CN209128106U - A kind of membrane stack device for viscose sodium sulfate waste liquor processing - Google Patents
A kind of membrane stack device for viscose sodium sulfate waste liquor processing Download PDFInfo
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- CN209128106U CN209128106U CN201821814571.9U CN201821814571U CN209128106U CN 209128106 U CN209128106 U CN 209128106U CN 201821814571 U CN201821814571 U CN 201821814571U CN 209128106 U CN209128106 U CN 209128106U
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- 239000012528 membrane Substances 0.000 title claims abstract description 180
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 title claims abstract description 70
- 229910052938 sodium sulfate Inorganic materials 0.000 title claims abstract description 44
- 235000011152 sodium sulphate Nutrition 0.000 title claims abstract description 44
- 229920000297 Rayon Polymers 0.000 title claims abstract description 25
- 239000002699 waste material Substances 0.000 title claims abstract description 21
- 238000012545 processing Methods 0.000 title claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 106
- 238000005192 partition Methods 0.000 claims abstract description 97
- 239000002253 acid Substances 0.000 claims abstract description 55
- 239000012267 brine Substances 0.000 claims abstract description 48
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims abstract description 48
- 150000003839 salts Chemical class 0.000 claims abstract description 46
- 239000003513 alkali Substances 0.000 claims abstract description 35
- 230000008676 import Effects 0.000 claims abstract description 33
- -1 partition Substances 0.000 claims abstract description 11
- 101100532451 Rattus norvegicus Slc22a17 gene Proteins 0.000 claims description 4
- 230000005611 electricity Effects 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 229920002379 silicone rubber Polymers 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 19
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 239000003292 glue Substances 0.000 abstract description 6
- 239000010808 liquid waste Substances 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 81
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 60
- 235000011121 sodium hydroxide Nutrition 0.000 description 27
- 239000000243 solution Substances 0.000 description 14
- 238000000909 electrodialysis Methods 0.000 description 13
- 230000001112 coagulating effect Effects 0.000 description 11
- 238000007599 discharging Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 150000001450 anions Chemical class 0.000 description 7
- 238000000354 decomposition reaction Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 238000004064 recycling Methods 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- 150000001768 cations Chemical class 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 229920002678 cellulose Polymers 0.000 description 4
- 239000001913 cellulose Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- 238000005349 anion exchange Methods 0.000 description 3
- 238000005341 cation exchange Methods 0.000 description 3
- 238000010494 dissociation reaction Methods 0.000 description 3
- 230000005593 dissociations Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 230000003020 moisturizing effect Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
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- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
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- 230000008025 crystallization Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 230000005685 electric field effect Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 230000000903 blocking effect Effects 0.000 description 1
- 150000007516 brønsted-lowry acids Chemical class 0.000 description 1
- 150000007528 brønsted-lowry bases Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
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- 238000010612 desalination reaction Methods 0.000 description 1
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- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 230000007646 directional migration Effects 0.000 description 1
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- 235000013399 edible fruits Nutrition 0.000 description 1
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- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
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- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
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- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The utility model discloses a kind of membrane stack devices for viscose sodium sulfate waste liquor processing, belong to viscose glue liquid waste disposal technique field.Including spaced diaphragm block and diaphragm plate, end is diaphragm plate, and two diaphragm plates of end are connected with pole plate respectively；Power interface, pole water inlet and pole water out are provided on pole plate；One pole plate connects positive pole by power interface, another pole plate connects power cathode by power interface；Diaphragm block includes the multipair diaphragm and partition overlapped, and every a pair of diaphragm includes cavity block, anode membrane and Bipolar Membrane；Diaphragm block repeats to be arranged according to the arrangement of Bipolar Membrane, partition, cavity block, partition, anode membrane, partition；Partition one end connects brine inlet, sour water import or buck import；The partition other end connects brine outlet, sour water outlet or buck outlet.The membrane stack device can be suitable for industrialized production, produce the lower alkali of salt content, the lower acid of salt content.
Description
Technical field
The utility model relates to viscose glue liquid waste disposal technique fields, more particularly to one kind to be used for viscose sodium sulfate waste liquor
The membrane stack device of processing.
Background technique
Viscose glue and acid coagulating bath act in viscose rayon forming process in chemical fibre industry, are neutralized alkali, fiber
Plain sodium sulfonate is decomposed and regenerates cellulose hydrate, cellulose sulfonate, free NaOH during this in viscose glue and because
The Na that side reaction generates2CS3, the side reaction products such as polysulfide can generate sodium sulphate with the sulfuric acid reaction in coagulating bath.It is viscous
Include the acid bath process of consumption sulfuric acid in glue fiber production, further includes the sheet steeping process for consuming sodium hydroxide, alkali cellulose
Sulphonic acid ester dissolution process, concise compresses and washes process and sour water neutralisation treatment operation at waste gas absorption process.
