CN108927004A - A kind of new process for making saltcake be converted into bronsted lowry acids and bases bronsted lowry with bipolar membrane electrodialysis method - Google Patents
A kind of new process for making saltcake be converted into bronsted lowry acids and bases bronsted lowry with bipolar membrane electrodialysis method Download PDFInfo
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- CN108927004A CN108927004A CN201810848562.XA CN201810848562A CN108927004A CN 108927004 A CN108927004 A CN 108927004A CN 201810848562 A CN201810848562 A CN 201810848562A CN 108927004 A CN108927004 A CN 108927004A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
- B01D61/44—Ion-selective electrodialysis
- B01D61/445—Ion-selective electrodialysis with bipolar membranes; Water splitting
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/74—Preparation
- C01B17/745—Preparation from sulfates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D1/00—Oxides or hydroxides of sodium, potassium or alkali metals in general
- C01D1/04—Hydroxides
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Abstract
The present invention relates to a kind of new processes for making saltcake be converted into bronsted lowry acids and bases bronsted lowry with bipolar membrane electrodialysis method, after dissolving deployed required concentration, sodium hydroxide is added and adjusts pH value, sodium hydroxide is added and not only realizes adjusting pH value, the zinc ion in metabisulfite solution is maximumlly changed into zinc hydroxide precipitation and realizes separation of solid and liquid, then zinc ion sediment is removed by ultrafiltration surge tank, using Bag filter, ion exchange resin system, Bipolar Membrane is entered back into after the filtration filter of PP millipore filter, the sulfuric acid generated by bipolar membrane electrodialysis system is concentrated using hyperfiltration, sodium hydroxide enters electrodialysis system and is concentrated.The present invention not only simplifies entire process flow and occupied area is small, farthest reduce the presence of the metal ions such as zinc ion and other impurity in solution, reduction is damaged caused by Bipolar Membrane, improve its service life, and the ion exchange resin system regeneration intervals phase is extended, it is also convenient for carrying out backwash recycling and reusing to zinc ion.
Description
Technical field
The present invention relates to a kind of new processes of waste disposal in Chemical Manufacture, and more specifically, the present invention is a kind of with double
Pole membrane electrodialysis method makes viscose rayon saltcake be converted into the new process that corresponding bronsted lowry acids and bases bronsted lowry carries out reuse.
Background technique
As China's textile industry scale constantly expands and viscose rayon demand is constantly promoted, contaminated wastewater also increasingly plus
Play, the work that this results in contaminated wastewater to administer is very severe, list wastewater treating technology in viscose rayon production with regard to China
There is also very big problem for status, be mainly reflected in administering method without novelty, low efficiency, it is at high cost, using limited etc..
Viscose rayon basic process mainly has: (1) prepared by viscose glue: preparing alkali cellulose including dipping squeezing, yellow prepares cellulose Huang
Acid esters, dissolution deaeration filtering etc..(2) fiberizing: viscose glue passes through spinning head after filtering before measuring and spinning, and forms more
Viscose glue thread is solidified into fibre bundle into spinning coagulation bath, and strand stretches by two baths, concise (including wash, takes off thereafter
Sulphur, bleaching, oil bath, drying etc.), curling cutting etc..Carbon disulfide, hydrogen sulfide and sulphur are released simultaneously, coagulating bath is by sulfuric acid, sulphur
Sour zinc, sodium sulphate are constituted.The main function of sodium sulphate is that viscose glue liquid stream is promoted to solidify and inhibit sulfuric acid dissociation in coagulating bath, makes fibre
The reproduction speed for tieing up plain sulphonic acid ester delays, and improves the concentration of sodium sulphate in coagulating bath, and spinning operation is easier to, and tow is not easily broken
Head, and the degree of dissociation of sulfuric acid can be reduced, make tow that still there is certain residual ester value when leaving coagulating bath.In spinning process
In, the sodium sulphate content in coagulating bath, which can be continuously increased, leads to not reach technique requirement, it can only carry out discharging at regular time and quantity,
Acid, salt, metal ion in waste liquid etc. will cause serious environmental pollution, huge pressure brought to sewage treatment and is caused
The huge waste of resource.(3) acid station: moisture extra in coagulating bath is removed using multistage concentration and evaporation, it is (impure to extract saltcake
More, added value itself is low so that it can not generate economic benefit, and processing is difficult) remove the sulfuric acid being continuously generated in coagulating bath
Sodium, then eo-acid and zinc sulfate are added, to keep the stable components of coagulating bath.Viscose rayon is produced by each road in process of production
A large amount of industrial chemicals will be had after process and process flow and is changed into waste pollution to atmosphere and water body, and wherein sodium sulphate is exactly
Constitute a main aspect of wastewater source.
Bipolar membrane electrodialysis (BPED) is under DC electric field effect, using anions and canons exchange membrane to yin, yang in solution
The selective penetrated property of ion makes in solution in a kind of physical and chemical process of the solute of ionic condition and solvent separation.Generally by
Anion exchange resin layer (AL), cation exchange resin layer (CL) and intermediate catalyst layer composition.Under the action of DC electric field,
H2O is dissociated into H+ and OH- and passes through anode membrane and cavity block respectively in Bipolar Membrane, as H+ and OH-ion source.Using this feature,
The bipolar membrane electrodialysis system that Bipolar Membrane and anions and canons exchange membrane are combined into, can be in the case where not introducing new component
Corresponding bronsted lowry acids and bases bronsted lowry is converted by the salt in aqueous solution, this technology is known as bipolar membrane electrodialysis technology.Compared with traditional handicraft,
Bipolar membrane electrodialysis technology has the prominent technical advantages such as energy-efficient, environmental-friendly, operation is convenient.In traditional chemical separating work
The renovating of skill develops during clean manufacturing and circular economy and plays the role to become more and more important.
