CN103397406A - Pretreatment technique for recovering pressing alkali liquor in viscose fiber production by diffusion dialysis - Google Patents
Pretreatment technique for recovering pressing alkali liquor in viscose fiber production by diffusion dialysis Download PDFInfo
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Abstract
The invention relates to a pretreatment technique for recovering pressing alkali liquor in viscose fiber production by diffusion dialysis, belonging to the technical field of viscose fiber production. The technique comprises the following steps: filtering pressing alkali liquor, of which the sodium hydroxide concentration is 50-200 g/L and the hemicellulose concentration is 20-150 g/L, with a frame filter, filtering with a microfiltration membrane, and filtering with an ultrafiltration membrane to lower the large granule impurity concentration, thereby obtaining a pretreatment solution for diffusion dialysis treatment of a cation-exchange membrane. Aiming at the diffusion dialysis technique for recovering viscose fiber pressing alkali liquor, the invention adopts the specific pretreatment method to treat the pressing alkali liquor, and the pressing alkali liquor enters the diffusion dialysis process, thereby enhancing the alkali and hemicellulose recovery rate in the pressing alkali liquor, reducing the damage of the alkali liquor on the diffusion dialysis membrane system, avoiding blocking the diffusion dialysis membrane, prolonging the service life of the membrane, and ensuring the smooth performance of the diffusion dialysis and subsequent procedure.
Description
Technical field
The present invention relates to the technique that in a kind of Chemical Manufacture, material is processed, more particularly, the present invention relates to diffusion dialysis and reclaim the pretreating process of press lye in viscose production, belong to the viscose 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 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 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 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 lacks 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 solution is moved to low concentration one side by film by high concentration one side, and this process is take concentration difference as power.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 starts systematically to study the diffusion of solution, studied again subsequently the characteristic of different solutes by pellicle (film that parchment or celloidin etc. are made), find intransitable phenomenon of the molecule of some solutes or colloidal particle that ion can be larger by the pore of pellicle, Graham Sodd method of investing claims that this phenomenon is dialysis.The equipment of around this principle making is called dialyzer, is usually used in the purification of the macromolecular compounds such as the concentrated and sour ﹑ protein of core of colloidal solution.The 1950's, the diffusion dialysis device of amberplex as barrier film appearred using.
The domestic diffusion dialysis film of just having developed as far back as 1964.But due to the restriction of film preparation technique, the structure of the similar homogeneous phase ionic membrane of resulting film, be all this type of film 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, and homo-ion repulsion and the electroneutral of application Donnan (Donnan) balance are kept 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, for example the mixed solution of hydrochloric acid and aluminium chloride and water are placed in respectively the both sides of anion-exchange membrane, due to the concentration of the acid of solution side and salt 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, has the characteristic that attracts electronegative ion hydration and repel positively charged ion hydration in solution, therefore 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 due to 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 solution will be separated into water inlet side like this, and passing through of this Hydrogen ion is the key of diffusion dialysis.Amberplex used need to possess some suitable performances, and such as the stability in acid solution, high hydrogen ion percent of pass, 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 to control, and is designed to full-automatic mode, is provided with grid spacer between 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 chemical fibre waste fluid and the method for hemicellulose ", and this patent provides a kind of alkali in chemical fibre waste fluid and method of hemicellulose of reclaiming.Method of the present invention comprises the steps: the pressed liquor that contains alkali and hemicellulose is entered membrane separation device through pre-filtering and essence 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 liquid, in concentrate, final alkali content is the 5-30 grams per liter, 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 filter liquor in 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 the return period of investment short, economic benefit height and the good characteristics of environmental 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 viscose production is had certain recovering effect, still exists the rate of recovery not high, and energy consumption is large, can't online recycling and recycle.
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 is mainly to be used in acid recovery, and be used for diffusion dialysis film that alkali reclaims seldom, even the recovery for alkali in alkali lye, also to reclaim for other industry alkali lye, the akaline liquid that the constituent of its recycle object, index parameter and viscose 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 viscose 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 production ", this patent discloses the alkali recovery process of squeezing waste liquid in a kind of viscose production, allow squeezing waste liquid and the distilled water cation-exchange membrane diffusion dialysis device inner chamber of flowing through simultaneously, control the flow velocity of squeezing waste liquid and water, so that the squeezing waste liquid that flows out, NaOH content is 15-25g/L 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 production cost.
