CN103349908A - Method for squeezing alkali liquid in diffusion dialysis recycling viscose manufacture - Google Patents
Method for squeezing alkali liquid in diffusion dialysis recycling viscose manufacture Download PDFInfo
- Publication number
- CN103349908A CN103349908A CN2013103117756A CN201310311775A CN103349908A CN 103349908 A CN103349908 A CN 103349908A CN 2013103117756 A CN2013103117756 A CN 2013103117756A CN 201310311775 A CN201310311775 A CN 201310311775A CN 103349908 A CN103349908 A CN 103349908A
- Authority
- CN
- China
- Prior art keywords
- diffusion dialysis
- concentration
- lye
- press
- cation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000009792 diffusion process Methods 0.000 title claims abstract description 131
- 238000000502 dialysis Methods 0.000 title claims abstract description 129
- 238000000034 method Methods 0.000 title claims abstract description 101
- 239000003513 alkali Substances 0.000 title claims abstract description 77
- 239000007788 liquid Substances 0.000 title claims abstract description 54
- 229920000297 Rayon Polymers 0.000 title claims abstract description 50
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 37
- 238000004064 recycling Methods 0.000 title abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 278
- 239000012528 membrane Substances 0.000 claims abstract description 79
- 229920002488 Hemicellulose Polymers 0.000 claims abstract description 71
- 238000005341 cation exchange Methods 0.000 claims abstract description 61
- 238000001914 filtration Methods 0.000 claims abstract description 52
- 238000011084 recovery Methods 0.000 claims abstract description 46
- 230000008569 process Effects 0.000 claims abstract description 44
- 210000004379 membrane Anatomy 0.000 claims description 73
- 239000012535 impurity Substances 0.000 claims description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 210000002469 basement membrane Anatomy 0.000 claims description 22
- -1 polypropylene Polymers 0.000 claims description 20
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 15
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 15
- 238000010521 absorption reaction Methods 0.000 claims description 14
- 239000004744 fabric Substances 0.000 claims description 12
- 239000004743 Polypropylene Substances 0.000 claims description 11
- 229920001155 polypropylene Polymers 0.000 claims description 11
- 150000003460 sulfonic acids Chemical class 0.000 claims description 9
- 239000004677 Nylon Substances 0.000 claims description 8
- 229920001778 nylon Polymers 0.000 claims description 8
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 8
- 239000004800 polyvinyl chloride Substances 0.000 claims description 8
- 230000009467 reduction Effects 0.000 claims description 8
- 238000005516 engineering process Methods 0.000 abstract description 11
- 238000007781 pre-processing Methods 0.000 abstract 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 117
- 239000002253 acid Substances 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- 239000002699 waste material Substances 0.000 description 16
- 239000012530 fluid Substances 0.000 description 12
- 238000012805 post-processing Methods 0.000 description 12
- 238000000108 ultra-filtration Methods 0.000 description 12
- 239000011229 interlayer Substances 0.000 description 10
- 239000000835 fiber Substances 0.000 description 9
- 238000012545 processing Methods 0.000 description 9
- 238000005265 energy consumption Methods 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000000428 dust Substances 0.000 description 6
- 238000006277 sulfonation reaction Methods 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 230000004913 activation Effects 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000012141 concentrate Substances 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 4
- 230000008676 import Effects 0.000 description 4
- 238000001223 reverse osmosis Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 3
- 239000003011 anion exchange membrane Substances 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 230000036571 hydration Effects 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- 238000001471 micro-filtration Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 235000012489 doughnuts Nutrition 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005374 membrane filtration Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- VAOCPAMSLUNLGC-UHFFFAOYSA-N metronidazole Chemical compound CC1=NC=C([N+]([O-])=O)N1CCO VAOCPAMSLUNLGC-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 241001330002 Bambuseae Species 0.000 description 1
- 239000004801 Chlorinated PVC Substances 0.000 description 1
- 241000370738 Chlorion Species 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229920000457 chlorinated polyvinyl chloride Polymers 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000010808 liquid waste Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000003020 moisturizing effect Effects 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 description 1
- 229910000367 silver sulfate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Images
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to a method for squeezing alkali liquid in diffusion dialysis recycling viscose manufacture, and belongs to the technical field of viscose manufacture. The method comprises the following steps: preprocessing the squeezed alkali liquid, which contains sodium hydroxide with the concentration of 50-200 g/L and hemicelluloses with the concentration of 20-150 g/L, to obtain the preprocessing liquid; entering diffusion dialysis membrane group, and obtaining recycling liquid through diffusion dialysis using cation exchange membrane, wherein the gage pressure of the diffusion dialysis process is 0.03-0.08 Pa. The method aims at the diffusion dialysis technology for recycling viscose squeezed alkali, adopts filtration preprocessing to process the squeezed alkali liquid before entering, increases the recovery rate of alkali and hemicelluloses in the squeezed alkali liquid, reduces damage to the diffusion dialysis membrane system caused by the alkali liquid, prevents blockage of the diffusion dialysis membrane, prolongs the service life of the membrane, and guarantees the smooth progress of diffusion dialysis and follow-up handling.
Description
Technical field
The present invention relates to the method that material is processed in a kind of Chemical Manufacture, more particularly, the present invention relates to the method that press lye in the viscose rayon production is reclaimed in a kind of diffusion dialysis, belong to the viscose rayon production technical field.
Background technology
Production process of viscose fiber in chemical fibre industry can produce the akaline liquid that contains high-enriched organics (take hemicellulose as main).If let alone direct discharging, will cause serious environmental pollution.Process this alkali lye if adopt the method for neutralization, a large amount of acid will be consumed, and cause a large amount of inorganic salts of formation in the alkali lye, therefore the alkali in this alkali lye is reclaimed, and make wherein organic matter become the solid matter that can carry out harmless treatment to be only the processing mode more friendly to environment.
Viscose staple fibre is the cellulose reprocessing product that is present in the natural products, have the suction moisturizing, smooth nice and cool, ventilative, antistatic, the characteristic such as gorgeous dyes.Its production process is to use bamboo, wood, cotton, it is raw material that fiber crops etc. are rich in the prepared pulp of cellulosic plant, flood through caustic soda, yellow, and thereby regeneration obtains the viscose rayon product in acid coagulating bath, flood at caustic soda, the link of squeezing can produce above-mentioned akaline liquid, this akaline liquid is called press lye, be different from the spent lye that other industry produces, its composition is mainly NaOH and hemicellulose, at present the alkali in this alkali lye is reclaimed and also lack effective means, although adopt Nanofiltering membrane to reclaim alkali in the minority field, but still exist the rate of recovery low, the shortcoming that operating cost is high.
