchange capacity of the 3rd batch is 17.2mg/g, and ammonium sulfate purity is 95.8%, and the exchange capacity of the 4th batch is
16.8mg/g, ammonium sulfate purity is 94.6%, and the exchange capacity of the 5th batch is 16.1mg/g, and ammonium sulfate purity is 93.1%.Put
Big experiment result shows that resins exchange rate is high, and gained ammonium sulfate purity is high, and absorption property stabilization, the resin after regeneration treatment is inhaled
Attached performance is preferable, keeps adsorption rate higher.
Embodiment 3:
1) large pores cation exchange resin Amberlite FPC 22Na are filled in exchange column using wet method, first
It is 7~9 with the flow velocity washing resin of 6BV/h to efflux pH value to use deionized water, is then 3BV, molar concentration with volume
It is that the ammonium sulfate of 2mol/L is extremely flowed out with 2BV/h flow velocity drip washing resins, then deionized water with the flow velocity washing resin of 6BV/h
Liquid pH value is 7~9, obtains NH4 +Type cationic ion-exchange resin
2) by NH4 +Type cationic ion-exchange resin is filled in cation exchange column using wet method, is 7 by pH value at room temperature
The regeneration double salting liquids of accessory substance with the flow velocity of 8BV/h by resin bed, Na+With the NH combined on resin4 +Generation exchanges anti-
Should, post bottom ammonium sulfate efflux is collected, with the Na in efflux+Concentration reaches 5mg/L for terminal, determines Amberlite
The ion exchange capacity Q of FPC22Na resins is 16.5mg/g, is dried at 55 DEG C in the ammonium sulfate vacuum drying chamber that will be collected
Afterwards, it is 96.8% to measure ammonium sulfate purity.
Embodiment 4:
1) large pores cation exchange resin Amberlite 252Na are filled in exchange column using wet method, are adopted first
With the flow velocity washing resin of 7BV/h to efflux pH value it is 7~9 with deionized water, is then 1.5mol/L, body with molar concentration
Product is 5BV, flow velocity is the ammonium chloride solution drip washing resin of 1.8BV/h, then deionized water is with the flow velocity washing resin of 6BV/h to stream
It is 7~9 to go out liquid pH value, obtains NH4 +Type cationic ion-exchange resin;
2) by NH4 +Type cationic ion-exchange resin is filled in cation exchange column using wet method, is 6 by pH value at room temperature
The regeneration double salting liquids of accessory substance with the flow velocity of 6BV/h by resin bed, Na+With the NH combined on resin4 +Generation exchanges anti-
Should, post bottom ammonium sulfate efflux is collected, with the Na in efflux+Concentration reaches 5mg/L for terminal, determines
The ion exchange capacity Q of Amberlite252Na resins is 18.1mg/g, 55 in the ammonium sulfate vacuum drying chamber that will be collected
After being dried at DEG C, it is 97.5% to measure ammonium sulfate purity.
For the mixed liquor containing ammonium ion and sodium ion in solution, anion is other ions, such as carbanion,
Chlorion, bicarbonate radical etc., can equally be purified using the method in the present invention.
Existing sodium acid carbonate desulfurization technology cost of material is high and the process problem of accessory substance in order to solve for the present invention, for carbon
Sodium sulfate byproduct and the double salting liquids of ammonium sulfate, convert to the ammonium sulfate in double salting liquids after sour hydrogen sodium regenerative process acidifying
Purify, and be firstly introduced the double salting liquids of gained after ion exchange resin is acidified to sodium acid carbonate regenerative process accessory substance and purify
Treatment, and achieves preferable effect, so as to obtain high-purity sulfuric acid ammonium, develops that a kind of selectivity is good, the rate of recovery is high, can follow
Ring using, it is low in the pollution of the environment, be suitable to industrialized production ammonium sulfate ion exchange preparation technology.Whole sodium acid carbonate is improve to take off
The green economy of sulphur technique.