The alkali that adopts the diffusion dialysis technology to be applied to the squeezing waste liquid in viscose production in above-mentioned patent reclaims, but the rate of recovery is not high, sodium hydrate content in liquid after treatment is only 15-25g/L, 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 process.
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 production ", this patent relates to the secondary treatment method of discarded alkali lye in a kind of viscose 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 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 prior art, still can produce secondary waste alkali lye through the discarded alkali lye of once recycling, if directly discharging, can cause the problem of considerable damage to environment, provide a kind of processing method of secondary waste alkali lye, by diffusion dialysis, can reclaim to greatest extent the NaOH in discarded alkali lye, reduce environmental pollution, improved ecological benefits, reduced simultaneously the cost of environmental protection treatment.
In above-mentioned patent, the same alkali that adopts the diffusion dialysis technology to be applied to the squeezing waste liquid in viscose production reclaims, although mentioned in technical scheme first waste liquid carried out conventional preliminary treatment, but still can't reclaim and to process for the diffusion dialysis film that the press lye in viscose carries out specific cation-exchange membrane, can directly affect carrying out smoothly of the recovery of diffusion dialysis film and subsequent treatment and recycling, and the scope of the press lye that can process is narrower, processes yield low.
Summary of the invention
the present invention is intended to solve existing problem and the defect that is applied to reclaim the diffusion dialysis technology existence of the press lye in viscose production, provide a kind of diffusion dialysis to reclaim the pretreating process of press lye in viscose production, only for the cation-exchange membrane diffusion dialysis technique that is applied to reclaim the viscose press lye, adopt specific preprocess method to process the press lye of specific indexes, obtain entering again cation-exchange membrane diffusion dialysis process after suitable pretreatment fluid, the rate of recovery and the yield of alkali and hemicellulose in the raising press lye, reduce the damage of alkali lye to 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 pretreating process of press lye in viscose 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 is first 1100-1300g/m through the aperture of filter cloth
2The flame filter press filtration treatment, then be the micropore filtering film filtration treatment of 0.1-1 micron through aperture, the ultrafiltration membrance filter that is 20-1000A ° through aperture is again processed, and reduces large granular impurity concentration, obtains carrying out for cation-exchange membrane the pretreatment fluid that diffusion dialysis is processed.
It is 50-200g/L that flame filter press of the present invention, micropore filtering film and ultrafiltration membrance filter are processed the naoh concentration of controlling in the pretreatment fluid that obtains, 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.
Of the present invention through before the flame filter press filtration, the temperature of press lye being controlled to be 5-50 ℃.
The pressure of flame filter press of the present invention is controlled to be 0.05-0.5Mpa.
The filter area of flame filter press of the present invention is controlled to be 1m with the ratio of the flow of press lye
2: 15-25m
3/ h.
Micropore filtering film of the present invention adopts the polypropylene microfiltration membranes.
The hole of micropore filtering film of the present invention be shaped as circle.
The pressure of micro porous filtration of the present invention is controlled to be 0.05-0.2Mpa.
Milipore filter of the present invention adopts Kynoar (PVDF).
The hole of milipore filter of the present invention be shaped as circle.
The pressure of ultrafiltration of the present invention is controlled to be 0.1-0.5Mpa.
The useful technique effect that the present invention brings:
1, the invention solves existing problem and the defect that is applied to reclaim the diffusion dialysis technology existence of the press lye in viscose production, for the diffusion dialysis technique that is applied to reclaim the viscose press lye, adopt specific preprocess method to process press lye, obtain the pretreatment fluid of specific indexes, enter again cation-exchange membrane diffusion dialysis process, can be applicable to alkali concn and the wider press lye of hemicellulose concentration range, 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, and guaranteed carrying out smoothly of diffusion dialysis and subsequent handling.The aperture of flame filter press filter cloth is 1100-1300g/cm
2The aperture of micropore filtering film is the 0.1-1 micron, the aperture of milipore filter is 20-1000A °, the selection in above-mentioned aperture is fit to process press lye of the present invention, effectively guaranteed the service life of filter plant, in addition can the large molecule of effectively catching and other impurity, and can so that press lye with speed preferably by the worry machine do not make again equipment or filter material because pressure is excessive along bad, extension device service life, the selection in three kinds of apertures acts synergistically mutually, effectively reduces the large granular impurity concentration in press lye.