Diffusion dialysis is to utilize pellicle or perm-selective ion-ex-change membrane, the process that the solute in the solution is moved to low concentration one side by film by high concentration one side, and this process is as power take concentration difference.It is mainly used in separating and purifying of organic and inorganic electrolyte.Aspect environmental project, be mainly used at present processing and the recovery of Suan ﹑ alkali wasteliquid.
The beginning of the fifties in 19th century, Englishize scholar T. Graham Sodd method of investing begins systematically to study the diffusion of solution, different solutes have been studied again subsequently by the characteristic of pellicle (film that parchment or celloidin etc. are made), find then intransitable phenomenon of can be by the pore of the pellicle larger colloidal particle of the molecule of some solutes or ion, Graham Sodd method of investing claims that this phenomenon is dialysis.The equipment of around this principle making is called dialyzer, the purification that is usually used in the concentrated of colloidal solution and examines the macromolecular compounds such as sour ﹑ protein.The 1950's, occurred with the diffusion dialysis device of amberplex as barrier film.
The domestic diffusion dialysis film of just having developed as far back as 1964.But because the restriction of film preparation technique, the structure of the similar homogeneous phase ionic membrane of resulting film is all this type of film such as polysulfones quaternary ammonium cavity block S203, DF120 and chlorinated polyvinyl chloride type weak alkaline ionexchange memberanes.
In the diffusion dialysis process, the motive force of ion transfer is the concentration difference of film both sides, uses homo-ion repulsion and the electroneutral of Donnan (Donnan) balance and keeps correlation theory, thereby realize that the selectively penetrating of ion reaches the purpose of separation.This process is divided into anode membrane diffusion dialysis (as being used for the recovery of alkali) and cavity block diffusion dialysis (as being used for the recovery of acid).Wherein cavity block diffusion dialysis technology utilizes anion-exchange membrane to hydrogen ion and the different realization acid of selection permeability of metal ion and separating of salt, the both sides that for example mixed solution and the water of hydrochloric acid and aluminium chloride placed respectively anion-exchange membrane, because the acid of solution side and the concentration of salt are far above the water side, the trend of the oriented water side infiltration of acid and salt, but anion-exchange membrane has the selection permeability, can not allow every kind of ion pass through with equal opportunity; At first anionic membrane skeleton itself is positively charged, in solution, has the characteristic that attracts electronegative ion hydration and repel positively charged ion hydration, so under the effect of concentration difference, the chlorion of solution side is attracted and successfully sees through the side that the fenestra road enters water; According to electroneutral requirement, also can carry the ion with positive charge secretly simultaneously, but because H
+Hydrated radius smaller, electric charge is less, and aluminum ions ion hydration radius is larger, again with high valence charge, therefore hydrogen ion can preferentially pass through film, and the acid in the solution will be separated into water inlet side like this, and passing through of this Hydrogen ion is the key of diffusion dialysis.Used amberplex need to possess some suitable performances, and such as the stability in acid solution, high hydrogen ion percent of pass is to the high rate of rejection of metal ion and low water percent of pass etc.The anode membrane diffusion dialysis process that is used for the alkali recovery is similar with it.
Abroad, the technical development of diffusion dialysis recovered acid is comparatively rapid, and wherein representative country is the U.S. and Japan.The Exergy technique company of the U.S. has developed a kind of new online diffusion dialysis technology, and has pushed commercial Application to.This process using amberplex is processed Waste Sulfuric Acid, and it is recycled.System utilizes flowmeter and liquid level gauge control, and is designed to full-automatic mode, is provided with grid spacer between the film, and is stable to keep lamination.The rate of recovery of acid can reach 88%, and the metal rejection reaches 95%, has greatly reduced the dialysis liquid measure of delivering to Waste Water Treatment, thereby has reduced the consumption of neutralization chemicals, and energy consumption also greatly reduces.
It is CN1450001 that State Intellectual Property Office discloses a publication number in 2003.10.22, name is called the patent of invention of " reclaiming alkali in the chemical fibre waste fluid and the method for hemicellulose ", and this patent provides a kind of alkali in the chemical fibre waste fluid and method of hemicellulose of reclaiming.Method of the present invention comprises the steps: that the pressed liquor that will contain alkali and hemicellulose enters membrane separation device through pre-filtering and smart filter, acquisition contains seeing through liquid and containing the concentrate of hemicellulose of alkali, what obtain can reach the 80-250 grams per liter through concentration of lye in the liquid, final alkali content is the 5-30 grams per liter in the concentrate, and hemicellulose level is the 100-200 grams per liter.Hemicellulose is not only effectively separated and purifying with alkali lye, and technical process is simple, and hemicellulose and the alkali in the filter liquor in the concentrate are convenient to be used respectively, have not only utilized resource but also protected environment.Adopt this technological transformation tradition liquid waste processing mode to have investment weak point return period, the high and good characteristics of environmental benefit of economic benefit.The popularization and application of this technology will promote the whole industrial level of chemical fibre industry.
Above-mentioned patent is to adopt conventional membrane filtration technique to carry out the recovery of alkali lye and hemicellulose, although the press lye in the viscose rayon production is had certain recovering effect, still exists the rate of recovery not high, and energy consumption is large, can't online recycling and recycling.
The above shows that all the technology of diffusion dialysis reclamation film has other membrane process and the incomparable advantage of the way of distillation, but present diffusion dialysis mainly is to be used in acid recovery, and be used for diffusion dialysis film that alkali reclaims seldom, even the recovery for alkali in the alkali lye, also be to reclaim for other industry alkali lye, the akaline liquid that the constituent of its recycle object, index parameter and viscose rayon industry produce differs larger, and the technology that existing diffusion dialysis can't be reclaimed alkali is directly used in the akaline liquid that produces in the viscose rayon technique.
It is CN102976450A that State Intellectual Property Office discloses a publication number in 2013.3.20, name is called the patent of invention of " alkali recovery process of squeezing waste liquid in a kind of viscose rayon production ", this patent disclosure a kind of viscose rayon produce in the alkali recovery process of squeezing waste liquid, allow squeezing waste liquid and the distilled water cation-exchange membrane diffusion dialysis device inner chamber of flowing through simultaneously, the flow velocity of control squeezing waste liquid and water is so that NaOH content is 15-25g/L the squeezing waste liquid that flows out in cation-exchange membrane diffusion dialysis device.The alkali that this technique can effectively reclaim in the squeezing waste liquid is used for producing, reducing sour consumption, reduced the sewage disposal difficulty and reduced energy consumption, can bring the beneficial effect that reduces the viscose rayon production cost.
The alkali that adopts the diffusion dialysis technology to be applied to the squeezing waste liquid in the viscose rayon production in the above-mentioned patent reclaims, but the rate of recovery is not high, sodium hydrate content in the liquid after treatment is 15-25g/L only, is difficult to direct reuse other need alkali links in viscose glue is produced, and causes waste.And will squeeze waste liquid and directly enter the diffusion dialysis treating apparatus, and can cause damage to film, affect carrying out smoothly of whole recovery technique.