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 cellulose sulfonic acid
The reproduction speed of ester delays, and improves the concentration of sodium sulphate in coagulating bath, and spinning operation is easier to, and tow is not easy to break end, and can drop
The degree of dissociation of low-sulfur acid, makes tow still have certain residual ester value when leaving coagulating bath, but the sodium sulphate in coagulating bath
Also unsuitable excessively high, otherwise fibre solidification can be made to overrun, fine structure cannot be formed, and coarse crystalline particle is generated, fiber
Ectonexine is also inhomogenous.
During the spinning process, the sodium sulphate content in coagulating bath is continuously increased so that its requirement for being unable to satisfy technique, such as
Fruit only passes through the raw material being consumed in addition coagulating bath will make the total amount of coagulating bath increase to supplement its concentration recycling
Add and can not store, can only at regular time and quantity discharge coagulating bath, acid therein, salt, metal ion etc. will cause serious ring
Border pollution brings huge pressure to sewage treatment and causes the huge waste of resource.And by sodium sulphate extra in acid bath
High temperature crystallization is carried out, sodium sulfate crystal is isolated, so that the content of the sodium sulphate in acid bath is met technique requirement, is not required to exhaust daily
Acid balances acid bath, by directly continuing to use for spinning workshop after charging, can reduce acid discharge, output anhydrous sodium sulphate reduces environmental protection
Pressure, but due to the impure more, added value of sodium sulphate high temperature crystallization is produced in coagulating bath anhydrous sodium sulphate itself it is low so that
It can not generate economic benefit, and a large amount of solid salt can not be handled, and still bring certain pressure to environmental protection.
Bipolar Membrane is a kind of novel ion-exchange composite membranes, it is usually by cation exchange layer (N type film), interface parent
Water layer (Catalytic Layer) and anion exchange layer (P type film) are combined, and are reaction films truly.In DC electric field
Under effect, hydrolytic dissociation can be respectively obtained hydrogen ion and hydroxide ion in film two sides by Bipolar Membrane.It, will be double using this feature
The bipolar membrane electrodialysis system that pole film and other anion and cation exchange membranes are combined into, can in the case where not introducing new component incite somebody to action
Salt in aqueous solution is converted into corresponding bronsted lowry acids and bases bronsted lowry, and this technology is known as bipolar membrane electrodialysis technology.It is double compared with traditional handicraft
Pole membrane electrodialysis technology has the prominent technical advantages such as energy-efficient, environmental-friendly, operation is convenient.In recent years, Bipolar Membrane electric osmose
Analysis technology technology is being studied and is obtaining fast development using two aspects, and membrane preparation technology and operation parameter optimization constantly obtain
New progress, desalination and soda acid preparation, the albumen of biological field and amino acid of the application range from chemical field are purified and are extended to
The fields such as the purifying, concentration of industrial wastewater in environment protection field, high purity water preparation, the renovating of traditional work point separating process,
Develop clean manufacturing and circular economy plays the role to become more and more important in the process.
From 50 mid-nineties 90 of 20th century, there have been development process can be divided into three to research report in relation to Bipolar Membrane
A stage: at 20th century of first stage, 50 mid-nineties 90 to initial stage in the 80's, this is that Bipolar Membrane develops very slow period,
Bipolar Membrane is only by two panels anion and cation exchange membrane direct pressing, poor performance, and water decomposition voltage is tens times higher than theoretical pressure drop,
Application study is also in the laboratory stage based on water decomposition；Second stage is from the 80's of 20th century first arrivals nineties
Just, due to the improvement of bipolar membrane preparation technology, monolithic type Bipolar Membrane is successfully had developed, performance greatly improves, and is making
It is applied successfully in soda acid and desulfurization technology, commodity Bipolar Membrane occurs in this stage.From 20th century, the 90's first arrival
The present is the period that Bipolar Membrane rapidly develops, with the further investigation to Bipolar Membrane course of work mechanism, from membrane structure, membrane material
With significant improvement has been carried out in preparation process, so that the performance of Bipolar Membrane is greatly improved, wherein mainly to cavity block and anode membrane
The improvement of contact interface occurs since at the beginning of initial simple " pressurized layer type " or " coating type " structure to the 80's of 20th century
" monolithic type " structure then occurs greatly reducing membrane voltage with the labyrinth of intermediate " Catalytic Layer " again.
Currently, bipolar membrane electrodialysis technology has played original work in optimization traditional industrial process and new industrial process
With.Its appearance changes traditional industry separation and preparation process, to solve in the fields such as environment, chemical industry, biology, marine chemical industry
Technical problem bring new vigor and vitality into, while to have been provided the problems such as solving the environment of facing mankind, resource, the energy
Effect means.
State Intellectual Property Office discloses a Publication No. CN102167293A in 2011.3.10, and entitled " one kind makes
The utility model patent of the method for producing sulfuric acid and sodium hydroxide with bipolar membrane electrodialysis device " discloses a kind of using double
The method that Polar Crystal Slab electrodialysis plant produces sulfuric acid and sodium hydroxide, this method are that metabisulfite solution is injected into anion selection
In the compartment that film and cation selective membrane are formed, injects water into Bipolar Membrane and formed with anion selective membrane, cation selective membrane
Compartment in, under the effect of DC electric field power, formed in cation selective membrane and Bipolar Membrane towards the anion selection face of anode
Compartment and/or the compartment that is formed of cation selective membrane and cathode in obtain sodium hydroxide, in anion selective membrane and Bipolar Membrane
Sulfuric acid is obtained in the compartment that the compartment and/or anion selective membrane and anode that cation selective face towards cathode is formed are formed.