2, to process the naoh concentration of controlling in the pretreatment fluid that obtains be 50-200g/L for flame filter press of the present invention, micropore filtering film and ultrafiltration membrance filter, and hemicellulose concentration is 20-150g/L, and other bulky grain concentration are 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 the infringement of other materials to 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, make in addition the recovery liquid that obtains after diffusion dialysis recovery efficient, high yield to separate NaOH and hemicellulose.
3, of the present invention through before the flame filter press filtration, the temperature of press lye being controlled to be 5-50 ℃.Before preliminary treatment, press lye is carried out temperature adjustment, and select this temperature range can effectively increase the speed of molecular motion, make filtration carry out smoothly, also can reduce the damage of temperature to filter material in cation-exchange membrane diffusion dialysis equipment, the service life of extension device.
4, the pressure of flame filter press of the present invention is controlled to be 0.05-0.5Mpa; The aperture of flame filter press filter cloth is 1100-1300g/cm
2The filter area of flame filter press and the discharge relation of press lye are 1m
2: 15-25m
3/ h.The preferred version that three technological parameters of above-mentioned plate-frame filtering are selected has formed a parameter system, can make spent lye not make again equipment or filter material with speed preferably by the worry machine damages because pressure is excessive, effectively hold back oarse-grained impurity, small part larger molecular organics and other impurity, and the flux that can take full advantage of the strainability of flame filter press and guarantee press lye.
5, micropore filtering film of the present invention adopts the polypropylene microfiltration membranes; The aperture of micropore filtering film is the 0.1-1 micron; The hole of micropore filtering film be shaped as circle; The pressure of micro porous filtration is controlled to be 0.05-0.2Mpa; The control of the selection of above-mentioned micropore filtering film, index and technological parameter makes the micro porous filtration equipment can be more alkaline-resisting, be fit to process press lye of the present invention, effectively guaranteed the service life of filter plant, in addition can the large molecule of effectively catching and other impurity, and can so that press lye with speed preferably by the worry machine do not make again equipment or filter material because pressure is excessive along bad, extension device service life.
6, milipore filter of the present invention adopts Kynoar (PVDF); The aperture of 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.Above-mentioned technological parameter selection, material selection etc. can make ultrafiltration membrance filter equipment more alkaline-resisting, be fit to process press lye of the present invention, extend the service life of considering core, equipment, in addition can the large molecule of effectively catching and other impurity, and can so that press lye with speed preferably by the worry machine do not make again equipment or filter material because pressure is excessive along bad, extension device service life.
7, above-mentioned plate-frame filtering, micro-filtration and ultrafiltration acting in conjunction, form pretreating process of the present invention, the technological parameter of above-mentioned two kinds of filter types 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 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, and guaranteed carrying out smoothly of diffusion dialysis and subsequent handling.
Description of drawings
Fig. 1 is the structural representation of 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 pretreating process of press lye in viscose production is reclaimed in diffusion dialysis, with naoh concentration, is 50g/L, and hemicellulose concentration is that the press lye of 20g/L is first 1100g/m through the filter cloth aperture
2The flame filter press filtration treatment, then be the micropore filtering film filtration treatment of 0.1 micron through aperture, the ultrafiltration membrance filter that is 20A ° through aperture is again processed, and reduces large granular impurity concentration, obtains carrying out for cation-exchange membrane the pretreatment fluid that diffusion dialysis is processed.
Embodiment 2
The pretreating process of press lye in viscose production is reclaimed in diffusion dialysis, it is characterized in that: be 200g/L with naoh concentration, hemicellulose concentration is that the press lye of 150g/L is first 1300g/m through the aperture of filter cloth
2The flame filter press filtration treatment, then be the micropore filtering film filtration treatment of 1 micron through aperture, the ultrafiltration membrance filter that is 1000A ° through aperture is again processed, and reduces large granular impurity concentration, obtains carrying out for cation-exchange membrane the pretreatment fluid that diffusion dialysis is processed.