State Intellectual Property Office discloses a publication number CN102107972A in 2011.06.29, and entitled " one kind is double
Pole film is to hyperfiltration Seawater desalination pretreatment method " patent of invention, the composite can be widely applied to sea water desalination occasion, but
It is not suitable for the sodium sulfate waste liquid generated in the viscose glue production process containing complicated ingredient impurity processing.
State Intellectual Property Office discloses 103341322 A of publication number CN, entitled " one kind in 2013.10.09
Bipolar membrane electrodialysis method produces the preprocess method of soda acid from viscose sodium sulfate waste liquor " patent of invention, disclose one kind
Using the preprocess method of bipolar membrane electrodialysis device production sulfuric acid and sodium hydroxide, although above-mentioned patent can accomplish to handle
Waste liquid, so that acid-alkali regeneration, certain protecting effect is played to environment, but that there are pre-treatment steps is various, cost input is big,
Energy consumption is higher, zinc ion removal is not thorough and the rate of recovery is low, resin regeneration frequency is higher and loss is big, zinc ion concentration it is excessively high into
The problems such as damaging and shortening the working life can be caused to film itself by entering bipolar membranous system.
Summary of the invention
In order to overcome above-mentioned deficiency in the prior art, the present invention provides a kind of gold such as the more reasonable simple, zinc ion of technique
Belong to ion and the removal of other objectionable impurities more thoroughly, beneficial to metal ion recovery rate is higher, resin regeneration interval is longer and
Can reduce whole system power consumption and extend Bipolar Membrane service life it is a kind of with bipolar membrane electrodialysis method make saltcake be converted into acid and
The new process of alkali.In addition, the bronsted lowry acids and bases bronsted lowry generated is back to use in viscose rayon production system by unique condensing mode, drop significantly
It is low as adding high cost investment caused by bronsted lowry acids and bases bronsted lowry, and this concentration technology can be with compared with than traditional evaporation and concentration
Save a large amount of energy consumption.Saltcake is turned waste into wealth by this whole set process, realizes the circulation of physical resources, promote the well-being of mankind and
The Nature.
The present invention is achieved through the following technical solutions:
A kind of new process for making saltcake be converted into bronsted lowry acids and bases bronsted lowry with bipolar membrane electrodialysis method, which comprises the following steps:
(1) saltcake addition demineralized water is dissolved in dissolving tank, obtains the metabisulfite solution that concentration is 10%~25%, then
Tank is adjusted into PH, sodium hydroxide is added in metabisulfite solution by pH value adjustment to 8.5~10；
(2) metabisulfite solution for adjusting precipitating by PH is entered in ultrafiltration system and removes zinc hydroxide colloid, has
Machine substance and solid suspension；
(3) will enter by the metabisulfite solution of ultrafiltration system filtering remaining in ion exchange resin system removal metabisulfite solution
Metal ion；
(4) refined filtration is carried out by PP millipore filter by the metabisulfite solution of ion exchange resin system；
(5) metabisulfite solution after PP millipore filter refined filtration generates sulfuric acid and hydrogen-oxygen into bipolar membrane electrodialysis system
Change sodium；Wherein enter metabisulfite solution the turbidity NTU≤1ppm, Zn of bipolar membrane electrodialysis system2+≤ 2ppm, Fe3+≤
0.1ppm、Ca2++Mg2+≤ 0.1ppm, solution temperature are 5~40 DEG C；
(6) sulfuric acid concentration generated by bipolar membrane electrodialysis system is controlled in 5~98g/l；Naoh concentration control 5~
80g/l, the sulfuric acid are concentrated using hyperfiltration, and the sodium hydroxide enters electrodialysis system and is concentrated.
Preferably, saltcake is quantitatively adding dissolving tank in step (1), demineralized water is quantitatively adding dissolving tank and is dissolved, institute
The delivery outlet for the dissolving tank stated connects PH by efferent duct and adjusts tank, and delivery outlet also connects dissolving tank input port by return pipe,
Solution concentration on online conductivity monitoring delivery outlet is set on delivery outlet, the data according to online conductivity are set on efferent duct
The valve that control opens or closes is carried out, the online conductivity detection underproof solution of solution concentration flows back into molten by return pipe
Solution tank adjusts tank until opening valve after the conductivity of dissolving tank delivery outlet is up to standard and entering PH.
Preferably, it includes that level-one PH adjusts tank and is connected to the second level PH that level-one PH adjusts tank downstream position that PH, which adjusts tank,
Adjust tank, the level-one PH adjusts tank under conditions of sodium sulfate concentration keeps 10%~25%, level-one PH adjust tank into
The sulfuric acid in sodium hydroxide and in saltcake is added in expects pipe road, PH is adjusted to 7~8, to reaction certain residence time, solution
Middle formation solid content, carries out sedimentation blowdown, then overflows to second level PH by the overflow passage that level-one PH adjusts tank top and adjusts
Tank is installed online PH monitoring on overflow passage, is monitored to overflowing liquid, and controls small flow sodium hydroxide solution and be added,
PH is adjusted to 8.5~10 and enters second level PH adjusting tank.
It is sufficiently mixed preferably, the PH solution for being adjusted to 8.5~10 is adjusted in tank in second level PH, second level PH tune
Whether section tank also passes through reflux pipe connection level-one PH and adjusts tank, reached by the online PH purpose monitoring that second level PH adjusts tank outlet
It is required that sending solution back to level-one PH adjusting tank when pH value is undesirable by reflux pipe and adjusting again, when pH value meets the requirements
Solution is sent to the ultrafiltration surge tank of ultrafiltration system with pump.
Preferably, its membrane aperture of PP millipore filter is 0.15~5 μm.
Preferably, ultrafiltration retaining molecular weight 20000D in ultrafiltration system, 5~40 DEG C of running temperature.
Preferably, membrane stack in Bipolar Membrane by 150~300 pairs of membrane modules by it is hydraulic it is tight lock, and membrane stack uses
Modularized design, according to it is different requirement and treatment conditions can parallel way connect or series system connection, the two can be switched.
Preferably, sulphuric acid concentration is concentrated in conjunction with multiple-effect evaporation method using reverse osmosis in step (6).