The method that the utility model uses can re-use sodium sulfate waste liquid, and producing can be with the sulfuric acid and hydroxide of secondary use
Sodium makes it turn waste into wealth, and has significant economic benefit and environmental benefit.
Although above-mentioned patent can accomplish to dispose waste liquid, so that acid-alkali regeneration, certain protecting effect is played to environment,
But still remain that the soda acid rate of recovery is not high, and energy consumption is high, it online recycling and can not recycle, and due to not filling entering film
Pre-treatment step before setting will lead to runner blocking, film resistance increase, the reduction of regenerated acid and alkali ability in film device, and
Service life of equipment is short.
State Intellectual Property Office disclosed a Publication No. CN203451221U on February 26th, 2014, and entitled one
Kind viscose sodium sulfate waste liquor discloses one kind using the utility model patent of the system of bipolar membrane electrodialysis method recycling soda acid
The system that viscose sodium sulfate waste liquor recycles soda acid using bipolar membrane electrodialysis method, including bipolar membrane electrodialysis film group device, sulphur
Acid recovery pipeline and alkali collection pipeline further include pretreatment unit and evaporation concentration device, the outlet end of the pretreatment unit
It is connected to the liquid feeding end of bipolar membrane electrodialysis film group device, going out sulfuric acid end and being concentrated by evaporation for the bipolar membrane electrodialysis film group device fills
That sets is connected into sulfuric acid end, and alkali end and evaporation concentration device be connected tos into alkali end out, the sulfuric acid end out of the evaporation concentration device
It is connected to respectively with retrieval of sulfuric acid pipeline with alkali collection pipeline with alkali end out.
It has the following problems:
1, the system of above-mentioned recycling soda acid can not be expanded to industrialized production, be only limited to the experimental stage.
2, the system of above-mentioned recycling soda acid has discharge, is unfavorable for environmentally friendly production.
3, the system of above-mentioned recycling soda acid produces alkali and produces sour salt content height, influences after being back to production process on viscose quality
Greatly.
Summary of the invention
In order to solve above-mentioned problems of the prior art, the utility model proposes one kind to be used for viscose rayon sulfuric acid
The membrane stack device of waste liquor of sodium processing, the membrane stack device can be suitable for industrialized production, produce the lower alkali of salt content, contain
The lower acid of salt amount.
A kind of membrane stack device for viscose sodium sulfate waste liquor processing, including spaced diaphragm block and film
Plate, end are diaphragm plate, and two diaphragm plates of end are connected with pole plate respectively；Be provided on the pole plate power interface, pole water into
Mouth and pole water out；One pole plate connects positive pole by power interface, another pole plate connects power supply by power interface
Cathode；The diaphragm block includes the multipair diaphragm and partition overlapped, and every a pair of diaphragm includes cavity block, anode membrane and bipolar
Film；The diaphragm block repeats to be arranged according to the arrangement of Bipolar Membrane, partition, cavity block, partition, anode membrane, partition；Described partition one end
Connect brine inlet, sour water import or buck import；The partition other end connection brine outlet, sour water outlet or buck
Outlet.
The electric current of membrane stack is set as 300~400A, and voltage is set as 200V~290V, and voltage increase illustrates that resistance increases,
Resistance increase illustrates concentration reduction.Concentration can be adjusted after increasing by moisturizing.
One end of partition is connected with brine inlet, sour water import and buck import, is respectively formed salt in diaphragm internal formation
Water inlet channel, sour water intake channel and buck intake channel；The other end of partition is connected with brine outlet, sour water outlet and alkali
Water out forms brine outlet channel, sour water exit passageway and buck exit passageway in diaphragm internal.
Diaphragm block includes 40 pairs of diaphragms overlapped, and every a pair of diaphragm includes cavity block, anode membrane and Bipolar Membrane, is amounted to
120 diaphragms.The runner with brine inlet, sour water import and buck inlet communication, sour water, buck and salt water are provided in diaphragm plate
By between runner inlet membrane.
Diaphragm block is according to Bipolar Membrane, partition, cavity block, partition, anode membrane, partition, Bipolar Membrane, partition, cavity block, partition, sun
The arrangement of film, partition repeats to be arranged.
Partition with a thickness of 2~3mm, partition, Bipolar Membrane, cavity block, anode membrane both ends be provided with multiple apertures；On partition
Aperture be correspondingly arranged on runner, including two sour runners, two alkali runners and three salt runners.