Embodiment 3
The pretreating process of press lye in viscose production is reclaimed in diffusion dialysis, it is characterized in that: be 125g/L with naoh concentration, hemicellulose concentration is that the press lye of 85g/L is first 1200g/m through the aperture of filter cloth
2The flame filter press filtration treatment, then be the micropore filtering film filtration treatment of 0.55 micron through aperture, the ultrafiltration membrance filter that is 510A ° through aperture is again processed, and reduces large granular impurity concentration, obtains carrying out for cation-exchange membrane the pretreatment fluid that diffusion dialysis is processed.
The pretreating process of press lye in viscose production is reclaimed in diffusion dialysis, it is characterized in that: be 180g/L with naoh concentration, hemicellulose concentration is that the press lye of 36g/L is first 1150g/m through the aperture of filter cloth
2The flame filter press filtration treatment, then be the micropore filtering film filtration treatment of 0.83 micron through aperture, the ultrafiltration membrance filter that is 820A ° through aperture is again processed, and reduces large granular impurity concentration, obtains carrying out for cation-exchange membrane the pretreatment fluid that diffusion dialysis is processed.
On the basis of embodiment 1-4, preferred:
The index of the pretreatment fluid that the process preliminary treatment obtains:
It is 50g/L that described flame filter press, micropore filtering film and ultrafiltration membrance filter are processed the naoh concentration of controlling in the pretreatment fluid that obtains, and hemicellulose concentration is 20g/L, and large granular impurity concentration is less than 1g/L.
Temperature adjustment before preliminary treatment is processed:
Described through before the flame filter press filtration, the temperature of press lye being controlled to be 5 ℃.
Plate-frame filtering:
The pressure of described flame filter press is controlled to be 0.05Mpa.
The filter area of described flame filter press is controlled to be 1m with the ratio of the flow of press lye
2: 15m
3/ h.
Micro porous filtration:
Described micropore filtering film adopts the polypropylene microfiltration membranes.
The hole of described micropore filtering film be shaped as circle.
The pressure of described micro porous filtration is controlled to be 0.05Mpa.
Ultrafiltration:
Described milipore filter adopts Kynoar (PVDF).
The hole of described milipore filter be shaped as circle.
The pressure of described ultrafiltration is controlled to be 0.1Mpa.
Embodiment 6
On the basis of embodiment 1-4, preferred:
The index of the pretreatment fluid that the process preliminary treatment obtains:
It is 200g/L that described flame filter press, micropore filtering film and ultrafiltration membrance filter are processed the naoh concentration of controlling in the pretreatment fluid that obtains, and hemicellulose concentration is 150g/L, and large granular impurity concentration is less than 1g/L.
Temperature adjustment before preliminary treatment is processed:
Described through before the flame filter press filtration, the temperature of press lye being controlled to be 50 ℃.
Plate-frame filtering:
The pressure of described flame filter press is controlled to be 0.5Mpa.
The filter area of described flame filter press is controlled to be 1m with the ratio of the flow of press lye
2: 25m
3/ h.
Micro porous filtration:
Described micropore filtering film adopts the polypropylene microfiltration membranes.
The hole of described micropore filtering film be shaped as circle.
The pressure of described micro porous filtration is controlled to be 0.2Mpa.
Ultrafiltration:
Described milipore filter adopts Kynoar (PVDF).
The hole of described milipore filter be shaped as circle.
The pressure of described ultrafiltration is controlled to be 0.5Mpa.
Embodiment 7
On the basis of embodiment 1-4, preferred:
The index of the pretreatment fluid that the process preliminary treatment obtains:
It is 125g/L that described flame filter press, micropore filtering film and ultrafiltration membrance filter are processed the naoh concentration of controlling in the pretreatment fluid that obtains, and hemicellulose concentration is 85g/L, and large granular impurity concentration is less than 1g/L.
Temperature adjustment before preliminary treatment is processed:
Described through before the flame filter press filtration, the temperature of press lye being controlled to be 28 ℃.