Preferably, sodium hydroxide concentration is concentrated in conjunction with multiple-effect evaporation method using electrodialysis in step (6).
Preferably, the electrodialytic membrane stack for concentrated sodium hydroxide passes through screw-pressing by 100~300 pairs of membrane modules
It forms, the membrane module can be in series or in parallel.
This new process not only simplifies entire process flow, reduces cost input and occupied area is small, but also most
Reduce to big degree the presence of the metal ions such as zinc ion and other impurity in solution, additionally it is possible to improve the metals such as zinc ion from
The sub- rate of recovery reduces the power consumption of whole system, and reduction is damaged caused by Bipolar Membrane, improves its service life, and extend
The ion exchange resin system regeneration intervals phase.By 7~10d of traditional handicraft regeneration period, new process extends the regeneration period at least
30d is also convenient for carrying out zinc ion sour backwash recycling and reusing.The bronsted lowry acids and bases bronsted lowry of generation is back to use viscous by unique condensing mode
In glue fiber production system, cost input is not only greatly reduced, but also can be saved greatly compared with than traditional evaporation and concentration
The energy consumption of amount.
The present invention is added sodium hydroxide and adjusts pH value, reasonably control solution concentration after dissolving deployed required concentration,
Sodium hydroxide is added not only realizes and adjust pH value, but also maximumlly by the transformation of the metal ions such as zinc ion in metabisulfite solution
For precipitating realize be separated by solid-liquid separation, then by ultrafiltration system removal zinc ion sediment, compared with the prior art in, the present invention is not
Only removal effect is more preferable, zinc ion sediment and other impurity substantially completely retaining without porous ultrafiltration membrane by ultrafiltration system, and
The characteristics of due to ultrafiltration apparatus itself, can recycle the metal ions such as zinc ion, recovery utilization rate after backwash
It is high.The metal ions such as remaining remaining zinc ion, are removed by ion exchange resin system, and ion exchange resin system resin is clear
Wash journey mainly has washing, acidolysis analysis, primary washing acid, secondary washing acid, alkali neutralization and washing alkali, wherein washing alkali is reversed
Operation, remaining is positive operation, zinc recovery >=95%.
Solution before the present invention enters ion exchange resin system is also more pure compared with the prior art, then extends
The ion exchange resin system regeneration intervals phase.
Enter bipolar membrane electrodialysis system using the metabisulfite solution after PP micro porous filtration and generates corresponding sulfuric acid and hydrogen
Sodium oxide molybdena.
Allow access into the metabisulfite solution of bipolar membrane electrodialysis system: turbidity NTU≤1ppm, Zn2+≤ 2ppm, Fe3+≤
0.1ppm、Ca2++Mg2+≤ 0.1ppm, solution temperature are 5~40 DEG C.
Compared with the prior art, the present invention enter bipolar membrane electrodialysis system metabisulfite solution it is more pure.
In the present invention each membrane stack of Bipolar Membrane by 150~300 pairs of membrane modules by it is hydraulic it is tight lock, membrane stack use mould
Blockization design, according to different requirements and treatment conditions can parallel way connect or series system connection, the two can switch at any time, then
It is more flexible when production.The amberplex of Bipolar Membrane is divided into homogeneous membrane and heterogeneous membrane according to different production methods, mainly
Using homogeneous membrane.It is to be directly prepared by the high molecular material of ion-exchange group or be directly connected on polymeric membrane base
The high molecular material generation chemistry knot of active group and manufactured amberplex, this kind of film intermediate ion cation exchange groups and film forming
It closes, forms substantially uniformity, diaphragm is relatively thin, and film resistance is low, and rupture strength is higher, strong alkali-acid resistance, and energy consumption is also low.
The sulfuric acid concentration that bipolar membrane electrodialysis system generates is controlled in 5~98g/l；Naoh concentration control for 5~
80g/l, sulfuric acid and sodium hydroxide after bipolar membrane electrodialysis pass through reverse osmosis and electrodialysis methods respectively and are concentrated again.
And the difference of required solution concentration, concentration means also have certain adjustment.When concentration concentration requires high, sulfuric acid solution concentration
It is concentrated in conjunction with multiple-effect evaporation method using reverse osmosis, sodium hydroxide solution concentration is using electrodialysis in conjunction with multiple-effect evaporation method
It is concentrated.
The present invention through bipolar membrane electrodialysis system and by concentration can be made required concentration sulfuric acid and sodium hydroxide it is molten
Liquid.Sulfuric acid solution can be used as ion exchange resin regeneration backwash acid solution, and the acid bath of viscose rayon production is transported to after can also being concentrated
Sulfuric acid circulation and stress reutilization system is formed in process.Sodium hydroxide solution can be used as ion exchange resin regeneration backwash lye,
Sheet steeping process, the alkali cellulose sulphonic acid ester dissolution process, waste gas absorption work of viscose rayon production are transported to after can also being concentrated
Sequence, concise process, sodium sulphate dissolution allotment process, sour water neutralisation treatment operation etc. of compressing and washing form alkali circulation and stress recycling system
System, reduces the production cost of viscose rayon.
The beneficial effects of the present invention are: the present invention not only simplifies entire process flow and occupied area is small, maximum
Reduce to degree the presence of the metal ions such as zinc ion and other impurity in solution, reduction is damaged caused by Bipolar Membrane, mentioned
Its high service life, and the ion exchange resin system regeneration intervals phase is extended, it is also convenient for carrying out backwash recycling to zinc ion
It recycles.The bronsted lowry acids and bases bronsted lowry of generation is back to use in viscose rayon production system by unique condensing mode, is not only greatly reduced
Cost input, and a large amount of energy consumption can be saved compared with than traditional evaporation and concentration.
Specific embodiment
Invention is described in further detail With reference to embodiment.