When the two sides of partition are set as anode membrane and cavity block, the chamber forming salt room of diaphragm internal.Aperture and salt on the partition
The connection of water inlet channel.Salt water passes through the salt runner connecting with aperture, goes out from the brine inlet channel of partition to the salt water of partition
Mouth channel is mobile.Salt room two sides are anode membrane and cavity block, Na+Across anode membrane, SO42-pass through cavity block, and the salinity across salt room drops
It is low.Then it is connect with brine outlet channel.
When the two sides of partition are set as Bipolar Membrane and cavity block, the chamber of diaphragm internal forms acid compartment.Aperture on the partition with
The connection of sour water intake channel.Aperture on the partition is connect with sour water intake channel.Sour water passes through the sour runner connecting with aperture,
It exports and moves from the sour water intake channel of partition to the sour water of partition.Acid compartment two sides are Bipolar Membrane and cavity block, H+Across Bipolar Membrane
Anode membrane, SO42-pass through cavity block, and the acid concentration across acid compartment increases.Then it is connect with sour water exit passageway.
When the two sides of partition are set as anode membrane and Bipolar Membrane, the chamber of diaphragm internal forms alkaline chamber.Aperture on the partition with
The connection of buck intake channel.Aperture on the partition is connect with buck intake channel.Buck passes through the alkali runner connecting with aperture,
It is mobile from the buck intake channel of partition to the buck exit passageway of partition.Alkaline chamber two sides are anode membrane and Bipolar Membrane, Na+It passes through
Anode membrane, OH-pass through Bipolar Membrane cavity block, and the alkali concentration across alkaline chamber increases.Then it is connect with buck exit passageway.
When the above salt water, sour water and buck are by corresponding salt room, acid compartment and alkaline chamber, ion is fixed under DC electric field effect
To migration and the selective penetrated property of amberplex, Bipolar Membrane effect is to make water decomposition.
1 pair of diaphragm is correspondingly arranged on a salt room, the corresponding brine outlet in 20 salt rooms, and 20 pairs of films, one salt water goes out
Mouthful, 40 pairs of diaphragms are correspondingly arranged there are two brine outlet.
1 pair of diaphragm is correspondingly arranged on an acid compartment, the corresponding sour water outlet of 20 acid compartments, and 20 pairs of films, one sour water goes out
Mouthful, 40 pairs of diaphragms be correspondingly arranged there are two sour water export.
1 pair of diaphragm is correspondingly arranged on an alkaline chamber, the corresponding buck outlet of 20 alkaline chambers, and 20 pairs of films, one buck goes out
Mouthful, 40 pairs of diaphragms be correspondingly arranged there are two buck export.
When the two sides of partition are set as anode membrane and cavity block, the chamber forming salt room of diaphragm internal.Aperture and salt on the partition
The connection of water inlet channel.Salt water passes through the salt runner connecting with aperture, goes out from the brine inlet channel of partition to the salt water of partition
Mouth channel is mobile.Salt room two sides are anode membrane and cavity block, Na+Across anode membrane, SO42-pass through cavity block, and the salinity across salt room drops
It is low.Then it is connect with brine outlet channel.
When the two sides of partition are set as Bipolar Membrane and cavity block, the chamber of diaphragm internal forms acid compartment.Aperture on the partition with
The connection of sour water intake channel.Aperture on the partition is connect with sour water intake channel.Sour water passes through the sour runner connecting with aperture,
It exports and moves from the sour water intake channel of partition to the sour water of partition.Acid compartment two sides are Bipolar Membrane and cavity block, H+Across Bipolar Membrane
Anode membrane, SO42-pass through cavity block, and the acid concentration across acid compartment increases.Then it is connect with sour water exit passageway.
When the two sides of partition are set as anode membrane and Bipolar Membrane, the chamber of diaphragm internal forms alkaline chamber.Aperture on the partition with
The connection of buck intake channel.Aperture on the partition is connect with buck intake channel.Buck passes through the alkali runner connecting with aperture,
It is mobile from the buck intake channel of partition to the buck exit passageway of partition.Alkaline chamber two sides are anode membrane and Bipolar Membrane, Na+It passes through
Anode membrane, OH-pass through Bipolar Membrane cavity block, and the alkali concentration across alkaline chamber increases.Then it is connect with buck exit passageway.
The Bipolar Membrane, cavity block and anode membrane are the rectangle of 1500mm*500mm, gross area 0.75m2, effective coverage is long
1200mm*420mm, effective area 0.5m2, effective area accounting 66.67%.
The membrane voltage (10A/dm2,30 DEG C) of Bipolar Membrane is 1.2V；Water decomposition efficiency >=98%；Rupture strength >=0.4Mpa；
With a thickness of 0.22mm.
Anode membrane correlation is highly acid anode membrane, has high-intensitive characteristic according to the index of CSE-2；Membrane impedance is 1.9 Ω cm
²；Rupture strength is greater than 0.35 Mpa；With a thickness of 0.15mm.
Cavity block correlation is alkalescent cavity block, has the characteristic for being not easy acid according to the index of ACM；Membrane impedance is 2.6 Ω cm
²；Rupture strength is greater than 0.15 Mpa；With a thickness of 0.11mm.