It is CN102941017A that State Intellectual Property Office discloses a publication number in 2013.2.27, name is called the patent of invention of " secondary treatment method of discarded alkali lye in a kind of viscose rayon production ", this patent relates to the secondary treatment method of discarded alkali lye in a kind of viscose rayon production, belongs to field of viscose fiber.The present invention will be through conventional pretreated, naoh concentration is 70-90g/L, discarded alkali lye and the demineralized water of half fiber content 60-70g/L are delivered to respectively the diffusion dialysis membrane stack, carry out diffusion dialysis, the flow-rate ratio of described preliminary treatment spent lye and demineralized water is 1-2:1, the alkali lye that will hang down hemicellulose concentration after the diffusion dialysis separates with the alkali lye of height half fine concentration, and the alkali lye of described low hemicellulose concentration is back to production.The invention solves in the prior art, still can produce secondary waste alkali lye through the discarded alkali lye of once recycling, if directly discharging, can cause to environment the problem of considerable damage, provide a kind of processing method of secondary waste alkali lye, by diffusion dialysis, can reclaim to greatest extent the NaOH in the discarded alkali lye, reduce environmental pollution, improved ecological benefits, reduced simultaneously the cost of environmental protection treatment.
The same alkali that adopts the diffusion dialysis technology to be applied to the squeezing waste liquid in the viscose rayon production reclaims in the above-mentioned patent, although mentioned in the technical scheme first waste liquid carried out conventional preliminary treatment, but still can't carry out for the press lye of the high concentration in the viscose rayon recovery of diffusion dialysis film processes, can directly affect the concentration range of diffusion dialysis film recovery and carrying out smoothly of subsequent treatment and recycling, and the scope of the press lye that can process is narrower, and it is low to process yield.
Summary of the invention
The present invention is intended to solve existing problem and the defective that is applied to reclaim the diffusion dialysis technology existence of the press lye in the viscose rayon production, provide a kind of diffusion dialysis to reclaim the method for the press lye of variable concentrations that viscose rayon produces in producing and hemicellulose level, only for the diffusion dialysis technique that is applied to reclaim the viscose rayon press lye, adopt specific preprocess method that press lye is processed, enter again the diffusion dialysis process, the rate of recovery of alkali and hemicellulose in the raising press lye, reduce alkali lye to the damage of diffusion dialysis film system, improve the service life of film, and guarantee carrying out smoothly of diffusion dialysis and subsequent handling.
In order to realize the foregoing invention purpose, concrete technical scheme of the present invention is as follows:
The method of press lye in the viscose rayon production is reclaimed in a kind of diffusion dialysis, it is characterized in that: be 50-200g/L with naoh concentration, hemicellulose concentration is that the press lye of 20-150g/L reduces large granular impurity concentration through filtering preliminary treatment, then enter in the diffusion dialysis film group device with demineralized water as absorption liquid, mode with cross-flow flows, carry out diffusion dialysis by cation-exchange membrane, be recycled alkali lye; Gauge pressure in the described diffusion dialysis process is 0.03-0.08MPa.
Naoh concentration in the press lye of process filtration preliminary treatment reduction large granular impurity concentration of the present invention is controlled to be 50-200g/L, and hemicellulose concentration is controlled to be 20-150g/L, and large granular impurity content is controlled to be less than 1g/L.
Above-mentioned large granular impurity comprises bulky grain dust impurity, bulky grain metal impurities etc.
Cation-exchange membrane of the present invention be the cloth of a kind of or two kinds of cospinning shapes in nylon, polypropylene, polyvinyl chloride, the polytetrafluoroethylene (PTFE) as basement membrane, be filmed the alkaline-resisting cation-exchange membrane that forms with rubbing method with perfluorinated sulfonic acid again.
The thickness of above-mentioned basement membrane is 0.05-2mm.
The aperture of cation-exchange membrane of the present invention is 5-10nm.
Width of flow path in the diffusion dialysis film group device of the present invention is 0.2-1mm.
The flow control of press lye of the present invention is 2-20mm/s, and the flow control of described demineralized water is 3-25mm/s.
In the diffusion dialysis film group device of the present invention, the clearance control between every adjacent two cation-exchange membranes is 0.4-0.9mm.
Naoh concentration in the recovery alkali lye of the present invention is controlled to be 40-160g/L, and hemicellulose concentration is controlled to be＜10g/L.
The useful technique effect that the present invention brings:
1, the invention solves the existing not resisting high-concentration alkali that is applied to reclaim the diffusion dialysis technology existence of the press lye in the viscose rayon production, problem and the defective not high to the hemicellulose rejection, for the diffusion dialysis technique that is applied to reclaim the viscose rayon press lye, adopted the preprocess method that filters that press lye is processed, removed large granular impurity, enter again the diffusion dialysis process, improved the rate of recovery of alkali and hemicellulose in the press lye, reduce alkali lye to the damage of diffusion dialysis film system, prevent the obstruction to the diffusion dialysis film, improve the service life of film, and guaranteed carrying out smoothly of diffusion dialysis and subsequent handling; Gauge pressure in the diffusion dialysis is 0.03-0.08MPa in addition, can guarantee passing through smoothly of liquid, can prolong again the service life of cation-exchange membrane, and can effectively prevent the generation of seepage; Adopt demineralized water as absorption liquid, reduce fouling, the service life of further improving cation-exchange membrane and film group device; Adopt the mode of cross-flow can further improve the rate of recovery of alkali, because the driving force of diffusion dialysis comes from the concentration difference of the alkali lye of film both sides, can make in the flow process of alkali lye in film with the mode of cross-flow to remain concentration difference.
2, the naoh concentration in the press lye of process preliminary treatment removal large granular impurity of the present invention is controlled to be 50-200g/L, and hemicellulose concentration is controlled to be 20-150g/L, and other large granular impurity content are controlled to be less than 1g/L.Greatly reduce the content of large granular impurity, the index of above-mentioned pretreatment fluid is the integral body of three parameters, obtain by specific pretreatment mode, the combination of three parameters, synergy, can reduce other materials to the infringement of film, reduce the frequency that film group device cleans, the service life of extension device, guarantee carrying out smoothly of diffusion dialysis processing procedure and subsequent treatment operation, reduce energy consumption, in addition so that the recovery liquid that obtains after the diffusion dialysis can recovery efficient, high yield separate NaOH and hemicellulose.