Embodiment one:
A kind of new process for making saltcake be converted into bronsted lowry acids and bases bronsted lowry with bipolar membrane electrodialysis method, comprising the following steps:
(1) saltcake addition demineralized water is dissolved in dissolving tank, obtains the metabisulfite solution that concentration is 10%, subsequently into
PH adjusts tank, and sodium hydroxide is added in metabisulfite solution by PH and is adjusted to 8.5.When dissolution, saltcake is quantitatively adding dissolving tank, removes
Meter brine is added dissolving tank and is dissolved, and the delivery outlet of dissolving tank connects PH by efferent duct and adjusts tank, and delivery outlet also passes through
Return pipe connects dissolving tank input port, is arranged the solution concentration on online conductivity monitoring delivery outlet on delivery outlet, on efferent duct
It is arranged and carries out the valve that control opens or closes according to the data of online conductivity, the underproof solution of solution concentration passes through reflux
Pipe flows back into dissolving tank until the conductivity late gate up to standard of dissolving tank outlet, which is opened, enters PH adjusting tank.It includes one that PH, which adjusts tank,
Grade PH adjusts tank and the second level PH of connection level-one PH adjusting tank downstream position adjusts tank, and level-one PH adjusts tank and protects in sodium sulfate concentration
Under conditions of holding 10%, the sulfuric acid in sodium hydroxide and in saltcake is added in the feeding pipe that level-one PH adjusts tank, PH is adjusted
To 7, to reacting certain residence time, most of zinc ion is precipitated in the form of zinc hydroxide in solution, solid content in solution
Sedimentation blowdown is carried out, second level PH is then overflowed to by the overflow passage that level-one PH adjusts tank top and adjusts tank, in overflow passage
The upper online PH monitoring of installation, is monitored overflowing liquid, and control small flow sodium hydroxide solution and be added, PH is adjusted to 8.5
Tank is adjusted into second level PH.The PH solution for being adjusted to 8.5 is adjusted in tank in second level PH and is sufficiently mixed, second level PH adjusts tank
Level-one PH is also connected by reflux pipe and adjusts tank, monitors whether to reach requirement by the PH that second level PH adjusts tank outlet, works as pH value
It is undesirable, solution is sent back to level-one PH adjusting tank by reflux pipe and adjusted again, uses pump by solution when pH value meets the requirements
It is sent to ultrafiltration surge tank.
(2) metabisulfite solution for adjusting precipitating by PH is entered into removal zinc hydroxide glue in ultrafiltration system
Body, organic substance and solid suspension；It allows more pure metabisulfite solution to enter subsequent technique, extends amberlite
The service life of rouge system regeneration interval and bipolar membranous system；Ultrafiltration retaining molecular weight 20000D in ultrafiltration system, operation
5~40 DEG C of temperature.
(3) ion exchange resin system removal metabisulfite solution will be entered by the metabisulfite solution of ultrafiltration system filtering
The metal ion of middle remnants；Reduce influence of the metal ion to bipolar membrane electrodialysis system.
(4) refined filtration is carried out by PP millipore filter by the metabisulfite solution of ion exchange resin system；It can be obtained
Meet the metabisulfite solution into bipolar membrane electrodialysis system technical indicator；Its membrane aperture of PP millipore filter is 0.15~5 μm.
(5) metabisulfite solution after PP millipore filter refined filtration, into bipolar membrane electrodialysis system generate sulfuric acid and
Sodium hydroxide；Wherein enter metabisulfite solution the turbidity NTU≤1ppm, Zn of bipolar membrane electrodialysis system2+≤ 2ppm, Fe3+≤
0.1ppm、Ca2++Mg2+≤ 0.1ppm, solution temperature are 5 DEG C.Membrane stack in Bipolar Membrane passes through liquid by 150~300 pairs of membrane modules
Compression is locked, and membrane stack uses modularized design, according to different requirements and treatment conditions can parallel way connect or series connection side
Formula connection, the two can switch at any time.
(6) it controls by the sulfuric acid concentration that bipolar membrane electrodialysis system generates in 5~98g/l, turbidity NTU≤1ppm,
Middle sodium sulfate concentration≤10g/l；Naoh concentration control be 5~80g/l, turbidity NTU≤1ppm, wherein sodium sulfate concentration≤
10g/l, sulfuric acid are concentrated using hyperfiltration, and sodium hydroxide enters another electrodialysis system and is concentrated.In concentration, according to
It is different in concentration means according to concentration concentration.When be concentrated concentration require it is high when, sulfuric acid solution concentration using it is reverse osmosis with it is more
Effect evaporation, which combines, to be concentrated, and sodium hydroxide solution concentration is concentrated in conjunction with multiple-effect evaporation method using electrodialysis.For
The electrodialytic membrane stack of concentrated sodium hydroxide is formed by 100~300 pairs of membrane modules by screw-pressing, membrane module can connect or
Person is in parallel.When deploying solution concentration, the raw bronsted lowry acids and bases bronsted lowry content of concentration too low yield is also low, and when concentration is higher, sodium sulphate is easy analysis
Crystal has an impact to subsequent technique out, and PH metal ions such as zinc ion in 8.5 ~ 10 sections are changed into precipitating can be more thorough,
Effect is more preferable.