The running temperature of membrane stack is 20~40 DEG C, and the operating pressure of membrane stack is 0.03~0.1Mpa.
The side of one pole plate is provided with pressure plate, which is clamped by fastening bolt；The side of another pole plate
Organic frame is set.
One end of pressure plate also sets gradually organic frame beam and hydraulic press piston boit.
Be passed through treated metabisulfite solution in the salt circulating tank of the utility model, in sour circulating tank and alkali circulating tank in
It is placed with the sulfuric acid solution and sodium hydroxide solution to start circulation, is placed in the water pot of pole to conductive sodium hydroxide
Solution.
The concentration of weak brine is gradually reduced with multistage membrane stack, and the dilute sulfuric acid inside viscose rayon is gradually resolved into
Finished acid and product caustic soda, are recycled.
The utility model bring beneficial effect has:
(1) by ion, the selection of directional migration and amberplex under DC electric field effect penetrates the utility model
Property, Bipolar Membrane effect is to make water decomposition, sodium sulphate, sulfuric acid and the hydrogen-oxygen entered from brine inlet, sour water import and buck import
Change sodium, concentration reduces respectively, increases and increases.
(2) Bipolar Membrane passes through experiment screening, and excellent combination property, hydrolysis ionization voltage is very low (to dissociate electricity close to theoretical
Pressure), impedance is low, therefore film operational efficiency is higher, and energy consumption is very low.
(3) yin, yang film is by screening, and good using selective penetrated property, the lower film of impedance keeps membrane stack operation energy consumption lower,
Product purity is higher.
(4) structure of membrane stack diaphragm and filter design keeps membrane stack easy to assembly, and modular assembly facilitates membrane stack to safeguard.
Detailed description of the invention
Fig. 1 is the schematic diagram of the utility model.
Fig. 2 is the schematic diagram of salt room.
Fig. 3 is the schematic diagram of acid compartment.
Fig. 4 is the schematic diagram of alkaline chamber.
Fig. 5 is the schematic diagram of partition.
Fig. 6 is schematic illustration.
Wherein, 110, diaphragm block, 120, diaphragm plate, 130, pole plate, 140, power interface, 150, pole water inlet, 160, pole
Water out, 111, partition, 112, cavity block, 113, anode membrane, 114, Bipolar Membrane, 170, brine inlet, 180, sour water import, 190,
Buck import, 200 brine outlets, 210, sour water outlet, the outlet of 220 bucks, 171, brine inlet channel, 181, sour water import it is logical
Road, 191, buck intake channel, 201 brine outlet channels, 211, sour water exit passageway, 221, buck exit passageway, 230, open
Hole, 240, runner, 115, salt room, 116, acid compartment, 117, alkaline chamber, 250, pressure plate, 260, fastening bolt, 270, rack, 280,
Rack beam, 290, hydraulic press piston boit.
Specific embodiment
Embodiment 1
A kind of membrane stack device for viscose sodium sulfate waste liquor processing, including 110 He of spaced diaphragm block
Diaphragm plate 120, end are diaphragm plate 120, and two diaphragm plates 120 of end are connected with a pole plate 130 respectively；On the pole plate 130
It is provided with power interface 140, pole water inlet and pole water out；One pole plate 130 connects positive pole by power interface 140,
Another pole plate 130 connects power cathode by power interface 140；The diaphragm block 110 includes the multipair film overlapped
Piece and partition, every a pair of diaphragm includes cavity block, anode membrane and Bipolar Membrane；The diaphragm block 110 according to Bipolar Membrane, partition, cavity block,
The arrangement of partition, anode membrane, partition repeats to be arranged；Partition one end connection brine inlet, sour water import or buck import；Institute
State partition other end connection brine outlet, sour water outlet 210 or buck outlet.
The electric current of membrane stack is set as 300~400A, and pressure is set as 200V~290V, and voltage increase illustrates that resistance increases,
Resistance increase illustrates concentration reduction.Concentration can be adjusted after increasing by moisturizing.
The running temperature of membrane stack is 20~40 DEG C, and the operating pressure of membrane stack is 0.03~0.1Mpa.
Membrane stack includes spaced diaphragm block 110 and diaphragm plate 120, and end is diaphragm plate 120, and two diaphragm plates 120 divide
It is not connected with pole plate 130；Power interface 140, pole water inlet and pole water out are provided on pole plate 130.One pole plate 130 passes through
Power interface 140 connects positive pole, another pole plate 130 connects power cathode by power interface 140.
One end of diaphragm plate 120 is connected with brine inlet, sour water import and buck import, and difference is formed inside diaphragm plate 120
Form brine inlet channel, sour water intake channel and buck intake channel；The other end of diaphragm plate 120 is connected with brine outlet, acid
It is logical to form brine outlet channel, sour water exit passageway 211 and buck outlet inside diaphragm plate 120 for water out 210 and buck outlet
Road 221.