Plate-frame filtering:
The pressure of described flame filter press is controlled to be 0.275Mpa.
The filter area of described flame filter press is controlled to be 1m with the ratio of the flow of press lye
2: 20m
3/ h.
Micro porous filtration:
Described micropore filtering film adopts the polypropylene microfiltration membranes.
The hole of described micropore filtering film be shaped as circle.
The pressure of described micro porous filtration is controlled to be 0.125Mpa.
Ultrafiltration:
Described milipore filter adopts Kynoar (PVDF).
The hole of described milipore filter be shaped as circle.
The pressure of described ultrafiltration is controlled to be 0.3Mpa.
Embodiment 8
On the basis of embodiment 1-4, preferred:
The index of the pretreatment fluid that the process preliminary treatment obtains:
It is 180g/L that described flame filter press, micropore filtering film and ultrafiltration membrance filter are processed the naoh concentration of controlling in the pretreatment fluid that obtains, and hemicellulose concentration is 36g/L, and large granular impurity concentration is less than 1g/L.
Temperature adjustment before preliminary treatment is processed:
Described through before the flame filter press filtration, the temperature of press lye being controlled to be 39 ℃.
Plate-frame filtering:
The pressure of described flame filter press is controlled to be 0.4Mpa.
The filter area of described flame filter press is controlled to be 1m with the ratio of the flow of press lye
2: 21m
3/ h.
Micro porous filtration:
Described micropore filtering film adopts the polypropylene microfiltration membranes.
The hole of described micropore filtering film be shaped as circle.
The pressure of described micro porous filtration is controlled to be 0.07Mpa.
Ultrafiltration:
Described milipore filter adopts Kynoar (PVDF).
The hole of described milipore filter be shaped as circle.
The pressure of described ultrafiltration is controlled to be 0.4Mpa.
Embodiment 9
Carry out diffusion dialysis by cation-exchange membrane:
The method of press lye in viscose 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, then enter in the diffusion dialysis film group device with the 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 described diffusion dialysis process is 0.03-0.08MPa.
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 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.
Described cation-exchange membrane be cloth take a kind of or two kinds of cospinning shapes in nylon, polypropylene, polyvinyl chloride, polytetrafluoroethylene (PTFE) as basement membrane, then be filmed the alkaline-resisting cation-exchange membrane that forms with rubbing method with perfluorinated sulfonic acid.
The thickness of above-mentioned basement membrane is 0.05-2mm.
The aperture of described cation-exchange membrane is 5-10nm.
Width of flow path in described diffusion dialysis film group device is 0.2-1mm.
The flow control of described press lye is 2-20mm/s, and the flow control of described demineralized water is 3-25mm/s.
In described diffusion dialysis film group device, the clearance control between every adjacent two cation-exchange membranes is 0.4-0.9mm.
Naoh concentration in described recovery alkali lye is controlled to be 40-160g/L, and hemicellulose concentration is controlled to be＜10g/L.
The post processing after completing is reclaimed in diffusion dialysis:
The post-processing approach of press lye in viscose 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 is 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.
The naoh concentration that described cation-exchange membrane diffusion dialysis is processed in the recovery liquid of controlling the low hemicellulose level that 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 of controlling in the alkali lye that 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 of controlling in the alkali lye that 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 for reclaiming in liquid and add demineralized water to dilute to low hemicellulose.
The naoh concentration that described cation-exchange membrane diffusion dialysis is processed in the raffinate of controlling the high hemicellulose content that 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, discharge after biochemical treatment is up to standard.
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 11
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 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 being placed under electron beam irradiation and is activating under 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 in step B is carried out the functional group grafting;
D, sulfonation are processed
The basement membrane of process grafting in step C, take silver sulfate as catalyst, is carried out sulfonation take the concentrated sulfuric acid as sulfonating agent, then, through cooling, separation, take out and obtain the cation-exchange membrane that is applicable to press lye in the production of diffusion dialysis recovery viscose of the present invention.
In step C, describedly with carrying out the functional group grafting through the basement membrane of irradiation activation in step B, refer to will be in step B through the basement membrane of irradiation activation, be soaked in the mixed solution of styrene, divinylbenzene and benzoyl peroxide and carry out the functional group grafting.