A kind of embodiment two: new process for making saltcake be converted into bronsted lowry acids and bases bronsted lowry with bipolar membrane electrodialysis method, comprising the following steps:
(1) saltcake addition demineralized water is dissolved in dissolving tank, obtains the metabisulfite solution that concentration is 14%, subsequently into
PH adjusts tank, and sodium hydroxide is added in metabisulfite solution by PH and is adjusted to 9.When dissolution, saltcake is quantitatively adding dissolving tank, desalination
Water is quantitatively adding dissolving tank and is dissolved, and the delivery outlet of dissolving tank connects PH by efferent duct and adjusts tank, and delivery outlet also passes through back
Flow tube connects dissolving tank input port, and the solution concentration on online conductivity monitoring delivery outlet is arranged on delivery outlet, sets on efferent duct
It sets and carries out the valve that control opens or closes according to the data of online conductivity, the underproof solution of solution concentration passes through return pipe
Dissolving tank is flowed back into until the conductivity late gate up to standard of dissolving tank outlet, which is opened, enters PH adjusting tank.It includes level-one that PH, which adjusts tank,
PH adjusts tank and connects the second level PH adjusting tank that level-one PH adjusts tank downstream position, and level-one PH adjusts tank and keeps in sodium sulfate concentration
Under conditions of 14%, the sulfuric acid in sodium hydroxide and in saltcake is added in the feeding pipe that level-one PH adjusts tank, PH adjusting is arrived
7.5, to reacting certain residence time, most of zinc ion is precipitated in the form of zinc hydroxide in solution, solid content in solution
Blowdown is settled, second level PH is then overflowed to by the overflow passage that level-one PH adjusts tank top and adjusts tank, is pacified on overflow passage
It is monitored mounted in line PH, overflowing liquid is monitored, and controlled small flow sodium hydroxide solution and be added, PH is adjusted to 9 and enters two
Grade PH adjusts tank.The PH solution for being adjusted to 9 is adjusted in tank in second level PH and is sufficiently mixed, second level PH adjusts tank and also passes through instead
Flow tube connects level-one PH and adjusts tank, monitors whether to reach requirement by the PH that second level PH adjusts tank outlet, want when pH value is not met
It asks, solution is sent back to level-one PH adjusting tank by reflux pipe and adjusted again, solution is sent to ultrafiltration with pump when pH value meets the requirements
Surge tank.
(2) metabisulfite solution for adjusting precipitating by PH is entered into removal zinc hydroxide glue in ultrafiltration system
Body, organic substance and solid suspension；It allows more pure metabisulfite solution to enter subsequent technique, extends amberlite
The service life of rouge system regeneration interval and bipolar membranous system；Ultrafiltration retaining molecular weight 20000D in ultrafiltration system, operation
5~40 DEG C of temperature.
(3) ion exchange resin system removal metabisulfite solution will be entered by the metabisulfite solution of ultrafiltration system filtering
The metal ion of middle remnants；Reduce influence of the metal ion to bipolar membrane electrodialysis system.
(4) refined filtration is carried out by PP millipore filter by the metabisulfite solution of ion exchange resin system；It can be obtained
Meet the metabisulfite solution into bipolar membrane electrodialysis system technical indicator；Its membrane aperture of PP millipore filter is 0.15~5 μm.
(5) metabisulfite solution after PP millipore filter refined filtration, into bipolar membrane electrodialysis system generate sulfuric acid and
Sodium hydroxide；Wherein enter metabisulfite solution the turbidity NTU≤1ppm, Zn of bipolar membrane electrodialysis system2+≤ 2ppm, Fe3+≤
0.1ppm、Ca2++Mg2+≤ 0.1ppm, solution temperature are 20 DEG C.Membrane stack in Bipolar Membrane passes through liquid by 150~300 pairs of membrane modules
Compression is locked, and membrane stack uses modularized design, according to different requirements and treatment conditions can parallel way connect or series connection side
Formula connection, the two can switch at any time.The amberplex of Bipolar Membrane is divided into homogeneous membrane and heterogeneous membrane according to different production methods, main
To use homogeneous membrane.It is to be directly prepared by the high molecular material of ion-exchange group or directly connected on polymeric membrane base
Connect active group and manufactured amberplex, chemistry knot occurs for the high molecular material of this kind of film intermediate ion cation exchange groups and film forming
It closes, forms substantially uniformity, diaphragm is relatively thin, and film resistance is low, and rupture strength is higher, strong alkali-acid resistance, and energy consumption is also low.Bipolar Membrane electricity
The workshop of electrodialysis system is kept for 5~40 DEG C, keeps distribution room temperature to be lower than 40 DEG C, control room room temperature is maintained at 25 DEG C or so.
(6) sulfuric acid concentration generated by bipolar membrane electrodialysis system is controlled in 5~98g/l；Naoh concentration control
For 5~80g/l, sulfuric acid is concentrated using hyperfiltration, and sodium hydroxide enters another electrodialysis system and is concentrated.It is being concentrated
When, it is different in concentration means according to concentration concentration.Sulfuric acid solution concentration using it is reverse osmosis in conjunction with multiple-effect evaporation method into
Row concentration, sodium hydroxide solution concentration are concentrated in conjunction with multiple-effect evaporation method using electrodialysis.For concentrated sodium hydroxide
Electrodialytic membrane stack is formed by 100~300 pairs of membrane modules by screw-pressing, and membrane module can be in series or in parallel.
A kind of embodiment three: new process for making saltcake be converted into bronsted lowry acids and bases bronsted lowry with bipolar membrane electrodialysis method, comprising the following steps:
(1) saltcake addition demineralized water is dissolved in dissolving tank, obtains the metabisulfite solution that concentration is 16%, subsequently into
PH adjusts tank, and sodium hydroxide is added in metabisulfite solution by PH and is adjusted to 9.5.When dissolution, saltcake is quantitatively adding dissolving tank, removes
Meter brine is added dissolving tank and is dissolved, and the delivery outlet of dissolving tank connects PH by efferent duct and adjusts tank, and delivery outlet also passes through
Return pipe connects dissolving tank input port, is arranged the solution concentration on online conductivity monitoring delivery outlet on delivery outlet, on efferent duct
It is arranged and carries out the valve that control opens or closes according to the data of online conductivity, the underproof solution of solution concentration passes through reflux
Pipe flows back into dissolving tank until the conductivity late gate up to standard of dissolving tank outlet, which is opened, enters PH adjusting tank.It includes one that PH, which adjusts tank,
Grade PH adjusts tank and the second level PH of connection level-one PH adjusting tank downstream position adjusts tank, and level-one PH adjusts tank and protects in sodium sulfate concentration
Under conditions of holding 16%, the sulfuric acid in sodium hydroxide and in saltcake is added in the feeding pipe that level-one PH adjusts tank, PH is adjusted
To 7.5, to reacting certain residence time, most of zinc ion is precipitated in the form of zinc hydroxide in solution, solid in solution
Object settles blowdown, then overflows to second level PH by the overflow passage that level-one PH adjusts tank top and adjusts tank, on overflow passage
Online PH monitoring is installed, overflowing liquid is monitored, and controls small flow sodium hydroxide solution and is added, by PH be adjusted to 9.5 into
Enter second level PH and adjusts tank.The PH solution for being adjusted to 9.5 is adjusted in tank in second level PH and is sufficiently mixed, second level PH adjusts tank also
By reflux pipe connect level-one PH adjust tank, by second level PH adjust tank outlet PH monitor whether to reach requirement, when pH value not
It meets the requirements, solution is sent back to level-one PH adjusting tank by reflux pipe and adjusted again, sent solution with pump when pH value meets the requirements
To ultrafiltration surge tank.