Diaphragm block 110 includes 40 pairs of diaphragms overlapped, and every a pair of diaphragm includes cavity block, anode membrane and Bipolar Membrane, is total to
Count 120 diaphragms.It is provided in diaphragm plate 120 and the runner 240 of brine inlet, sour water import and buck inlet communication, sour water, alkali
Water and salt water pass through between 240 inlet membrane of runner.
1 pair of diaphragm is correspondingly arranged on the corresponding brine outlet in the salt room 115 of salt room 115,20,20 pairs of films, one salt
Water out, 40 pairs of diaphragms are correspondingly arranged there are two brine outlet.
1 pair of diaphragm is correspondingly arranged on the corresponding sour water of 116,20 acid compartments 116 of an acid compartment and exports 210,20 pairs of films one
A sour water exports 210,40 pairs of diaphragms and is correspondingly arranged that there are two sour water outlets 210.
1 pair of diaphragm is correspondingly arranged on the corresponding buck outlet of 117,20 alkaline chambers 117 of an alkaline chamber, 20 pairs of films, one alkali
Water out, 40 pairs of diaphragms be correspondingly arranged there are two buck export.
Diaphragm block 110 according to Bipolar Membrane, partition, cavity block, partition, anode membrane, partition, Bipolar Membrane, partition, cavity block, partition,
The arrangement of anode membrane, partition repeats to be arranged.
Partition with a thickness of 2~3mm, partition, Bipolar Membrane, cavity block, anode membrane both ends be provided with 7 apertures 230；Partition
On aperture 230 be correspondingly arranged on runner 240, including two sour 240, two alkali runners 240 of runner and three salt runners 240.
When the two sides of partition are set as anode membrane and cavity block, the chamber forming salt room 115 of diaphragm internal.The two sides of partition are set as
When Bipolar Membrane and cavity block, the chamber of diaphragm internal forms acid compartment 116.Aperture 230 on the partition is connect with sour water intake channel.It should
Aperture 230 on partition is connect with sour water intake channel.Sour water passes through the sour runner 240 connecting with aperture 230, from the acid of partition
Water inlet channel is mobile to the sour water of partition outlet 210.116 two sides of acid compartment are Bipolar Membrane and cavity block, and H+ passes through Bipolar Membrane sun
Film, SO42-pass through cavity block, and the acid concentration across acid compartment 116 increases.Then it is connect with sour water exit passageway 211.
When the two sides of partition are set as anode membrane and Bipolar Membrane, the chamber of diaphragm internal forms alkaline chamber 117.Aperture on the partition
230 connect with buck intake channel.Aperture 230 on the partition is connect with buck intake channel.Buck passes through to be connected with aperture 230
The alkali runner 240 connect, it is mobile from the buck intake channel of partition to the buck exit passageway 221 of partition.117 two sides of alkaline chamber are sun
Film and Bipolar Membrane, Na+ pass through anode membrane, and OH-passes through Bipolar Membrane cavity block, and the alkali concentration across alkaline chamber 117 increases.Then with buck
Exit passageway 221 connects.
The rectangle of the Bipolar Membrane, cavity block and anode membrane for 1500mm*500mm, gross area 0.75m2, effective coverage are long
1200mm*420mm, effective area 0.5m2, effective area accounting 66.67%.
The membrane voltage (10A/dm2,30 DEG C) of Bipolar Membrane is 1.2V；Water decomposition efficiency >=98%；Rupture strength >=0.4Mpa；
With a thickness of 0.22mm.
Anode membrane correlation is highly acid anode membrane, has high-intensitive characteristic according to the index of CSE-2；Membrane impedance is 1.9 Ω cm
²；Rupture strength is greater than 0.35 Mpa；With a thickness of 0.15mm.
Cavity block correlation is alkalescent cavity block, has the characteristic for being not easy acid according to the index of ACM；Membrane impedance is 2.6 Ω cm
²；Rupture strength is greater than 0.15 Mpa；With a thickness of 0.11mm.
Embodiment 2
A kind of viscose sodium sulfate waste liquor multi-level handling system, including multi-stage treatment units and to provide conducting solution
Pole water pot；Every level-one processing unit includes sodium sulphate circulating tank, sulfuric acid circulating tank, sodium hydroxide circulating tank and membrane stack, spy
Sign is: the sodium sulphate circulating tank, sulfuric acid circulating tank, sodium hydroxide circulating tank are respectively from same membrane stack through the different disengaging degree of lip-roundings
Channel and composition coagulation device at independent loops；The sodium sulphate circulating tank, sulfuric acid circulating tank, sodium hydroxide circulating tank
It is carried out respectively by sodium sulphate circulating tank, sulfuric acid circulating tank, the sodium hydroxide circulating tank of respective pipeline and next stage respectively again
Connection, and the import of the sodium sulphate circulating tank of next stage is connect with the outlet of upper level sodium sulphate circulating tank, and the sulphur of next stage
The outlet import with the sulfuric acid circulating tank of upper level and sodium hydroxide circulating tank respectively of sour circulating tank and sodium hydroxide circulating tank
Connection；Sulfuric acid circulating tank, sodium hydroxide circulating tank in first order processing unit again respectively with sulfuric acid finished product box and sodium hydroxide
Finished product box connection；It is more than the processing unit at least two-stage.