The amount ratio of above-mentioned styrene, divinylbenzene and benzoyl peroxide is 70-90:10-20:0.1-1.
In step D, in described sulfonation process, sulfonation temperature is 40-60 ℃.
In step D, in described sulfonation process, the sulfonation time is 5-7 hour.
Embodiment 12
As shown in Figure 1, 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, 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 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 described dividing plate 10, thickness is 0.1-0.15mm.
In 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 absorption liquid runner interlayer 4 is 0.2-1mm.
Claims (11)
1. the pretreating process of press lye in viscose 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 is first 1100-1300g/m through the aperture of filter cloth
2The flame filter press filtration treatment, then be the micropore filtering film filtration treatment of 0.1-1 micron through aperture, the ultrafiltration membrance filter that is 20-1000A ° through aperture is again processed, and reduces large granular impurity concentration, obtains carrying out for cation-exchange membrane the pretreatment fluid that diffusion dialysis is processed.
2. the pretreating process of press lye in viscose production is reclaimed in diffusion dialysis according to claim 1, it is characterized in that: it is 50-200g/L that described flame filter press, micropore filtering film and ultrafiltration membrance filter are processed the naoh concentration of controlling in the pretreatment fluid that obtains, hemicellulose concentration is 20-150g/L, and large granular impurity concentration is less than 1g/L.
3. the pretreating process of press lye in viscose production is reclaimed in diffusion dialysis according to claim 1, it is characterized in that: described through before the flame filter press filtration, the temperature of press lye being controlled to be 5-50 ℃.
4. the pretreating process of press lye in viscose production is reclaimed in diffusion dialysis according to claim 1, and it is characterized in that: the pressure of described flame filter press is controlled to be 0.05-0.5Mpa.
5. the pretreating process of press lye in viscose production is reclaimed according to claim 1 or 4 described diffusion dialysis, and it is characterized in that: 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.
6. the pretreating process of press lye in viscose production is reclaimed in diffusion dialysis according to claim 1, and it is characterized in that: described micropore filtering film adopts the polypropylene microfiltration membranes.
According to claim 1 or 6 described diffusion dialysis reclaim viscoses produce in the pretreating process of press lye, it is characterized in that: the hole of described micropore filtering film be shaped as circle.
8. the pretreating process of press lye in viscose production is reclaimed according to claim 1 or 6 described diffusion dialysis, and it is characterized in that: the pressure of described micro porous filtration is controlled to be 0.05-0.2Mpa.
9. the pretreating process of press lye in viscose production is reclaimed in diffusion dialysis according to claim 1, and it is characterized in that: described milipore filter adopts Kynoar.
According to claim 1 or 9 described diffusion dialysis reclaim viscoses produce in the pretreating process of press lye, it is characterized in that: the hole of described milipore filter be shaped as circle.
11. the pretreating process of press lye in viscose production is reclaimed according to claim 1 or 9 described diffusion dialysis, it is characterized in that: the pressure of described ultrafiltration is controlled to be 0.1-0.5Mpa.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101070166A (en) * | 2007-02-14 | 2007-11-14 | 湖州东洋水处理设备有限公司 | Method and apparatus for purifying and recovering silking dirt alkali adopting superfiltering film |
| CN101851030A (en) * | 2009-03-30 | 2010-10-06 | 广州中科建禹水处理技术有限公司 | Technical method for purifying and reutilizing jean silkete alkali waste liquid by membrane method |
| 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 |
| CN103074796A (en) * | 2012-12-30 | 2013-05-01 | 山东天维膜技术有限公司 | Alkali recovery process for paper-making black liquid |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101070166A (en) * | 2007-02-14 | 2007-11-14 | 湖州东洋水处理设备有限公司 | Method and apparatus for purifying and recovering silking dirt alkali adopting superfiltering film |
| CN101851030A (en) * | 2009-03-30 | 2010-10-06 | 广州中科建禹水处理技术有限公司 | Technical method for purifying and reutilizing jean silkete alkali waste liquid by membrane method |
| 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 |
| CN103074796A (en) * | 2012-12-30 | 2013-05-01 | 山东天维膜技术有限公司 | Alkali recovery process for paper-making black liquid |
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