(2) metabisulfite solution for adjusting precipitating by PH is entered into removal zinc hydroxide glue in ultrafiltration system
Body, organic substance and solid suspension；It allows more pure metabisulfite solution to enter subsequent technique, extends amberlite
The service life of rouge system regeneration interval and bipolar membranous system；Ultrafiltration retaining molecular weight 20000D in ultrafiltration system, operation
5~40 DEG C of temperature.
(3) ion exchange resin system removal metabisulfite solution will be entered by the metabisulfite solution of ultrafiltration system filtering
The metal ion of middle remnants；Reduce influence of the metal ion to bipolar membrane electrodialysis system.
(4) refined filtration is carried out by PP millipore filter by the metabisulfite solution of ion exchange resin system；It can be obtained
Meet the metabisulfite solution into bipolar membrane electrodialysis system technical indicator；Its membrane aperture of PP millipore filter is 0.15~5 μm.
(5) metabisulfite solution after PP millipore filter refined filtration, into bipolar membrane electrodialysis system generate sulfuric acid and
Sodium hydroxide；Wherein enter metabisulfite solution the turbidity NTU≤1ppm, Zn of bipolar membrane electrodialysis system2+≤ 2ppm, Fe3+≤
0.1ppm、Ca2++Mg2+≤ 0.1ppm, solution temperature are 30 DEG C.Membrane stack in Bipolar Membrane passes through liquid by 150~300 pairs of membrane modules
Compression is locked, and membrane stack uses modularized design, according to different requirements and treatment conditions can parallel way connect or series connection side
Formula connection, the two can switch at any time.The amberplex of Bipolar Membrane is divided into homogeneous membrane and heterogeneous membrane according to different production methods, main
To use homogeneous membrane.It is to be directly prepared by the high molecular material of ion-exchange group or directly connected on polymeric membrane base
Connect active group and manufactured amberplex, chemistry knot occurs for the high molecular material of this kind of film intermediate ion cation exchange groups and film forming
It closes, forms substantially uniformity, diaphragm is relatively thin, and film resistance is low, and rupture strength is higher, strong alkali-acid resistance, and energy consumption is also low.Bipolar Membrane electricity
The workshop of electrodialysis system is kept for 5~40 DEG C, keeps distribution room temperature to be lower than 40 DEG C, control room room temperature is maintained at 25 DEG C or so.
(6) sulfuric acid concentration generated by bipolar membrane electrodialysis system is controlled in 5~98g/l；Naoh concentration control
For 5~80g/l, sulfuric acid is concentrated using hyperfiltration, and sodium hydroxide enters another electrodialysis system and is concentrated.It is being concentrated
When, it is different in concentration means according to concentration concentration.Sulfuric acid solution concentration using it is reverse osmosis in conjunction with multiple-effect evaporation method into
Row concentration, sodium hydroxide solution concentration are concentrated in conjunction with multiple-effect evaporation method using electrodialysis.For concentrated sodium hydroxide
Electrodialytic membrane stack is formed by 100~300 pairs of membrane modules by screw-pressing, and membrane module can be in series or in parallel.
A kind of example IV: new process for making saltcake be converted into bronsted lowry acids and bases bronsted lowry with bipolar membrane electrodialysis method, comprising the following steps:
(1) saltcake addition demineralized water is dissolved in dissolving tank, obtains the metabisulfite solution that concentration is 25%, subsequently into
PH adjusts tank, and sodium hydroxide is added in metabisulfite solution by PH and is adjusted to 10.When dissolution, saltcake is quantitatively adding dissolving tank, removes
Meter brine is added dissolving tank and is dissolved, and the delivery outlet of dissolving tank connects PH by efferent duct and adjusts tank, and delivery outlet also passes through
Return pipe connects dissolving tank input port, is arranged the solution concentration on online conductivity monitoring delivery outlet on delivery outlet, on efferent duct
It is arranged and carries out the valve that control opens or closes according to the data of online conductivity, the underproof solution of solution concentration passes through reflux
Pipe flows back into dissolving tank until the conductivity late gate up to standard of dissolving tank outlet, which is opened, enters PH adjusting tank.It includes one that PH, which adjusts tank,
Grade PH adjusts tank and the second level PH of connection level-one PH adjusting tank downstream position adjusts tank, and level-one PH adjusts tank and protects in sodium sulfate concentration
Under conditions of holding 25%, the sulfuric acid in sodium hydroxide and in saltcake is added in the feeding pipe that level-one PH adjusts tank, PH is adjusted
To 8, to reacting certain residence time, most of zinc ion is precipitated in the form of zinc hydroxide in solution, solid content in solution
Blowdown is settled, second level PH is then overflowed to by the overflow passage that level-one PH adjusts tank top and adjusts tank, is pacified on overflow passage
It is monitored mounted in line PH, overflowing liquid is monitored, and controlled small flow sodium hydroxide solution and be added, PH is adjusted to 10 and enters two
Grade PH adjusts tank.The PH solution for being adjusted to 10 is adjusted in tank in second level PH and is sufficiently mixed, second level PH adjusts tank and also passes through
Reflux pipe connects level-one PH and adjusts tank, monitors whether to reach requirement by the PH that second level PH adjusts tank outlet, when pH value is not met
Adjusted again it is required that by reflux pipe sending solution back to level-one PH and adjusting tank, when pH value meet the requirements with pump solution is sent to it is super
Filter surge tank.