The membrane stack includes spaced diaphragm block 110 and diaphragm plate 120, and end is diaphragm plate 120, two films of end
Plate 120 is connected with a pole plate 130 respectively；Power interface 140, pole water inlet and pole water out are provided on the pole plate 130；
One pole plate 130 connects positive pole by power interface 140, another pole plate 130 connects power supply by power interface 140 and bears
Pole；The diaphragm block 110 includes the multipair diaphragm and partition overlapped, and every a pair of diaphragm includes cavity block, anode membrane and bipolar
Film；The diaphragm block 110 repeats to be arranged according to the arrangement of Bipolar Membrane, partition, cavity block, partition, anode membrane, partition；The partition
One end connects brine inlet, sour water import or buck import；The partition other end connection brine outlet, sour water outlet 210
Or buck outlet.
The overflow port of level-one sodium sulphate circulating tank is connected to the import of second level sodium sulphate circulating tank；Second level sodium sulphate circulating tank
Overflow port be connected to the import of three-level sodium sulphate circulating tank.
The overflow port of three-level sulfuric acid circulating tank is connected to the import of second level acid circulating box；The overflow port of second level sulfuric acid circulating tank
It is connected to the import of primary acids circulating box；Level-one sulfuric acid circulating tank connects sour finished product box.
The overflow port of three sodium hydroxide circulating tanks is connected to the import of second level alkali circulating box；Two sodium hydroxide circulating tanks
Overflow port be connected to the import of level-one alkali circulating box；One sodium hydroxide circulating tank connects alkali finished product box.
Level-one sodium sulphate circulating tank, sulfuric acid circulating tank, sodium hydroxide circulating tank and pole water pot generated in membrane stack weak brine,
Finished acid, product caustic soda.
It is 280g/L that primary cycle, which obtains concentration, and discharging flow is the level-one weak brine of 5m3/h.Level-one weak brine passes through one
The overflow port of grade sodium sulphate circulating tank enters in second level sodium sulphate circulating tank, into second level bipolar membrane electrodialysis treatment, obtains
It is 180 brine inlet g/L to concentration, discharging flow is the second level weak brine of 5m3/h.Second level weak brine is followed by second level sodium sulphate
The overflow port of ring tank enters in three-level sodium sulphate circulating tank, and into three-level bipolar membrane electrodialysis treatment, obtaining concentration is
100g/L, discharging flow are the three-level weak brine of 5m3/h.And so on, three-level weak brine overflow to dilute salt or next stage sulphur
In sour sodium circulating tank, obtaining concentration is 50g/L, and discharging flow is the weak brine of 5m3/h.
The discharging flow for the acid that three-level circulation is prepared is 3.09~10.98m3/h, and concentration is 9.78~34.78g/L,
It is back in the sulfuric acid circulating tank of second level.The discharging flow of the standby acid of two-stage system is 3.09~10.98m3/h, concentration 25.43
~90.43g/L is back in the sulfuric acid circulating tank of level-one.The discharging flow for the finished acid that level-one is prepared be 3.09~
10.98m3/h, concentration are 45~160g/L, and level-one sulfuric acid circulating tank connects sour finished product box.
The discharging flow of alkali that three-level circulation is prepared is 3.59~12.78m3/h, concentration be 9.78~34.78 g/
L is back in the sodium hydroxide circulating tank of second level.The discharging flow of the standby alkali of two-stage system is 3.59~12.78m3/h, and concentration is
25.43~90.43 g/L are back in the sodium hydroxide circulating tank of level-one.The discharging flow for the product caustic soda that level-one is prepared
For 3.59~12.78m3/h, concentration is 45~160 g/L, and a sodium hydroxide circulating tank connects alkali finished product box.
Salt circulating tank, sour circulating tank, alkali circulating tank and pole water pot pass sequentially through circulating pump, filter, cooling device respectively
Enter to the import of membrane stack.
Circulating pump is to transport the solution in circulating tank.
Inflow temperature of the cooling device to adjust membrane stack.
Cooling device is plate heat exchanger, heat pump or compression refigerating machine.Cooling device enters the solution of membrane stack to adjust
Feeding temperature is controlled at 17~37 DEG C；After membrane stack, the temperature of solution is 34 ~ 35 DEG C.
Salt circulating tank, sour circulating tank, alkali circulating tank and pole water pot are additionally provided with before the import for entering membrane stack into valve
And pressure transmitter.It is consistent with sour circulating tank, alkali circulating tank, the pressure of pole water pot to control salt circulating tank, reduce pressure not
Unanimously to the damage of diaphragm.
The both ends of filter are additionally provided with pressure transmitter.The pressure transmitter of the both ends setting of filter can observe pressure
Difference illustrates that impurity is excessive, needs replacing filter core when pressure difference is excessive.
Filter core is arranged to remove the impurity in metabisulfite solution in filter interior.The aperture of filter interior filter core is
25-50μm.Here impurity is some solid particle polluters that storage tank, pipeline are brought into transmission process.