3, cation-exchange membrane of the present invention is with nylon, polypropylene, polyvinyl chloride, the cloth of a kind of or two kinds of cospinning shapes in the polytetrafluoroethylene (PTFE) is basement membrane, be filmed the alkaline-resisting cation-exchange membrane that forms with rubbing method with perfluorinated sulfonic acid again, adopt perfluorinated sulfonic acid diffusion dialysis film, improved the rate of recovery of alkali in the press lye, improved alkaline-resisting concentration, improved half-and-half cellulosic rejection, reduce alkali lye to the damage of diffusion dialysis film system, prevent the obstruction to the diffusion dialysis film, improve the service life of film, and guaranteed carrying out smoothly of diffusion dialysis and subsequent handling.
4, the present invention is preferred, and the thickness of basement membrane is 0.05-2mm, the resistance in the time of can effectively reducing diffusion dialysis; The aperture of cation-exchange membrane of the present invention is 5-10nm, can strengthen the diffusion dialysis handling property, reduces film and pollutes, prolongs membrane lifetime and improve diffuser efficiency; The flow control of press lye of the present invention is 2-20mm/s, and the flow control of described demineralized water is 3-25mm/s, and when guaranteeing diffusion velocity, the control resistance arrives minimum, and can control pressure reduction, prevents seepage.
5, in the diffusion dialysis film group device of the present invention, the clearance control between every adjacent two cation-exchange membranes is 0.4-0.9mm, and the selection of this technological parameter can increase Reynolds number, increases diffusion coefficient, improves diffusion velocity, and then enhances productivity.
6, the naoh concentration in the recovery alkali lye of the present invention is controlled to be 40-160g/L, hemicellulose concentration is controlled to be＜10g/L, controlling above-mentioned concentration is in order to make press lye reach a suitable concentration difference in film group device, so that chemical recovery system reaches a higher rate of recovery, also provide a comparatively suitable concentration to post processing, water in the time of can reducing the energy consumption of evaporation and concentration and reduce dilution is so that whole system technique and energy consumption are optimized.
7, technological parameter during diffusion dialysis recovery viscose rayon of the present invention is produced in the press lye is as a complete parameter system, complement each other, can be applicable to alkali concn and the wider press lye of hemicellulose concentration range, the pretreatment fluid that obtains through the filtration preliminary treatment enters the cation-exchange membrane diffusion dialysis again, the rate of recovery and the yield of alkali and hemicellulose in the press lye have been improved, reduced the damage of alkali lye to cation-exchange membrane diffusion dialysis film system, prevent the obstruction to the diffusion dialysis cation-exchange membrane, improve the service life of film, optimize technique and energy consumption, and guaranteed carrying out smoothly of diffusion dialysis and subsequent handling.
Description of drawings
Accompanying drawingStructural representation for cation-exchange membrane diffusion dialysis device film group device of the present invention;
Reference numeral: 1 be the first clamping plate, 2 be the second clamping plate, 3 for press lye runner interlayer, 4 for absorption liquid runner interlayer, 5 for the press lye import, 6 for the absorption liquid import, 7 for raffinate outlet, 8 for reclaim the liquid outlet, 9 for cation-exchange membrane, 10 be dividing plate.
The specific embodiment
Embodiment 1
The method of press lye in the viscose rayon production is reclaimed in a kind of diffusion dialysis, be 50g/L with naoh concentration, hemicellulose concentration is that the press lye of 20g/L reduces large granular impurity concentration through filtering preliminary treatment, then enter in the diffusion dialysis film group device with demineralized water as absorption liquid, mode with cross-flow flows, carry out diffusion dialysis by cation-exchange membrane, be recycled alkali lye; Gauge pressure in the described diffusion dialysis process is 0.03MPa.
Embodiment 2
The method of press lye in the viscose rayon production is reclaimed in a kind of diffusion dialysis, be 200g/L with naoh concentration, hemicellulose concentration is that the press lye of 150g/L reduces large granular impurity concentration through filtering preliminary treatment, then enter in the diffusion dialysis film group device with demineralized water as absorption liquid, mode with cross-flow flows, carry out diffusion dialysis by cation-exchange membrane, be recycled alkali lye; Gauge pressure in the described diffusion dialysis process is 0.08MPa.
Embodiment 3
The method of press lye in the viscose rayon production is reclaimed in a kind of diffusion dialysis, be 125g/L with naoh concentration, hemicellulose concentration is that the press lye of 85g/L reduces large granular impurity concentration through filtering preliminary treatment, then enter in the diffusion dialysis film group device with demineralized water as absorption liquid, mode with cross-flow flows, carry out diffusion dialysis by cation-exchange membrane, be recycled alkali lye; Gauge pressure in the described diffusion dialysis process is 0.055MPa.
The method of press lye in the viscose rayon production is reclaimed in a kind of diffusion dialysis, be 180g/L with naoh concentration, hemicellulose concentration is that the press lye of 36g/L reduces large granular impurity concentration through filtering preliminary treatment, then enter in the diffusion dialysis film group device with demineralized water as absorption liquid, mode with cross-flow flows, carry out diffusion dialysis by cation-exchange membrane, be recycled alkali lye; Gauge pressure in the described diffusion dialysis process is 0.07MPa.
On the basis of embodiment 1-4, preferred:
Naoh concentration in the press lye of described process filtration preliminary treatment reduction large granular impurity concentration is controlled to be 50g/L, and hemicellulose concentration is controlled to be 20g/L, and large granular impurity content is controlled to be less than 1g/L.
Described cation-exchange membrane be the cloth of a kind of or two kinds of cospinning shapes in nylon, polypropylene, polyvinyl chloride, the polytetrafluoroethylene (PTFE) as basement membrane, be filmed the alkaline-resisting cation-exchange membrane that forms with rubbing method with perfluorinated sulfonic acid again.
The thickness of described basement membrane is 0.05mm.
The aperture of described cation-exchange membrane is 5nm.
Width of flow path in the described diffusion dialysis film group device is 0.2mm.
The flow control of described press lye is 2mm/s, and the flow control of described demineralized water is 3mm/s.
In the described diffusion dialysis film group device, the clearance control between every adjacent two cation-exchange membranes is 0.4mm.
Naoh concentration in the described recovery alkali lye is controlled to be 40g/L, and hemicellulose concentration is controlled to be＜10g/L.
Embodiment 6
On the basis of embodiment 1-4, preferred:
Naoh concentration in the press lye of described process filtration preliminary treatment reduction large granular impurity concentration is controlled to be 200g/L, and hemicellulose concentration is controlled to be 150g/L, and large granular impurity content is controlled to be less than 1g/L.
Described cation-exchange membrane be the cloth of a kind of or two kinds of cospinning shapes in nylon, polypropylene, polyvinyl chloride, the polytetrafluoroethylene (PTFE) as basement membrane, be filmed the alkaline-resisting cation-exchange membrane that forms with rubbing method with perfluorinated sulfonic acid again.
The thickness of described basement membrane is 2mm.