Claims (1)
1. in a kind of fume desulfurizing agent regenerative process ammonium sulfate and sodium sulphate mixed solution isolation and purification method, its feature exists
In by NH4 +Type cationic ion-exchange resin is filled in cation exchange column using wet method, at room temperature, fume desulfurizing agent is regenerated
During pH value be 4~8 ammonium sulfate and sodium sulphate mixed solution by resin bed, Na+With the NH on resin4 +Exchange
Reaction, collects post bottom ammonium sulfate efflux, with the Na in ammonium sulfate efflux+Concentration reaches 5mg/L to collect terminal;To collect
Ammonium sulfate efflux dry after, obtain ammonium sulfate, complete to isolate and purify;The NH4 +Type cationic ion-exchange resin is containing sulfonic acid
The resin of base;
By the NH after failure4 +It is 7~9 that type cationic ion-exchange resin is first washed with deionized to efflux pH value, then uses carbonic acid
Hydrogen ammonium salt solution, ammonium chloride solution or ammonium sulfate drip washing resin, it is 7~9 to be finally washed with deionized to efflux pH value,
Obtain NH4 +Type cationic ion-exchange resin, NH4 +Type cationic ion-exchange resin can be reused;
The pH value is that the flow velocity that 4~8 ammonium sulfate and sodium sulphate mixed solution pass through resin bed is 2~8BV/h;
The molar concentration of the ammonium bicarbonate soln, ammonium chloride solution or ammonium sulfate be 1~2mol/L, volume be 3~
5BV;
The flow velocity of the ammonium bicarbonate soln, ammonium chloride solution or ammonium sulfate is 1.5~2BV/h;
Described is gel-network precipitation method Seplite LSI-010, macroporous type cation exchange containing sulfonic resin
Resin A mberlite FPC22Na or Amberlite 252Na;
The mobility of the deionized water is 6~8BV/h.
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CN109136574A (en) * | 2018-10-22 | 2019-01-04 | 湘潭大学 | A kind of pre- sulfur method of lead plaster based on the double salt of sodium ammonium |
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS524500A (en) * | 1975-07-01 | 1977-01-13 | Asahi Chem Ind Co Ltd | Recoverring method of ammonium sulfate from waste solution |
JPS5394447A (en) * | 1977-01-31 | 1978-08-18 | Mitsui Eng & Shipbuild Co Ltd | Method of traeting waste water containing ammonia nitrogen |
CN87103546A (en) * | 1987-05-18 | 1987-11-04 | 黄圣恒 | From diluted thioamine liquid, reclaim the method for solid ammonium sulfate |
CN1089235A (en) * | 1993-12-29 | 1994-07-13 | 张祥林 | The method of the single-phase decomposition system sodium bicarbonate of sodium sulfate and bicarbonate of ammonia |
CN101367568A (en) * | 2008-09-19 | 2009-02-18 | 广西大学 | Process for the separation of strong-acid cation exchange fibre of indium and cadmium |
CN103420448A (en) * | 2013-08-22 | 2013-12-04 | 张家港燎原环保科技有限公司 | Thiosulfate removing method for coke oven gas desulfuration liquid waste using ion exchange resin |
-
2016
- 2016-01-20 CN CN201610038209.6A patent/CN105645514B/en not_active Expired - Fee Related
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS524500A (en) * | 1975-07-01 | 1977-01-13 | Asahi Chem Ind Co Ltd | Recoverring method of ammonium sulfate from waste solution |
JPS5394447A (en) * | 1977-01-31 | 1978-08-18 | Mitsui Eng & Shipbuild Co Ltd | Method of traeting waste water containing ammonia nitrogen |
CN87103546A (en) * | 1987-05-18 | 1987-11-04 | 黄圣恒 | From diluted thioamine liquid, reclaim the method for solid ammonium sulfate |
CN1089235A (en) * | 1993-12-29 | 1994-07-13 | 张祥林 | The method of the single-phase decomposition system sodium bicarbonate of sodium sulfate and bicarbonate of ammonia |
CN101367568A (en) * | 2008-09-19 | 2009-02-18 | 广西大学 | Process for the separation of strong-acid cation exchange fibre of indium and cadmium |
CN103420448A (en) * | 2013-08-22 | 2013-12-04 | 张家港燎原环保科技有限公司 | Thiosulfate removing method for coke oven gas desulfuration liquid waste using ion exchange resin |
Non-Patent Citations (1)
Title |
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离子交换法制备纯硫代硫酸铵;曾庆华;《化工技术与开发》(第02期);33-34页 * |
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