(2) metabisulfite solution for adjusting precipitating by PH is entered into removal zinc hydroxide glue in ultrafiltration system
Body, organic substance and solid suspension；It allows more pure metabisulfite solution to enter subsequent technique, extends amberlite
The service life of rouge system regeneration interval and bipolar membranous system；Ultrafiltration retaining molecular weight 20000D in ultrafiltration system, operation
5~40 DEG C of temperature.
(3) ion exchange resin system removal metabisulfite solution will be entered by the metabisulfite solution of ultrafiltration system filtering
The metal ion of middle remnants；Reduce influence of the metal ion to bipolar membrane electrodialysis system.
(4) refined filtration is carried out by PP millipore filter by the metabisulfite solution of ion exchange resin system；It can be obtained
Meet the metabisulfite solution into bipolar membrane electrodialysis system technical indicator；Its membrane aperture of PP millipore filter is 0.15~5 μm.
(5) metabisulfite solution after PP millipore filter refined filtration, into bipolar membrane electrodialysis system generate sulfuric acid and
Sodium hydroxide；Wherein enter metabisulfite solution the turbidity NTU≤1ppm, Zn of bipolar membrane electrodialysis system2+≤ 2ppm, Fe3+≤
0.1ppm、Ca2++Mg2+≤ 0.1ppm, solution temperature are 40 DEG C.Membrane stack in Bipolar Membrane passes through liquid by 150~300 pairs of membrane modules
Compression is locked, and membrane stack uses modularized design, according to different requirements and treatment conditions can parallel way connect or series connection side
Formula connection, the two can switch at any time.The amberplex of Bipolar Membrane is divided into homogeneous membrane and heterogeneous membrane according to different production methods, main
To use homogeneous membrane.It is to be directly prepared by the high molecular material of ion-exchange group or directly connected on polymeric membrane base
Connect active group and manufactured amberplex, chemistry knot occurs for the high molecular material of this kind of film intermediate ion cation exchange groups and film forming
It closes, forms substantially uniformity, diaphragm is relatively thin, and film resistance is low, and rupture strength is higher, strong alkali-acid resistance, and energy consumption is also low.Bipolar Membrane electricity
The workshop of electrodialysis system is kept for 5~40 DEG C, keeps distribution room temperature to be lower than 40 DEG C, control room room temperature is maintained at 25 DEG C or so.
(6) sulfuric acid concentration generated by bipolar membrane electrodialysis system is controlled in 5~98g/l；Naoh concentration control
For 5~80g/l, sulfuric acid is concentrated using hyperfiltration, and sodium hydroxide enters another electrodialysis system and is concentrated.It is being concentrated
When, it is different in concentration means according to concentration concentration.Sulfuric acid solution concentration using it is reverse osmosis in conjunction with multiple-effect evaporation method into
Row concentration, sodium hydroxide solution concentration are concentrated in conjunction with multiple-effect evaporation method using electrodialysis.For concentrated sodium hydroxide
Electrodialytic membrane stack is formed by 100~300 pairs of membrane modules by screw-pressing, and membrane module can be in series or in parallel.
The present invention is added sodium hydroxide and adjusts pH value, reasonably control solution concentration, be added after dissolving deployed concentration
Sodium hydroxide, which is not only realized, adjusts pH value, and maximumlly the metal ions such as zinc ion in metabisulfite solution are changed into it is heavy
Form sediment realize be separated by solid-liquid separation, then by ultrafiltration system removal zinc ion sediment, compared with the prior art in, the present invention is not only gone
Except effect is more preferable, zinc ion sediment and other impurities substantially completely retaining without porous ultrafiltration membrane by ultrafiltration system, and due to
The characteristics of ultrafiltration apparatus itself, can recycle the metal ions such as zinc ion after backwash, and recovery utilization rate is high.
The metal ions such as remaining remaining zinc ion, are removed by ion exchange resin system, and resin cleaning process mainly has washing, acid
Parsing, primary washing acid, secondary washing acid, alkali neutralization and washing alkali, wherein washing alkali is inverted running, remaining is positive fortune
Row.
Compared with the prior art, more pure into the metabisulfite solution of bipolar membrane electrodialysis system.
Certain density sulfuric acid and sodium hydroxide solution can be made through bipolar membrane electrodialysis system in the present invention.Sulfuric acid solution can
As ion exchange resin regeneration backwash acid solution, it is transported to after can also being concentrated in the acid bath process of viscose rayon production and forms sulfuric acid
Circulation and stress reutilization system.Sodium hydroxide solution can be used as ion exchange resin regeneration backwash lye, convey after can also being concentrated
The sheet steeping process that produces to viscose rayon, waste gas absorption process, concise compresses and washes work at alkali cellulose sulphonic acid ester dissolution process
Sequence, sodium sulphate dissolution allotment process, sour water neutralisation treatment operation etc. form alkali circulation and stress reutilization system, reduce viscose glue fibre
The production cost of dimension.
This new process not only simplifies entire process flow, reduces cost input and occupied area is small, utmostly
Ground reduces the presence of the metal ions such as zinc ion and other impurity in solution, additionally it is possible to improve the recycling of the metal ions such as zinc ion
Rate reduces the power consumption of whole system, and reduction is damaged caused by Bipolar Membrane, improves its service life, and extends ion friendship
It changes the resin system regeneration intervals phase, 7~10d of traditional handicraft regeneration period, new process regeneration period at least 30d is also convenient for zinc
The metal ions such as ion carry out sour backwash recycling and reusing.The bronsted lowry acids and bases bronsted lowry of generation is back to use viscose glue fibre by unique condensing mode
Tie up production system in, high cost investment caused by greatly reducing as adding bronsted lowry acids and bases bronsted lowry, and this concentration technology with than pass
The evaporation and concentration of system, which is compared, can save a large amount of energy consumption.