The aperture of described cation-exchange membrane is 10nm.
Width of flow path in the described diffusion dialysis film group device is 1mm.
The flow control of described press lye is 20mm/s, and the flow control of described demineralized water is 25mm/s.
In the described diffusion dialysis film group device, the clearance control between every adjacent two cation-exchange membranes is 0.9mm.
Naoh concentration in the described recovery alkali lye is controlled to be 160g/L, and hemicellulose concentration is controlled to be＜10g/L.
Embodiment 7
On the basis of embodiment 1-4, preferred:
Naoh concentration in the press lye of described process filtration preliminary treatment reduction large granular impurity concentration is controlled to be 125g/L, and hemicellulose concentration is controlled to be 85g/L, and large granular impurity content is controlled to be less than 1g/L.
Described cation-exchange membrane be the cloth of a kind of or two kinds of cospinning shapes in nylon, polypropylene, polyvinyl chloride, the polytetrafluoroethylene (PTFE) as basement membrane, be filmed the alkaline-resisting cation-exchange membrane that forms with rubbing method with perfluorinated sulfonic acid again.
The thickness of described basement membrane is 1.025mm.
The aperture of described cation-exchange membrane is 7.5nm.
Width of flow path in the described diffusion dialysis film group device is 0.6mm.
The flow control of described press lye is 11mm/s, and the flow control of described demineralized water is 14mm/s.
In the described diffusion dialysis film group device, the clearance control between every adjacent two cation-exchange membranes is 0.65mm.
Naoh concentration in the described recovery alkali lye is controlled to be 100g/L, and hemicellulose concentration is controlled to be＜10g/L.
Embodiment 8
On the basis of embodiment 1-4, preferred:
Naoh concentration in the press lye of described process filtration preliminary treatment reduction large granular impurity concentration is controlled to be 75g/L, and hemicellulose concentration is controlled to be 110g/L, and large granular impurity content is controlled to be less than 1g/L.
Described cation-exchange membrane be the cloth of a kind of or two kinds of cospinning shapes in nylon, polypropylene, polyvinyl chloride, the polytetrafluoroethylene (PTFE) as basement membrane, be filmed the alkaline-resisting cation-exchange membrane that forms with rubbing method with perfluorinated sulfonic acid again.
The thickness of described basement membrane is 0.08mm.
The aperture of described cation-exchange membrane is 8.5nm.
Width of flow path in the described diffusion dialysis film group device is 0.75mm.
The flow control of described press lye is 5mm/s, and the flow control of described demineralized water is 21mm/s.
In the described diffusion dialysis film group device, the clearance control between every adjacent two cation-exchange membranes is 0.7mm.
Naoh concentration in the described recovery alkali lye is controlled to be 55g/L, and hemicellulose concentration is controlled to be＜10g/L.
Embodiment 9
The preprocess method of flame filter press filtration treatment and the combination of micropore filtering film filtration treatment:
The preprocess method of press lye in the viscose rayon production is reclaimed in a kind of diffusion dialysis, be 50-200g/L with naoh concentration, hemicellulose concentration is that the press lye of 20-150g/L passes through first the flame filter press filtration treatment, pass through again the micropore filtering film filtration treatment, reduce large granular impurity concentration, obtain carrying out the pretreatment fluid that diffusion dialysis is processed for cation-exchange membrane.
Naoh concentration in the pretreatment fluid that described flame filter press and the control of micropore filtering film filtration treatment obtain is 50-200g/L, and hemicellulose concentration is 20-150g/L, and large granular impurity concentration is less than 1g/L.
Above-mentioned large granular impurity comprises bulky grain dust impurity, bulky grain metal impurities etc.
Temperature with press lye before described process flame filter press filters is controlled to be 5-50 ℃.
The pressure of described flame filter press is controlled to be 0.05-0.5Mpa.
The aperture of described flame filter press filter cloth is 1100-1300g/m
2
The filter area of described flame filter press is controlled to be 1m with the ratio of the flow of press lye
2: 15-25m
3/ h.
Described micropore filtering film adopts the polypropylene micro-filtration membrane.
The aperture of described micropore filtering film is the 0.1-1 micron.
The hole of described micropore filtering film be shaped as circle.
The pressure of described micro porous filtration is controlled to be 0.05-0.2Mpa.
Micro porous filtration membrane filtration and ultrafiltration membrance filter are processed the preprocess method of combination:
The preprocess method of press lye in the viscose rayon production is reclaimed in diffusion dialysis, be 50-200g/L with naoh concentration, hemicellulose concentration is that the press lye of 20-150g/L passes through first the micropore filtering film filtration treatment, process through ultrafiltration membrance filter again, reduce large granular impurity concentration, obtain carrying out the pretreatment fluid that diffusion dialysis is processed for cation-exchange membrane.
Naoh concentration in the pretreatment fluid that described micropore filtering film and ultrafiltration membrance filter processing controls obtain is 50-200g/L, and hemicellulose concentration is 20-150g/L, and other large granular impurity concentration are less than 1g/L.
Above-mentioned large granular impurity comprises bulky grain dust impurity, bulky grain metal impurities etc.
Temperature with press lye before the described process micropore filtering film filtration treatment is controlled to be 5-50 ℃.
Described micropore filtering film adopts the polypropylene micro-filtration membrane.
The aperture of described micropore filtering film is the 0.1-1 micron.
The hole of described micropore filtering film be shaped as circle.
The pressure of described micro porous filtration is controlled to be 0.05-0.2Mpa.
Described milipore filter adopts Kynoar (PVDF).
The aperture of described milipore filter is 20-1000A °.
The hole of described milipore filter be shaped as circle.
The pressure of described ultrafiltration is controlled to be 0.1-0.5Mpa.
Embodiment 11
Flame filter press filtration treatment and ultrafiltration membrance filter are processed the preprocess method of combination:
The pretreating process of press lye in the viscose rayon production is reclaimed in a kind of diffusion dialysis, be 50-200g/L with naoh concentration, hemicellulose concentration is that the press lye of 20-150g/L passes through first the flame filter press filtration treatment, process through ultrafiltration membrance filter again, reduce large granular impurity concentration, obtain carrying out the pretreatment fluid that diffusion dialysis is processed for cation-exchange membrane.
Naoh concentration in the pretreatment fluid that described flame filter press and ultrafiltration membrance filter processing controls obtain is 50-200g/L, and hemicellulose concentration is 20-150g/L, and large granular impurity concentration is less than 1g/L.
Above-mentioned large granular impurity comprises bulky grain dust impurity, bulky grain metal impurities etc.
Temperature with press lye before described process flame filter press filters is controlled to be 5-50 ℃.
The pressure of described flame filter press is controlled to be 0.05-0.5Mpa.