The outlet end of plate heat exchanger is additionally provided with thermometer, inflow temperature of the thermometer to monitor membrane stack, water inlet
Temperature is controlled at 17~37 DEG C, and temperature increases in membrane stack, and the leaving water temperature of membrane stack is 20~40 DEG C.There is wave according to season difference
Dynamic, the inflow temperature for controlling membrane stack can indirectly control leaving water temperature.
The exit of membrane stack is provided with out valve and conductivity meter, and conductivity meter also can be used to detectable concentration, can be by following
The moisturizing of ring tank adjusts concentration.
Be passed through treated metabisulfite solution in the salt circulating tank of the utility model, in sour circulating tank and alkali circulating tank in
It is placed with the sulfuric acid solution and sodium hydroxide solution to start circulation, is placed in the water pot of pole to conductive sodium hydroxide
Solution.
More than, it is only the preferred embodiment of the utility model, limitation in any form not is done to the utility model, it is all
It is any simple modification made by the above technical examples according to the technical essence of the present invention, equivalent variations, each falls within this reality
Within novel protection scope.
Claims (7)
1. a kind of membrane stack device for viscose sodium sulfate waste liquor processing, it is characterised in that: including spaced diaphragm
Unit (110) and diaphragm plate (120), end are diaphragm plate (120), and two diaphragm plates (120) of end connect with pole plate (130) respectively
It connects；Power interface (140), pole water inlet and pole water out are provided on the pole plate (130)；One pole plate (130) passes through electricity
Source interface (140) connects positive pole, another pole plate (130) connects power cathode by power interface (140)；The diaphragm
Unit (110) includes the multipair diaphragm and partition overlapped, and every a pair of diaphragm includes cavity block, anode membrane and Bipolar Membrane；The film
Blade unit (110) repeats to be arranged according to the arrangement of Bipolar Membrane, partition, cavity block, partition, anode membrane, partition；Partition one end connection
Brine inlet, sour water import or buck import；The partition other end connection brine outlet, sour water outlet (210) or alkali
Water out.
2. as described in claim 1 for viscose sodium sulfate waste liquor processing membrane stack device, it is characterised in that: it is described every
One end of plate is connected with brine inlet, sour water import and buck import, is respectively formed brine inlet in diaphragm internal formation
Channel, sour water intake channel and buck intake channel；The other end of the partition is connected with brine outlet, sour water outlet (210)
It is exported with buck, forms brine outlet channel, sour water exit passageway (211) and buck exit passageway in the diaphragm internal
(221).
3. as described in claim 1 for viscose sodium sulfate waste liquor processing membrane stack device, it is characterised in that: it is described every
Plate with a thickness of 2~3mm；The partition includes silicon rubber partition and intermediate lining net；The partition, Bipolar Membrane, cavity block and anode membrane
Both ends be provided with multiple apertures (230)；Aperture (230) on the partition is correspondingly arranged on runner (240).
4. the membrane stack device for viscose sodium sulfate waste liquor processing as described in claim 1, it is characterised in that: 1 pair of film
Piece is correspondingly arranged on a salt room (115), an acid compartment (116) and an alkaline chamber (117)；One salt room (115) is one corresponding
Brine inlet channel and a brine outlet channel；One corresponding sour water intake channel of acid compartment (116) and a sour water go out
Mouth channel (211)；One corresponding buck intake channel of alkaline chamber (117) and a buck exit passageway (221).
5. the membrane stack device for viscose sodium sulfate waste liquor processing as described in claim 1, it is characterised in that: described double
Pole film, cavity block and anode membrane are the rectangle of 1500mm* 500mm；The Bipolar Membrane, cavity block and anode membrane are close to the partition respectively and are set
It sets.
6. the membrane stack device for viscose sodium sulfate waste liquor processing as described in claim 1, it is characterised in that: a pole
The side of plate (130) is provided with pressure plate (250), which is clamped by fastening bolt (260)；Another pole plate
(130) it is connect with rack (270).
7. the membrane stack device for viscose sodium sulfate waste liquor processing as claimed in claim 6, it is characterised in that: the pressure
One end of tight plate (250) also sets gradually rack beam (280) and hydraulic press piston boit (290)；The hydraulic press piston boit (290)
It is fixedly connected with rack (270).
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| CN110975405A (en) * | 2019-12-20 | 2020-04-10 | 宜宾海丝特纤维有限责任公司 | Alkali liquor desalting process |
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| CN110975405A (en) * | 2019-12-20 | 2020-04-10 | 宜宾海丝特纤维有限责任公司 | Alkali liquor desalting process |
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Denomination of utility model: A membrane stack device for the treatment of sodium sulfate waste liquid from viscose fibers Granted publication date: 20190719 Pledgee: Yibin Development Holding Group Co.,Ltd. Pledgor: YIBIN GRACE GROUP Co.,Ltd.|YIBIN GRACE Co.,Ltd.|YIBIN HIEST FIBRE Ltd.,Corp. Registration number: Y2024980030046 |