Claims (10)
1. a kind of new process for making saltcake be converted into bronsted lowry acids and bases bronsted lowry with bipolar membrane electrodialysis method, which comprises the following steps:
(1) saltcake addition demineralized water is dissolved in dissolving tank, obtains the metabisulfite solution that concentration is 10%~25%, then
Tank is adjusted into PH, sodium hydroxide is added in metabisulfite solution by pH value adjustment to 8.5~10；
(2) metabisulfite solution for adjusting precipitating by PH is entered in ultrafiltration system and removes zinc hydroxide colloid, has
Machine substance and solid suspension；
(3) will enter by the metabisulfite solution of ultrafiltration system filtering remaining in ion exchange resin system removal metabisulfite solution
Metal ion；
(4) refined filtration is carried out by PP millipore filter by the metabisulfite solution of ion exchange resin system；
(5) metabisulfite solution after PP millipore filter refined filtration generates sulfuric acid and hydrogen-oxygen into bipolar membrane electrodialysis system
Change sodium；Wherein enter metabisulfite solution the turbidity NTU≤1ppm, Zn of bipolar membrane electrodialysis system2+≤ 2ppm, Fe3+≤
0.1ppm、Ca2++Mg2+≤ 0.1ppm, solution temperature are 5~40 DEG C；
(6) sulfuric acid concentration generated by bipolar membrane electrodialysis system is controlled in 5~98g/l；Naoh concentration control 5~
80g/l, the sulfuric acid are concentrated using hyperfiltration, and the sodium hydroxide enters electrodialysis system and is concentrated.
2. a kind of new process for making saltcake be converted into bronsted lowry acids and bases bronsted lowry with bipolar membrane electrodialysis method according to claim 1, special
Sign is: in the step (1), saltcake is quantitatively adding dissolving tank, and demineralized water is quantitatively adding dissolving tank and is dissolved, described
The delivery outlet of dissolving tank connects PH by efferent duct and adjusts tank, and delivery outlet also connects dissolving tank input port, output by return pipe
Solution concentration on online conductivity monitoring delivery outlet is set on mouth, and setting is carried out according to the data of online conductivity on efferent duct
The valve opened or closed is controlled, the online conductivity detection underproof solution of solution concentration flows back into dissolving tank by return pipe
Tank is adjusted until opening valve after the conductivity of dissolving tank delivery outlet is up to standard and entering PH.
3. a kind of new process for making saltcake be converted into bronsted lowry acids and bases bronsted lowry with bipolar membrane electrodialysis method according to claim 2, special
Sign is: it includes that level-one PH adjusts tank and is connected to the second level PH adjusting that level-one PH adjusts tank downstream position that the PH, which adjusts tank,
Tank, the level-one PH adjust tank under conditions of sodium sulfate concentration keeps 10%~25%, adjust the feed pipe of tank in level-one PH
The sulfuric acid in sodium hydroxide and in saltcake is added in road, PH is adjusted to 7~8, to reacting certain residence time, shape in solution
At solid content, sedimentation blowdown is carried out, second level PH is then overflowed to by the overflow passage that level-one PH adjusts tank top and adjusts tank,
Online PH monitoring is installed on overflow passage, overflowing liquid is monitored, and controls small flow sodium hydroxide solution and is added, by PH tune
It is whole to enter second level PH adjusting tank to 8.5~10.
4. a kind of new process for making saltcake be converted into bronsted lowry acids and bases bronsted lowry with bipolar membrane electrodialysis method according to claim 3, special
Sign is: the PH solution for being adjusted to 8.5~10 being adjusted in tank in second level PH and is sufficiently mixed, second level PH adjusts tank and also passes through
Reflux pipe connects level-one PH and adjusts tank, whether reaches requirement by the online PH purpose monitoring that second level PH adjusts tank outlet, works as PH
Be worth it is undesirable, by solution by reflux pipe send back to level-one PH adjust tank adjust again, when pH value meet the requirements with pump will be molten
Liquid is sent to the ultrafiltration surge tank of ultrafiltration system.
5. a kind of new process for making saltcake be converted into bronsted lowry acids and bases bronsted lowry with bipolar membrane electrodialysis method according to claim 1, special
Sign is: described its membrane aperture of PP millipore filter is 0.15~5 μm.
6. a kind of new process for making saltcake be converted into bronsted lowry acids and bases bronsted lowry with bipolar membrane electrodialysis method according to claim 1, special
Sign is: ultrafiltration retaining molecular weight 20000D in ultrafiltration system, 5~40 DEG C of running temperature.
7. described in any item according to claim 1~6 a kind of make saltcake be converted into the new of bronsted lowry acids and bases bronsted lowry with bipolar membrane electrodialysis method
Technique, it is characterised in that: membrane stack in the Bipolar Membrane by 150~300 pairs of membrane modules by it is hydraulic it is tight lock, and membrane stack is adopted
With modularized design, according to different requirements and treatment conditions can parallel way connect or series system connection, the two can be switched.
8. a kind of new process for making saltcake be converted into bronsted lowry acids and bases bronsted lowry with bipolar membrane electrodialysis method according to claim 1, special
Sign is: in step (6), sulphuric acid concentration is concentrated in conjunction with multiple-effect evaporation method using reverse osmosis.
9. a kind of new process for making saltcake be converted into bronsted lowry acids and bases bronsted lowry with bipolar membrane electrodialysis method according to claim 1, special
Sign is: in step (6), sodium hydroxide concentration is concentrated in conjunction with multiple-effect evaporation method using electrodialysis.
10. a kind of new process for making saltcake be converted into bronsted lowry acids and bases bronsted lowry with bipolar membrane electrodialysis method according to claim 1, special
Sign is: the electrodialytic membrane stack for concentrated sodium hydroxide is formed by 100~300 pairs of membrane modules by screw-pressing,
The membrane module can be in series or in parallel.
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Application publication date: 20181204 |