The aperture of described flame filter press filter cloth is 1100-1300g/m
2
The filter area of described flame filter press is controlled to be 1m with the ratio of the flow of press lye
2: 15-25m
3/ h.
Described milipore filter adopts Kynoar (PVDF).
The aperture of described milipore filter is 20-1000A °.
The hole of described milipore filter be shaped as circle.
The pressure of described ultrafiltration is controlled to be 0.1-0.5Mpa.
Embodiment 12
Flame filter press filtration treatment, micropore filtering film filtration treatment and ultrafiltration membrance filter are processed the preprocess method of combination:
The pretreating process of press lye in the viscose rayon production is reclaimed in diffusion dialysis, it is characterized in that: be 50-200g/L with naoh concentration, hemicellulose concentration is that the press lye of 20-150g/L passes through first the flame filter press filtration treatment, then pass through the micropore filtering film filtration treatment, process through ultrafiltration membrance filter again, reduce large granular impurity concentration, obtain carrying out the pretreatment fluid that diffusion dialysis is processed for cation-exchange membrane.
Naoh concentration in the pretreatment fluid that described flame filter press, micropore filtering film and ultrafiltration membrance filter processing controls obtain is 50-200g/L, and hemicellulose concentration is 20-150g/L, and large granular impurity concentration is less than 1g/L.
Above-mentioned large granular impurity comprises bulky grain dust, bulky grain metal impurities etc.
Temperature with press lye before described process flame filter press filters is controlled to be 5-50 ℃.
The pressure of described flame filter press is controlled to be 0.05-0.5Mpa.
The aperture of described flame filter press filter cloth is 1100-1300g/m
2
The filter area of described flame filter press is controlled to be 1m with the ratio of the flow of press lye
2: 15-25m
3/ h.
Described micropore filtering film adopts the polypropylene micro-filtration membrane.
The aperture of described micropore filtering film is the 0.1-1 micron.
The hole of described micropore filtering film be shaped as circle.
The pressure of described micro porous filtration is controlled to be 0.05-0.2Mpa.
Described milipore filter adopts Kynoar (PVDF).
The aperture of described milipore filter is 20-1000A °.
The hole of described milipore filter be shaped as circle.
The pressure of described ultrafiltration is controlled to be 0.1-0.5Mpa.
Embodiment 13
The post processing after finishing is reclaimed in diffusion dialysis:
The post-processing approach of press lye in the viscose rayon production is reclaimed in a kind of diffusion dialysis, be 50-200g/L with naoh concentration, hemicellulose concentration is that the press lye of 20-150g/L reduces large granular impurity concentration through filtering preliminary treatment, process through the cation-exchange membrane diffusion dialysis, the recovery liquid of the low hemicellulose level that separation is obtained and the raffinate of high hemicellulose content carry out post processing again; Described post processing concentrate for the recovery liquid that will hang down hemicellulose level or dilute post processing, recovery alkali lye, and during the raffinate of high hemicellulose content carried out and post processing, the recovery hemicellulose.
Naoh concentration in the press lye of described process filtration preliminary treatment reduction large granular impurity concentration is controlled to be 50-200g/L, and hemicellulose concentration is controlled to be 20-150g/L, and the concentration of large granular impurity is controlled to be less than 1g/L.
Above-mentioned large granular impurity comprises bulky grain dust impurity, bulky grain metal impurities etc.
Naoh concentration in the recovery liquid of the low hemicellulose level that described cation-exchange membrane diffusion dialysis processing controls obtains is 40-160g/L, and hemicellulose concentration is＜10g/L.
The described concentrated post processing that low hemicellulose recovery liquid is carried out, the naoh concentration in the alkali lye that control obtains is 160-420g/L, hemicellulose concentration is＜10g/L.
The described dilution post processing that low hemicellulose recovery liquid is carried out, the naoh concentration in the alkali lye that control obtains is 0.5-40g/L, hemicellulose concentration is＜10g/L.
The described concentrated post processing that low hemicellulose recovery liquid is carried out is reverse osmosis concentration or distillation and concentration.
Above-mentioned reverse osmosis concentration adopts doughnut formula membrane module, and the external diameter of doughnut is 50-200 μ m, and internal diameter is 25-42 μ m.
The pressure of above-mentioned reverse osmosis concentration is controlled to be 100-1000psi.
The temperature of above-mentioned reverse osmosis concentration is controlled to be 0-45 ℃.
The pressure of above-mentioned distillation and concentration is controlled to be 0.08-0.2Mpa.
The heating and temperature control of above-mentioned distillation and concentration is 80-120 ℃.
The condensation temperature of above-mentioned distillation and concentration is controlled to be 0-25 ℃.
The described dilution post processing that low hemicellulose recovery liquid is carried out is diluted for add demineralized water in low hemicellulose recovery liquid.
Naoh concentration in the raffinate of the high hemicellulose content that described cation-exchange membrane diffusion dialysis processing controls obtains is 8-15g/L, and hemicellulose concentration is 20-50g/L.
Described raffinate to high hemicellulose content carry out in and post processing refer to adopt the raffinate of acid solution and high hemicellulose content to carry out mix and blend, make hemicellulose precipitation, supernatant enter biochemistry pool and process, after biochemical treatment is up to standard, discharge.
The concentration of above-mentioned acid solution is 0.1-2.5mol/L.
The addition of above-mentioned acid solution is that the volume ratio of the raffinate of described acid solution and high hemicellulose content is 1:0.5-25.
Above-mentioned acid solution is sulfuric acid solution, hydrochloric acid solution or salpeter solution.
Embodiment 14
The preparation method who is used for the cation-exchange membrane of diffusion dialysis:
The selection of A, basement membrane
Select with a kind of cloth in nylon, polypropylene and the polyvinyl chloride, or the cloth of any two cospinning shape is basement membrane;
The irradiation activation of B, basement membrane
The basement membrane of steps A is activated placing under the electron beam irradiation under the nitrogen atmosphere, and the electron linear accelerator of 10Mev is adopted in described activation, and irradiation dose is controlled to be 2-20kgy.
C, functional group grafting are processed
Basement membrane through irradiation activation among the step B is carried out the functional group grafting;
D, sulfonation are processed
With among the step C through the basement membrane of grafting take silver sulfate as catalyst, carry out sulfonation take the concentrated sulfuric acid as sulfonating agent, again through cooling, separate, take out obtain of the present invention be applicable to diffusion dialysis reclaim viscose rayon produce in the cation-exchange membrane of press lye.
Among the step C, describedly refer to will be among the step B be soaked in the mixed solution of styrene, divinylbenzene and benzoyl peroxide through the basement membrane of irradiation activation and carry out the functional group grafting carrying out the functional group grafting through the basement membrane of irradiation activation among the step B.
The amount ratio of above-mentioned styrene, divinylbenzene and benzoyl peroxide is 70-90:10-20:0.1-1.
Among the step D, in the described sulfonation process, sulfonation temperature is 40-60 ℃.
Among the step D, in the described sulfonation process, the sulfonation time is 5-7 hour.
Embodiment 15
The film group device that is used for diffusion dialysis:
A kind of film group device that is applicable to press lye in the production of diffusion dialysis recovery viscose rayon, comprise the first clamping plate 1, the second clamping plate 2, dividing plate 10 and cation-exchange membrane 9, described dividing plate 10 is a plurality of with cation-exchange membrane 9, and the interval is alternately overlapping, and compress mutually, described dividing plate 10 is squeezed alkali lye runner interlayer 3 with cation-exchange membrane 9 and absorption liquid runner interlayer 4 clamps, and described press lye runner interlayer 3 and absorption liquid runner interlayer 4 are clamped by the first clamping plate 1 and the second clamping plate 2 again.
Described press lye runner interlayer 3 bottoms are provided with press lye import 5, and top is provided with raffinate outlet 7.
Described absorption liquid runner interlayer 4 bottoms are provided with absorption liquid import 6, and top is provided with reclaims liquid outlet 8.
Be provided with the polytetrafluoroethylene sealing gasket sheet between the described dividing plate 10, thickness is 0.1-0.15mm.
In the described cation-exchange membrane 9, the distance between every adjacent two cation-exchange membranes 9 is 0.4-0.9mm.
Described cation-exchange membrane 9 is the perfluorinated sulfonic acid cation-exchange membrane.
The aperture of described cation-exchange membrane 9 is 5-10nm.
Width of flow path in described press lye runner interlayer 3 and the absorption liquid runner interlayer 4 is 0.2-1mm.
Claims (9)
1. the method for press lye during a diffusion dialysis recovery viscose rayon is produced, it is characterized in that: be 50-200g/L with naoh concentration, hemicellulose concentration is that the press lye of 20-150g/L reduces large granular impurity concentration through filtering preliminary treatment, then enter in the diffusion dialysis film group device with demineralized water as absorption liquid, mode with cross-flow flows, carry out diffusion dialysis by cation-exchange membrane, be recycled alkali lye; Gauge pressure in the described diffusion dialysis process is 0.03-0.08MPa.
2. the method for press lye in the viscose rayon production is reclaimed in a kind of diffusion dialysis according to claim 1, it is characterized in that: the naoh concentration in the press lye of described process filtration preliminary treatment reduction large granular impurity concentration is controlled to be 50-200g/L, hemicellulose concentration is controlled to be 20-150g/L, and large granular impurity content is controlled to be less than 1g/L.
3. the method for press lye in the viscose rayon production is reclaimed in a kind of diffusion dialysis according to claim 1, it is characterized in that: described cation-exchange membrane be the cloth of a kind of or two kinds of cospinning shapes in nylon, polypropylene, polyvinyl chloride, the polytetrafluoroethylene (PTFE) as basement membrane, be filmed the alkaline-resisting cation-exchange membrane that forms with rubbing method with perfluorinated sulfonic acid again.
4. the method for press lye in the viscose rayon production is reclaimed in a kind of diffusion dialysis according to claim 3, and it is characterized in that: the thickness of described basement membrane is 0.05-2mm.
According to claim 1 or 3 described a kind of diffusion dialysis reclaim viscose rayons produce in the method for press lye, it is characterized in that: the aperture of described cation-exchange membrane is 5-10nm.
6. the method for press lye in the viscose rayon production is reclaimed in a kind of diffusion dialysis according to claim 1, and it is characterized in that: the width of flow path in the described diffusion dialysis film group device is 0.2-1mm.
7. the method for press lye in the viscose rayon production is reclaimed in a kind of diffusion dialysis according to claim 1, and it is characterized in that: the flow control of described press lye is 2-20mm/s, and the flow control of described demineralized water is 3-25mm/s.
8. the method for press lye in the viscose rayon production is reclaimed in a kind of diffusion dialysis according to claim 1, it is characterized in that: in the described diffusion dialysis film group device, the clearance control between every adjacent two cation-exchange membranes is 0.4-0.9mm.
9. the method for press lye in the viscose rayon production is reclaimed in a kind of diffusion dialysis according to claim 1, and it is characterized in that: the naoh concentration in the described recovery alkali lye is controlled to be 40-160g/L, and hemicellulose concentration is controlled to be＜10g/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310311775.6A CN103349908B (en) | 2013-07-24 | 2013-07-24 | Method for squeezing alkali liquid in diffusion dialysis recycling viscose manufacture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310311775.6A CN103349908B (en) | 2013-07-24 | 2013-07-24 | Method for squeezing alkali liquid in diffusion dialysis recycling viscose manufacture |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103349908A true CN103349908A (en) | 2013-10-16 |
| CN103349908B CN103349908B (en) | 2015-07-01 |
Family
ID=49306375
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310311775.6A Active CN103349908B (en) | 2013-07-24 | 2013-07-24 | Method for squeezing alkali liquid in diffusion dialysis recycling viscose manufacture |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103349908B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104402676A (en) * | 2014-11-07 | 2015-03-11 | 宜宾雅泰生物科技有限公司 | Membrane filtration technology for preparing xylitol from viscose fiber squeezed alkali solution |
| CN110776139A (en) * | 2019-10-31 | 2020-02-11 | 南京工大膜应用技术研究所有限公司 | Device and method for recovering waste acid generated in steel pickling through diffusion dialysis |
| EP3650411A1 (en) | 2018-11-12 | 2020-05-13 | Lenzing Aktiengesellschaft | Device and method for recovering alkaline solution and device and method for producing regenerated cellulose moulded bodies with such a method |
| EP3722501A1 (en) | 2019-04-12 | 2020-10-14 | Lenzing Aktiengesellschaft | Method for the recovery of alkaline solution and method for producing regenerated cellulose moulded parts comprising such a method |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0871376A (en) * | 1994-09-09 | 1996-03-19 | Nippon Riironaale Kk | Method and apparatus for recovering organic sulfonic acid from solution containing organic sulfonic acid and/ or organic sulfonate by diffusion dialysis or electrodialysis |
| CN1450001A (en) * | 2003-05-15 | 2003-10-22 | 凯能高科技工程（上海）有限公司 | Method for recovering alkali and hemicellulose from chemical fibre waste liquid |
| CN201305463Y (en) * | 2008-12-03 | 2009-09-09 | 上海轻工业研究所有限公司 | Waste acid or waste alkali recovery device for automatic diffusion dialysis industry |
| CN102643935A (en) * | 2012-04-11 | 2012-08-22 | 宜宾丝丽雅股份有限公司 | Method for preparing xylose by using squeezed waste alkali liquor in viscose fiber production process |
| CN102908916A (en) * | 2012-11-09 | 2013-02-06 | 杭州水处理技术研究开发中心有限公司 | Preparation method of hollow fiber dispersion and dialysis alkali recycling membrane |
| CN102941017A (en) * | 2012-11-26 | 2013-02-27 | 宜宾海丝特纤维有限责任公司 | Process for secondary treating of waste alkali liquid during production of viscose fibers |
| CN102976450A (en) * | 2012-12-30 | 2013-03-20 | 山东天维膜技术有限公司 | Process for recovering alkali from squeezed waste liquid in viscose fiber production |
-
2013
- 2013-07-24 CN CN201310311775.6A patent/CN103349908B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0871376A (en) * | 1994-09-09 | 1996-03-19 | Nippon Riironaale Kk | Method and apparatus for recovering organic sulfonic acid from solution containing organic sulfonic acid and/ or organic sulfonate by diffusion dialysis or electrodialysis |
| CN1450001A (en) * | 2003-05-15 | 2003-10-22 | 凯能高科技工程（上海）有限公司 | Method for recovering alkali and hemicellulose from chemical fibre waste liquid |
| CN201305463Y (en) * | 2008-12-03 | 2009-09-09 | 上海轻工业研究所有限公司 | Waste acid or waste alkali recovery device for automatic diffusion dialysis industry |
| CN102643935A (en) * | 2012-04-11 | 2012-08-22 | 宜宾丝丽雅股份有限公司 | Method for preparing xylose by using squeezed waste alkali liquor in viscose fiber production process |
| CN102908916A (en) * | 2012-11-09 | 2013-02-06 | 杭州水处理技术研究开发中心有限公司 | Preparation method of hollow fiber dispersion and dialysis alkali recycling membrane |
| CN102941017A (en) * | 2012-11-26 | 2013-02-27 | 宜宾海丝特纤维有限责任公司 | Process for secondary treating of waste alkali liquid during production of viscose fibers |
| CN102976450A (en) * | 2012-12-30 | 2013-03-20 | 山东天维膜技术有限公司 | Process for recovering alkali from squeezed waste liquid in viscose fiber production |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104402676A (en) * | 2014-11-07 | 2015-03-11 | 宜宾雅泰生物科技有限公司 | Membrane filtration technology for preparing xylitol from viscose fiber squeezed alkali solution |
| EP3650411A1 (en) | 2018-11-12 | 2020-05-13 | Lenzing Aktiengesellschaft | Device and method for recovering alkaline solution and device and method for producing regenerated cellulose moulded bodies with such a method |
| WO2020099125A1 (en) | 2018-11-12 | 2020-05-22 | Lenzing Aktiengesellschaft | Device and method for recovering alkaline solution, and device and method for producing regenerated cellulose molded bodies using such a method |
| CN112955408A (en) * | 2018-11-12 | 2021-06-11 | 连津格股份公司 | Device and method for recovering alkaline solution and device and method for producing regenerated cellulose moulded bodies having such a method |
| EP3722501A1 (en) | 2019-04-12 | 2020-10-14 | Lenzing Aktiengesellschaft | Method for the recovery of alkaline solution and method for producing regenerated cellulose moulded parts comprising such a method |
| WO2020207766A1 (en) | 2019-04-12 | 2020-10-15 | Lenzing Aktiengesellschaft | Process for recovering alkaline solution, and method for producing regenerated cellulose moulded bodies, which method comprises such a process |
| CN110776139A (en) * | 2019-10-31 | 2020-02-11 | 南京工大膜应用技术研究所有限公司 | Device and method for recovering waste acid generated in steel pickling through diffusion dialysis |
| CN110776139B (en) * | 2019-10-31 | 2021-10-26 | 南京工大膜应用技术研究所有限公司 | Device and method for recovering waste acid generated in steel pickling through diffusion dialysis |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103349908B (en) | 2015-07-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107381886A (en) | A kind of method of reverse osmosis concentrated water near-zero release | |
| CN103349909B (en) | Post-processing method for squeezed alkali liquid in diffusion dialysis recycling viscose manufacture | |
| CN103388198B (en) | A kind of bipolar membrane electrodialysis method is produced the method for soda acid from viscose rayon sodium sulphate waste liquid | |
| CN106277517B (en) | Regeneration and reuse treatment method for coal chemical industry strong salt wastewater and implementation system thereof | |
| CN103349908B (en) | Method for squeezing alkali liquid in diffusion dialysis recycling viscose manufacture | |
| CN105254083A (en) | Process and system for treating high salinity wastewater in coal chemical industry | |
| CN103341321A (en) | Viscose sodium sulfate waste liquor acid and alkali recycling technology by virtue of bipolar membrane electrodialysis method | |
| CN212669467U (en) | Catalytic cracking wet flue gas desulfurization waste water cyclic utilization system | |
| CN103351041B (en) | Electrodialysis alkali recovery process in a kind of viscose fiber production | |
| CN102908916B (en) | Preparation method of hollow fiber dispersion and dialysis alkali recycling membrane | |
| CN103349910B (en) | Pre-treatment method for pressed alkali liquor in manufacturing of recycling viscose by diffusion dialysis | |
| CN103388275B (en) | The pretreating process of Black Liquor by Electrodialysis alkali collection during a kind of pulp manufactures | |
| CN103397408B (en) | The preprocess method of press lye in viscose production is reclaimed in a kind of diffusion dialysis | |
| CN103362011B (en) | The preprocess method of black digestion liquid in pulp manufacture is reclaimed in diffusion dialysis | |
| CN103352388B (en) | The pretreating process of black digestion liquid in pulp manufacture is reclaimed in a kind of diffusion dialysis | |
| CN103352277B (en) | The pretreating process of press lye in viscose production is reclaimed in a kind of diffusion dialysis | |
| CN103397406B (en) | The pretreating process of press lye in viscose production is reclaimed in diffusion dialysis | |
| CN103352389B (en) | The preprocess method of black digestion liquid during pulp manufactures is reclaimed in a kind of diffusion dialysis | |
| CN103074796A (en) | Alkali recovery process for paper-making black liquid | |
| CN106673144B (en) | A kind of electric nanofiltration device with low salt rejection rate and high rejection to organics rate | |
| CN103397405B (en) | Pretreatment technique for recovering pressed liquor electrodialysis alkali in viscose fiber production | |
| CN103351069B (en) | The pretreatment technology of black digestion liquid in pulp manufacture is reclaimed in diffusion dialysis | |
| CN206368057U (en) | A kind of electric osmose chemical reaction water treatment facilities | |
| CN106892519A (en) | Mixed bed regenerates high-salinity wastewater zero-emission processing unit | |
| CN111825266A (en) | Catalytic cracking wet desulphurization waste water recycling system and method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |