CN109293112A - A kind of treatment method of viscose fiber acid waste water resource utilization - Google Patents

A kind of treatment method of viscose fiber acid waste water resource utilization Download PDF

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Publication number
CN109293112A
CN109293112A CN201811209613.0A CN201811209613A CN109293112A CN 109293112 A CN109293112 A CN 109293112A CN 201811209613 A CN201811209613 A CN 201811209613A CN 109293112 A CN109293112 A CN 109293112A
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water
reverse osmosis
acid
viscose fiber
tank
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CN109293112B (en
Inventor
何凡
谭瀚茗
张珂静
靳琰
郑贤江
王静
李长福
周恩年
罗书磊
黄金锋
游延贺
陶思远
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Korla Zhongtai Textile Technology Co ltd
Xinjiang Zhongtai Technology Engineering Co.,Ltd.
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Xinjiang Sino-Thai Innovation Technology Research Institute Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/02—Treatment of water, waste water, or sewage by heating
    • C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/20—Treatment of water, waste water, or sewage by degassing, i.e. liberation of dissolved gases
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/24—Treatment of water, waste water, or sewage by flotation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration

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  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Water Treatment By Sorption (AREA)

Abstract

本发明公开了一种粘胶纤维酸性废水资源化利用的处理方法，其包括：(1)将粘胶纤维酸性废水集中收集至原水池，依次进行吹脱和/或搅拌、过滤，脱除粘胶纤维酸性废水中的胶体物质和悬浮物，降低废水浊度以及H2S、CS2等的含量，得到淡黄色预处理液；(2)所述淡黄色预处理液经冷却、超滤、反渗透，得到无色反渗透产水和橙黄色反渗透浓水，再向橙黄色反渗透浓水内添加活性炭进行吸附、澄清，脱除其中的COD等，得到无色酸性浓水；(3)所述无色酸性浓水经过蒸发结晶，得到可回用的酸液和硫酸钠。本发明可以实现对粘胶纤维行业酸性废水的近零排放和其中酸、盐等的资源化利用，同时实现工业水回用，不仅绿色环保，而且可以有效节约企业生产成本。The invention discloses a treatment method for resource utilization of viscose fiber acidic wastewater, which comprises: (1) collecting the viscose fiber acidic wastewater into a raw water tank, and performing stripping and/or stirring and filtering in sequence to remove the viscosity The colloidal substances and suspended solids in the acid waste water of the glue fiber can reduce the turbidity of the waste water and the content of H 2 S, CS 2 , etc., to obtain a light yellow pretreatment liquid; (2) the light yellow pretreatment liquid is cooled, ultrafiltered, Reverse osmosis to obtain colorless reverse osmosis product water and orange-yellow reverse osmosis concentrated water, and then add activated carbon to the orange-yellow reverse osmosis concentrated water for adsorption, clarification, and removal of COD, etc., to obtain colorless acidic concentrated water; (3 ) The colorless acidic concentrated water is evaporated and crystallized to obtain reusable acid solution and sodium sulfate. The invention can realize near-zero discharge of acid waste water in viscose fiber industry and resource utilization of acid, salt, etc., and at the same time realize industrial water reuse, which is not only green and environmentally friendly, but also can effectively save the production cost of enterprises.

Description

A kind of processing method of viscose rayon acid waste water resource utilization
Technical field
The present invention relates to a kind of wastewater treatment method, in particular to a kind of place of viscose rayon acid waste water resource utilization Reason method.
Background technique
Currently, the acid waste water of viscose rayon plant emissions is mainly from refining workshop and acid station etc. is spun, acid waste water contains Sulfuric acid, sodium sulphate, zinc sulfate, aluminum sulfate, carbon disulfide, hydrogen sulfide, dissolved organic matter, suspended matter etc..Compare traditional place Reason mode is: acid waste water is emitted into sewage treatment plant, is mixed with alkaline waste water, and mixed waste water pH value is adjusted to Alkalescent generates zinc hydroxide solid precipitating to remove the zinc sulfate in waste water, and the waste water containing a large amount of salt is using materialization With biochemical two-stage treatment, wastewater supernatant fluid outlet that treated.Traditional treatment method converts the useful constituent in acid waste water At the unwanted salt of viscose glue enterprise, while the utilities such as sulfuric acid and zinc sulfate are wasted, the wave of great lot of water resources is also resulted in Take, leads to the additional consumption of corporate resources and energy.
Summary of the invention
The main purpose of the present invention is to provide a kind of processing methods of viscose rayon acid waste water resource utilization, thus Overcome deficiency in the prior art.
For realization aforementioned invention purpose, the technical solution adopted by the present invention includes:
The embodiment of the invention provides a kind of processing methods of viscose rayon acid waste water resource utilization comprising as follows Step:
Pre-treatment step, comprising: by viscose rayon acid waste water centralized collection to former pond, successively carry out stripping and/or Stirring, filtration treatment more than once reduce waste water to remove at least part of colloidal substance and the suspended matter in waste water Turbidity and content of acid gas obtain faint yellow pretreatment fluid；
Film concentration step, comprising: cooling, ultrafiltration, reverse osmosis, active carbon suction are successively carried out to the faint yellow pretreatment fluid Attached, clarifying treatment obtains colourless reverse osmosis produced water and colourless acid concentrated water；
Evaporative crystallization steps, comprising: crystallization treatment is evaporated to the colourless acid concentrated water, obtain can reuse acid solution And sodium sulphate.In some more specific embodiments, the pre-treatment step is specifically included: by viscose rayon spent acidic Water pump is delivered to former pond centralized collection, and overflow enters stripping pond, sufficiently after aeration, overflow to stirring pool, through being sufficiently stirred Afterwards, then it is delivered to the filtration treatment of more than one acidproof filter progress more than once, the turbidity of waste water is made to reach ultrafiltration system The requirement united to flow condition, obtains faint yellow pretreatment fluid；Wherein, the acidproof filter include quartz filter, The combination of any one or more in one or more levels millipore filter, tow filter device, and it is without being limited thereto.
In some more specific embodiments, the film concentration step is specifically included: will be yellowish by cooler Color pretreatment fluid is cooled to 25~50 DEG C, transports to ultrafiltration membrane system later and carries out ultrafiltration, obtained ultrafiltrate is anti-through counter-infiltration system Infiltration, obtains colourless reverse osmosis produced water and orange-yellow reverse osmosis concentrated water, later by orange-yellow reverse osmosis concentrated water through activated carbon adsorption COD and clarifying treatment obtain colourless acid concentrated water.
In some more specific embodiments, the processing method of the viscose rayon acid waste water resource utilization is also Can include: activated carbon adsorption spent acidic is used in any one of pre-treatment step, film concentration step and evaporative crystallization steps COD in water.In some more specific embodiments, the evaporative crystallization steps include: using thermal crystallization or cold Crystallisation is evaporated crystallization treatment to colourless acid concentrated water, to extract sodium sulphate therein；The temperature of the thermal crystallization At 32.8 DEG C or more, sodium sulphate is precipitated in the form of no crystal water for degree control, the temperature of the cold junction crystallization control 32.8 DEG C with Under, sodium sulphate is precipitated in the form of saltcake.
Compared with the prior art, the present invention may be implemented near-zero release to viscose rayon industry acid waste water and wherein acid, The resource utilization of salt etc., while realizing industry water reuse, it is not only environmentally protective, but also can be produced into effectively save enterprise This, improves Business Economic Benefit.
Specific embodiment
As previously mentioned, inventor is studied for a long period of time and largely practiced in view of the deficiencies in the prior art, it is able to propose this The technical solution of invention.Technical solution of the present invention will be clearly and completely described below, it is clear that described implementation Example is a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, ordinary skill Personnel's every other embodiment obtained without making creative work, shall fall within the protection scope of the present invention.
A kind of processing method of viscose rayon acid waste water resource utilization provided in an embodiment of the present invention includes following step It is rapid:
Pre-treatment step, comprising: by viscose rayon acid waste water centralized collection to former pond, successively carry out stripping and/or Stirring, filtration treatment more than once reduce waste water to remove at least part of colloidal substance and the suspended matter in waste water Turbidity and content of acid gas obtain faint yellow pretreatment fluid；
Film concentration step, comprising: cooling, ultrafiltration, reverse osmosis, active carbon suction are successively carried out to the faint yellow pretreatment fluid Attached, clarifying treatment obtains colourless reverse osmosis produced water and colourless acid concentrated water；
Evaporative crystallization steps, comprising: crystallization treatment is evaporated to the colourless acid concentrated water, obtain can reuse acid solution And sodium sulphate.Further, the viscose rayon acid waste water includes in the substances such as sulfuric acid, sodium sulphate, zinc sulfate, aluminum sulfate The combination of any one or more, and the water temperature of the viscose rayon acid waste water is 70~98 DEG C, COD content >= 1000mg/L。
For example, the viscose rayon acid waste water, which can be, rushes mao water and acid station waste discharge between spinning practice Deng, but not limited to this.
Further, viscose rayon acid waste water of the invention has the following characteristics that
(1) after the raw water temperature of acid water is quickly cooled to 25 DEG C by 90 DEG C, the turbidity of raw water will not be because of the change of temperature Change and vary widely, it may be assumed that will not be reduced because of temperature, and cause to be partly dissolved substance precipitation.
(2) raw water of acid water is standing 1~8 hour, and turbidity extends at any time increases to the left side 45NTU by 10NTU or so The right side, but there is no sediment；24 hours or so observation bottoms are stood still without precipitating, raw water becomes dim muddy from limpid bright state Turbid state.
(3) raw water of acid water such as stands 48 hours or so, examining bottom has very thin precipitating after standing longer time Object, sufficiently being shaken raw water becomes dim cloudy state, is heated to after raw water temperature still as dim cloudy state, then through a long time Standing will appear lumpy precipitate.
(4) raw water of acid water promotes the precipitation of pole fine suspension through stripping, stirring, and liquid turbidity is sequentially increased；This Outside, the acid waste water after stirring, which stands 1~8 hour turbidity, does not have significant change, and in economically viable settling time (≤ 8 hours) liquid do not have a clarifying effect, increase clarification to 24~48 hours, clarification bottom of pond portion just visible very finely divided sediment, therefore After agitation, clarification in (≤8 hours) does not have the precipitation of pole fine suspension and precipitating suspended matter within the economically viable time Positive effect.In some more specific embodiments, the pre-treatment step is specifically included: by viscose rayon spent acidic Water pump is delivered to former pond centralized collection, and overflow enters stripping pond, sufficiently after aeration, overflow to stirring pool, through being sufficiently stirred Afterwards, then be delivered to more than one acidproof filter and carry out filtration treatment more than once, make the turbidity of waste water be down to≤ 15NTU obtains faint yellow pretreatment fluid.
Wherein, the acidproof filter includes quartz filter, one or more levels millipore filter, tow filter device In the combination of any one or more, but not limited to this.
It is possible to further which viscose rayon acid waste water pump is delivered to former pond centralized collection, overflow enters stripping Pond, sufficiently after aeration, overflow to stirring pool；Stirring after a certain period of time, is delivered to that quartz filter, one or more levels is micro- with pump Hole filter, it is also possible to which turbidity is down to≤15NTU, obtains faint yellow pretreatment fluid by the acidproof filter such as tow filter device.
Further, the former pond, stripping pond and stirring pool are acidproof pond.
In some more specific embodiments, the pre-treatment step further include: be arranged in the stripping pond Multiple partitions to reduce the back-mixing of water flow, and guarantee raw water stripping time >=0.5h, and, it is arranged in the stripping Chi Ding Gas gathering mask, the collection for sour gas.
Further, the sour gas mainly contains H2S、CS2, aqueous vapor etc..
In some more specific embodiments, the pre-treatment step further include: be arranged in the stirring pool Multiple partitions, reducing the back-mixing of water flow, and, multiple blenders are set above the stirring pool, and guarantee that raw water is stirred Mixing the time is 0.5~6h.
Wherein, by the way that many places partition is arranged in the stripping pond, the back-mixing of water flow is reduced to the greatest extent, when guaranteeing raw water stripping Between >=0.5h, the H being dissolved in water2S、CS2Equal substances are taken out of, and stripping Chi Ding is provided with gas gathering mask, the receipts for sour gas Collection.
And it wherein reduces the back-mixing of water flow to the greatest extent by the way that many places partition is arranged in the stirring pool, is set above pond Several blenders are set, guarantee that raw water mixing time is 0.5~6h or so.
Further, the setting in the stripping pond, most of hydrogen sulfide, two sulphur that can be dissolved in acid waste water Change carbon removing, this greatly reduces the content of sulfide in step (1) pretreatment fluid, effectively reduce go to downstream it is reverse osmosis and The sulphur of crystallizing evaporator greatly extends the service life of reverse osmosis membrane and increases the heat transfer efficiency of crystallizing evaporator；Blast pond In air there are two effects: first is that the oxygen in air can react with hydrogen sulfide, generation elemental sulfur；Second is that air can incite somebody to action The hydrogen sulfide and carbon disulfide of dissolution are taken out of from water；Gas-water ratio is different during stripping, and required stripping time also can be different.
Further, one or more levels described millipore filter filtering accuracy is 1~10 μm, and filtering accuracy can be according to turbidity It is required that adjustment, filtrate turbidity≤15NTU after millipore filter, can requirement according to different ultrafiltration systems to flow condition, adjustment Suitable turbidity range.
In some more specific embodiments, the film concentration step is specifically included: will be yellowish by cooler Color pretreatment fluid is cooled to 25~50 DEG C, obtains the pretreatment fluid of proper temperature, transports to ultrafiltration membrane system later and carries out ultrafiltration, institute It is reverse osmosis through counter-infiltration system to obtain ultrafiltrate, obtains colourless reverse osmosis produced water and orange-yellow reverse osmosis concentrated water, it later will be orange-yellow Reverse osmosis concentrated water obtains colourless acid concentrated water through activated carbon adsorption COD and clarifying treatment.
Further, the position of the cooler and series are not restricted by, and pretreatment fluid reaches preference temperature.Example Such as, cooler can be added before former pond, the colourless acid concentrated water obtained with film upgrading unit exchanges heat, and realizes raw water heat benefit With, can after the pre-treatment again plus level-one cooler if pretreatment fluid temperature is still high.
More particularly, in the present invention, acid waste water is cooled to 25~50 DEG C by cooler by the pretreatment fluid, is obtained To the pretreatment fluid of proper temperature, the preference temperature is the temperature for being suitable for film process.Viscose rayon acid waste water temperature is higher, It should not be directly entered film separation system, though acid waste water carries out Temperature fall, temperature by former pond, stripping pond, stirring pool Still relatively high, thus cooler is set before ultrafiltration system and is cooled down.
Further, the mode of the ultrafiltration includes cross-flow or dead-end system, wherein the ultrafiltration membrane elements used include pipe Formula, board-like, dish-style, rolling or capillary type membrane component, and it is not limited to this.
Further, the ultrafiltration system includes intake by the UF that pipeline is connected to tank, UF intake pump, UF security personnel's filtering Device, UF film unit, UF circulating pump and UF produce water pot；Faint yellow pretreatment fluid after cooling successively pass through UF water inlet tank, UF into Enter UF film unit after water pump and UF cartridge filter and isolates bigger molecule suspended matter after ultrafiltration membrance filter therein, from And obtain the ultrafiltrate of reverse osmosis requirement.
Further, the counter-infiltration system includes the cartridge filter being connected to by pipeline, reverse osmosis high-pressure pump, RO film Unit, RO produce water pot and RO concentrated water tank, and the ultrafiltrate successively enters RO after cartridge filter and reverse osmosis high-pressure pump Film unit (including the reverse osmosis membrane stack of one or more snippets RO) obtains colourless reverse osmosis produced water (reverse osmosis produced water) into RO and produces water Tank, orange-yellow reverse osmosis concentrated water (RO concentrated water) enter RO concentrated water tank.
Further, the reverse osmosis operating pressure is controlled in 5~16MPaG, and concentrated water terminal salinity exists 110000mg/L~300000mg/L.Meet economy, the operating pressure of feasibility counter-infiltration system can further improve, obtain More high salt concentration, high terminal salinity can reduce evaporated crystallization device load, reduce cost of investment of equipment and device behaviour Make expense.
In some more specific embodiments, the film concentration step further include: to described orange-yellow reverse osmosis Active carbon is added in concentrated water to be adsorbed, adsorption time >=0.25h, to remove COD therein.In adsorption process, may be used also Blender is added to stir, the activated carbon adsorption time can increase or decrease according to charcoal adsorption effect, this process removes COD.
In some more specific embodiments, the film concentration step further include: complete with activated carbon adsorption In the orange-yellow reverse osmosis concentrated water after the operation of COD, regeneration treatment is carried out to the active carbon after using, realizes that active carbon is multiple It uses.
In the present invention, activated carbon adsorption removing COD has following effect and feature:
(1) removing COD can prevent the fouling of evaporator downstream crystallizer and reduce the ebullioscopic amplitude of solution.If downstream is steamed Crystallizer fouling is sent out, can be cleaned with appropriate alkaline liquor.
(2) removing COD prevents color to be enriched with, and guarantees viscose rayon product quality.
Further, present invention selection add active carbon to be considered for adsorption effect and economy at reverse osmosis concentrated water, Active carbon can be added in other positions by being not precluded.For example, in some embodiments, the viscose rayon acid waste water resource Change the processing method utilized further include: use in any one of pre-treatment step, film concentration step and evaporative crystallization steps COD in activated carbon adsorption acid waste water.
Further, for acidproof pond, the clarification bottom of pond portion is provided with scrapes the clarifying basin used in the clarifying treatment Mud machine, mud scraper can be with intermittently operated, and for being collected bottom of pond sediment in time to bottom of pond portion center, and the clarifying basin is It is operated batch-wise or continuously.Wherein, intermittently operated can guarantee that acid waste water is stood completely, either between continuous operation still It has a rest operation, clear necessary time is determined according to clarifying effect and economy.
In some more specific embodiments, the evaporative crystallization steps include: using thermal crystallization or cold junction Crystallization is evaporated crystallization treatment to colourless acid concentrated water, to extract sodium sulphate therein；The temperature of the thermal crystallization At 32.8 DEG C or more, sodium sulphate is precipitated in the form of no crystal water for control, the control of the temperature of the cold junction crystallization at 32.8 DEG C hereinafter, Sodium sulphate is precipitated in the form of saltcake.
Further, the mode of evaporative crystallization processing includes MVR evaporation, multiple-effect evaporation or multi-stage vacuum flash distillation etc., But not limited to this.
The present invention realizes the near-zero release and resource utilization to viscose rayon industry acid waste water, recycles acid waste water Industry water reuse is realized while middle acid, salt, is realized and is brought good economic benefits while green production for manufacturing enterprise, and is right Viscose rayon industry acid waste water " waste resource recovery ", which handles work, has practice and directive significance.More have below in conjunction with some The embodiment of body more at large illustrates technical solution of the present invention work.
Acid waste water handled by following examples is the fiber that the entrainment acid bath discharged between practice is spun by viscose rayon factory Flushing water, exhaust position 70~98 DEG C of water temperature, mainly contain sulfuric acid, sodium sulphate, zinc sulfate, aluminum sulfate, two after fibre cutting Nitric sulfid, hydrogen sulfide, dissolved organic matter, suspended matter etc., COD content >=1000mg/L.
The wastewater treatment method used in following examples includes: to collect viscose rayon acid waste water to former pond, is overflow It is flow to stripping pond (stripping 2h), it is micro- to be then delivered to quartz filter, level-one by pump for overflow later to stirring pool (stirring 2h) Suspended matter is filtered and is removed by hole filter (10 μm of filtering accuracy) and second level millipore filter (1 μm of filtering accuracy), is reduced acid The suspension content and turbidity of water；Using ultrafiltration membrane system, tiny suspended matter is further removed, ultrafiltration membrane produces water and enters RO Counter-infiltration system, by the fresh water of one, two, three section of reverse osmosis output enter RO produce water pot, by three sections of reverse osmosis outputs concentrated water into Enter RO concentrated water tank；RO concentrated water through activated carbon adsorption tank (stirring 0.5h), adds the 6/10000~15/10000 of concentrate quality again The active powdered carbon of (be approximately equivalent to raw water quality 2/10000~5/10000) removes COD, enters evaporation after sufficient standing clarification Crystallization apparatus, obtaining by evaporated crystallization device can reuse acid solution and sodium sulphate.The principle of pretreatment unit is: in acid waste water The substances such as the fiber and hemicellulose of dissolution, insoluble fine solid particles, fierce collision, a part in stripping and whipping process Substance is capable of forming big micelle and is precipitated from solubilised state, and it is anti-that certain oxidation occurs in the presence of oxygen for a part of substance Biggish solid suspension should be formed, while hydrogen sulfide, the carbon disulfide stripping in waste water being come out, the micelle of precipitation and generation Solid suspension be blocked by quartz filter and millipore filter, reduce and turbidity of wastewater and wherein vulcanize The content of hydrogen, carbon disulfide.The principle of ultrafiltration is: under certain pressure, acid waste water isolates larger point after ultrafiltration membrance filter Sub- suspended matter, acid waste water meets reverse osmosis requirement after ultrafiltration.Reverse osmosis principle is: reverse osmosis membrane is utilized, in acidity Water influent side applies certain pressure, enters hydrone through reverse osmosis membrane and produces water side, and it is few to remove water the substance other than molecule Amount penetrates reverse osmosis membrane.Activated carbon adsorption principle: active carbon porous structure Adsorption of Dissolved organic matter is utilized.Evaporative crystallization is former Reason: the sodium sulphate supersaturation in solution is precipitated in evaporation water, and obtaining can reuse acid solution and sodium sulphate.
Embodiment 1: after 70~98 DEG C of aforementioned acid Waste Water Centralized to former pond, overflow is into stripping pond, spent acidic The hydrogen sulfide and carbon disulfide dissolved in water can be taken out of by the air blasted in water, stripping 2h, and overflow later to stirring pool passes through Stirring promotes suspended matter to be precipitated, and stirs 2h, and turbidity rises to 50NTU from 10NTU；Then quartz filter and one are delivered to by pump Grade or multistage millipore filter, remove solid suspension and small micelle, the turbidity of acid waste water from 50NTU be down to 10NTU hereinafter, The hydrogen sulfide and carbon disulfide total amount of dissolution are down to 0.3mg/L or less by 4~12mg/L.
Embodiment 2: after 70~98 DEG C of aforementioned acid Waste Water Centralized to former pond, overflow is into stripping pond, spent acidic The hydrogen sulfide and carbon disulfide dissolved in water can be taken out of by the air blasted in water, stripping 2h, and overflow later to stirring pool passes through Stirring promotes suspended matter to be precipitated, and stirs 1h, and turbidity rises to 50NTU from 10NTU；Then quartz filter and one are delivered to by pump Grade or multistage millipore filter, remove solid suspension and small micelle, the turbidity of acid waste water from 50NTU be down to 10NTU hereinafter, The hydrogen sulfide and carbon disulfide total amount of dissolution are down to 0.3mg/L or less by 4~12mg/L.
Embodiment 3: after 70~98 DEG C of aforementioned acid Waste Water Centralized to former pond, overflow is into stripping pond, spent acidic The hydrogen sulfide and carbon disulfide dissolved in water can be taken out of by the air blasted in water, stripping 2h, and overflow later to stirring pool passes through Stirring promotes suspended matter to be precipitated, and stirs 2.5h, and turbidity rises to 50NTU from 10NTU；Then by pump be delivered to quartz filter and One or more levels millipore filter, removes solid suspension and small micelle, the turbidity of acid waste water from 50NTU be down to 10NTU with Under, the hydrogen sulfide and carbon disulfide total amount of dissolution are down to 0.3mg/L or less by 4~12mg/L.
Embodiment 4: pre-processing, after ultrafiltration acid waste water above-mentioned, and the 200L ultrafiltration obtained is produced water warp Tri- sections of 6MPaG, 8MPaG, 10MPaG reverse osmosis to carry out concentration experiment, and total salt quantity is dense through three sections by 60000mg/L~85000mg/L It is reduced to 205000mg/L~240000mg/L；This each section of producing water ratio of three sections of concentrations is more economical rationally, is conducive to save reverse osmosis Saturating equipment investment, and final salt concentration concentration is high, reduces evaporated crystallization device load, reduces cost of investment of equipment and device Operating cost.
Embodiment 5: acid waste water above-mentioned is pre-processed, ultrafiltration, it is reverse osmosis after, then active powdered carbon added in institute It obtains in reverse osmosis concentrated liquid, stirs 30min, the removal amount to COD is 600mg/g~1000mg/g, and adding quality is concentrate 6/10000~15/10000 (be approximately equivalent to raw water quality 2/10000~5/10000) of quality, divisible coloured COD and portion Divide colourless COD.
Comparative example 1: 70~98 DEG C of aforementioned acid water is collected to former pond, without any processing, turbidity is 10NTU, the hydrogen sulfide and carbon disulfide total amount of dissolution are 4~12mg/L.
Comparative example 2: directly standing 6h after 70~98 DEG C of aforementioned acid water is collected, acid without stripping and stirring The turbidity of waste water is 40~50NTU, 4~12mg/L of hydrogen sulfide and carbon disulfide total amount of dissolution.
Comparative example 3: stripping 1h after 70~98 DEG C of aforementioned acid water is collected, directly standing 4h, it is acid without stirring The turbidity of waste water is 40~50NTU or so, and the hydrogen sulfide and carbon disulfide total amount of dissolution are not more than 0.3~1.5mg/L.
Comparative example 4: stirring 1.5h after 70~98 DEG C of acid water is collected, directly standing 4h, without stripping, spent acidic 40~50NTU of water, 2~4.5mg/L of hydrogen sulfide and carbon disulfide total amount of dissolution.
Comparative example 5: refering to previous embodiment, acid waste water above-mentioned is pre-processed, after ultrafiltration, obtained 200L is surpassed Filter produce water through mono- section of 5MPaG it is reverse osmosis carry out concentration experiment, total salt quantity is concentrated by 60000mg/L~85000mg/L 110000mg/L~135000mg/L；This section processing concentrated water terminal salinity is lower, and subsequent evaporation crystallization apparatus load is big, if A standby cost of investment and device operating cost are big.
Comparative example 6: refering to previous embodiment, acid waste water above-mentioned is pre-processed, after ultrafiltration, obtained 200L is surpassed Filter produce water through mono- section of 6MPaG it is reverse osmosis carry out concentration experiment, total salt quantity is concentrated by 60000mg/L~85000mg/L 140000mg/L~170000mg/L；This section processing concentrated water terminal salinity is lower, and subsequent evaporation crystallization apparatus load is big, if A standby cost of investment and device operating cost are big.
Comparative example 7: refering to previous embodiment, acid waste water above-mentioned is pre-processed, after ultrafiltration, obtained 200L is surpassed Filter produce water through mono- section of 7MPaG it is reverse osmosis carry out concentration experiment, total salt quantity is concentrated by 60000mg/L~85000mg/L 170000mg/L~190000mg/L；This section processing concentrated water terminal salinity is slightly lower, and subsequent evaporation crystallization apparatus load is larger, Cost of investment of equipment and device operating cost are larger, and reverse osmosis equipment investment is larger.
Comparative example 8: refering to previous embodiment, acid waste water above-mentioned is pre-processed, after ultrafiltration, obtained 200L is surpassed Filter produce water through mono- section of 8MPaG it is reverse osmosis carry out concentration experiment, total salt quantity is concentrated by 60000mg/L~85000mg/L 185000mg/L~205000mg/L；This section processing concentrated water terminal salinity is slightly lower, and subsequent evaporation crystallization apparatus load is larger, Cost of investment of equipment and device operating cost are larger, and reverse osmosis equipment investment is larger.
Comparative example 9: refering to previous embodiment, acid waste water above-mentioned is pre-processed, after ultrafiltration, obtained 200L is surpassed Filter produce water through mono- section of 9MPaG it is reverse osmosis carry out concentration experiment, total salt quantity is concentrated by 60000mg/L~85000mg/L 195000mg/L~215000mg/L；This section processing concentrated water terminal salinity is slightly lower, and subsequent evaporation crystallization apparatus load is larger, Cost of investment of equipment and device operating cost are larger, and reverse osmosis equipment investment is larger.
Comparative example 10: refering to previous embodiment, pre-processing, after ultrafiltration acid waste water above-mentioned, by obtained 200L Ultrafiltration produce water through mono- section of 10MPaG it is reverse osmosis carry out concentration experiment, total salt quantity is concentrated by 60000mg/L~85000mg/L 205000mg/L~240000mg/L；This section processing concentrated water terminal salinity is high, can reduce subsequent evaporation crystallization apparatus load, Cost of investment of equipment and device operating cost are reduced, but reverse osmosis equipment investment is larger.
Comparative example 11: refering to previous embodiment, pre-processing, after ultrafiltration acid waste water above-mentioned, by identical work Property powdered carbon add and produced in water in ultrafiltration, stir 30min, be 200mg/g~300mg/g to the removal amount of COD.
It should be noted that each technical characteristic of embodiment described above can be combined arbitrarily, to make description letter Clean, combination not all possible to each technical characteristic in above-described embodiment is all described, as long as however, these technologies are special Contradiction is not present in the combination of sign, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.

Claims (10)

1.一种粘胶纤维酸性废水资源化利用的处理方法，其特征在于包括如下步骤：1. a treatment method for the utilization of viscose acid waste water resource, it is characterized in that comprising the steps: 预处理步骤，包括：将粘胶纤维酸性废水集中收集至原水池，依次进行吹脱和/或搅拌、一次以上的过滤处理，从而脱除废水中的至少部分的胶体物质和悬浮物，降低废水的浊度以及酸性气体含量，得到淡黄色预处理液；The pretreatment step includes: collecting viscose fiber acidic wastewater in a raw water tank, and performing stripping and/or stirring, and one or more filtration treatments in sequence, thereby removing at least part of colloidal substances and suspended solids in the wastewater, reducing wastewater The turbidity and acid gas content were obtained to obtain a pale yellow pretreatment solution; 膜浓缩步骤，包括：对所述淡黄色预处理液依次进行冷却、超滤、反渗透、活性炭吸附、澄清处理，得到无色反渗透产水和无色酸性浓水；The membrane concentration step includes: sequentially performing cooling, ultrafiltration, reverse osmosis, activated carbon adsorption, and clarification on the pale yellow pretreatment liquid to obtain colorless reverse osmosis product water and colorless acidic concentrated water; 蒸发结晶步骤，包括：对所述无色酸性浓水进行蒸发结晶处理，获得可回用的酸液和硫酸钠。The evaporative crystallization step includes: performing evaporative crystallization treatment on the colorless acidic concentrated water to obtain reusable acid solution and sodium sulfate. 2.根据权利要求1所述粘胶纤维酸性废水资源化利用的处理方法，其特征在于：所述粘胶纤维酸性废水包含硫酸、硫酸钠、硫酸锌、硫酸铝，并且所述粘胶纤维酸性废水的水温为70～98℃，COD含量≥1000mg/L。2. The treatment method for resource utilization of viscose fiber acidic wastewater according to claim 1, characterized in that: the viscose fiber acidic wastewater comprises sulfuric acid, sodium sulfate, zinc sulfate, aluminum sulfate, and the viscose fiber acidic wastewater comprises sulfuric acid, sodium sulfate, zinc sulfate, and aluminum sulfate. The water temperature of the wastewater is 70～98℃, and the COD content is ≥1000mg/L. 3.根据权利要求1所述粘胶纤维酸性废水资源化利用的处理方法，其特征在于，所述的预处理步骤具体包括：将粘胶纤维酸性废水用泵输送至原水池集中收集，溢流进入吹脱池，充分曝气后，溢流至搅拌池，经充分搅拌后，再输送至一个以上的耐酸过滤器进行一次以上的过滤处理，使废水的浊度达到超滤系统对进水条件的要求，得到淡黄色预处理液；其中，所述的耐酸过滤器包括石英砂过滤器、一级或多级微孔过滤器、丝束过滤器中的任意一种或多种的组合。3. The treatment method for resource utilization of viscose fiber acidic wastewater according to claim 1, characterized in that, the pretreatment step specifically comprises: pumping the viscose fiber acidic wastewater to a raw pool for centralized collection, overflowing After entering the stripping tank, after full aeration, it overflows to the stirring tank, and after full stirring, it is transported to more than one acid-resistant filter for more than one filtration treatment, so that the turbidity of the wastewater can reach the conditions of the ultrafiltration system for the influent water. According to the requirements of the invention, a light yellow pretreatment solution is obtained; wherein, the acid-resistant filter includes any one or a combination of a quartz sand filter, a one-stage or multi-stage microporous filter, and a tow filter. 4.根据权利要求3所述粘胶纤维酸性废水资源化利用的处理方法，其特征在于：所述原水池、吹脱池和搅拌池均为耐酸水池；和/或，所述酸性气体主要含有H2S、CS2及水气；和/或，所述的预处理步骤还包括：在所述吹脱池内设置多个隔板，用以减少水流的返混，并保证原水吹脱时间≥0.5h，以及，在所述吹脱池顶设置集气罩，用于酸性气体的收集；和/或，所述的预处理步骤还包括：在所述搅拌池内设置多个隔板，用以减少水流的返混，以及，在所述搅拌池上方设置多个搅拌器，并保证原水搅拌时间为0.5～6h。4. The method for treating viscose fiber acid waste water resource utilization according to claim 3, characterized in that: the raw water tank, the stripping tank and the stirring tank are all acid-resistant water tanks; and/or, the acid gas mainly contains H 2 S, CS 2 and water vapor; and/or, the pretreatment step further includes: disposing a plurality of baffles in the stripping tank to reduce back-mixing of the water flow and ensure that the raw water stripping time ≥ 0.5h, and, a gas collecting hood is set on the top of the stripping tank for the collection of acid gas; and/or, the pretreatment step also includes: setting a plurality of baffles in the stirring tank for the purpose of The back mixing of the water flow is reduced, and a plurality of stirrers are arranged above the stirring tank, and the stirring time of the raw water is guaranteed to be 0.5-6h. 5.根据权利要求1所述的处理方法，其特征在于，所述的膜浓缩步骤具体包括：通过冷却器将淡黄色预处理液冷却至25～50℃，之后输至超滤膜系统进行超滤，所获超滤液经反渗透系统反渗透，得到无色反渗透产水和橙黄色反渗透浓水，之后将橙黄色反渗透浓水经活性炭吸附COD及澄清处理，得到无色酸性浓水。5 . The processing method according to claim 1 , wherein the membrane concentration step specifically comprises: cooling the pale yellow pretreatment liquid to 25-50° C. by a cooler, and then transporting it to an ultrafiltration membrane system for ultrafiltration. 6 . Filtration, the obtained ultrafiltrate is reverse osmosis through the reverse osmosis system to obtain colorless reverse osmosis product water and orange-yellow reverse osmosis concentrated water, and then the orange-yellow reverse osmosis concentrated water is subjected to activated carbon adsorption COD and clarification treatment to obtain colorless acid concentrated water. water. 6.根据权利要求5所述粘胶纤维酸性废水资源化利用的处理方法，其特征在于，所述超滤的方式包括错流或死端方式，其中采用的超滤膜元件包括管式、板式、碟式、卷式或毛细管式膜元件；和/或，所述超滤系统包括通过管道连通的UF进水罐、UF进水泵、UF保安过滤器、UF膜单元、UF循环泵和UF产水罐；经冷却后的淡黄色预处理液依次经过UF进水罐、UF进水泵和UF保安过滤器后进入UF膜单元，从而获得反渗透进水要求的超滤液；和/或，所述反渗透系统包括通过管道连通的保安过滤器、反渗透高压泵、RO膜单元、RO产水罐和RO浓水罐，所述的超滤液依次经过保安过滤器和反渗透高压泵后进入RO膜单元，所获无色反渗透产水进入RO产水罐，橙黄色反渗透浓水进入RO浓水罐；和/或，所述反渗透的操作压力控制在5～16MPaG，浓水终点盐浓度在110000mg/L～300000mg/L。6. The treatment method for the resource utilization of viscose fiber acidic wastewater according to claim 5, wherein the ultrafiltration mode comprises cross-flow or dead-end mode, wherein the ultrafiltration membrane element adopted comprises tubular type, plate type , disc, coil or capillary membrane elements; and/or, the ultrafiltration system includes a UF inlet tank, a UF inlet pump, a UF security filter, a UF membrane unit, a UF circulating pump, and a UF production water tank; the cooled pale yellow pretreatment liquid enters the UF membrane unit after passing through the UF water inlet tank, the UF inlet water pump and the UF security filter in turn, so as to obtain the ultrafiltrate required by the reverse osmosis water inlet; and/or, so The reverse osmosis system comprises a security filter, a reverse osmosis high-pressure pump, an RO membrane unit, an RO water production tank and a RO concentrated water tank communicated through a pipeline, and the ultrafiltrate enters the security filter and the reverse osmosis high-pressure pump successively. RO membrane unit, the obtained colorless reverse osmosis product water enters the RO product water tank, and the orange-yellow reverse osmosis concentrated water enters the RO concentrated water tank; and/or, the operating pressure of the reverse osmosis is controlled at 5-16 MPaG, and the concentrated water end point The salt concentration is 110000mg/L～300000mg/L. 7.根据权利要求5所述粘胶纤维酸性废水资源化利用的处理方法，其特征在于，所述的膜浓缩步骤还包括：向所述橙黄色反渗透浓水内加入活性炭进行吸附，吸附时间≥0.25h，从而去除其中的COD；和/或，在完成以活性炭吸附所述橙黄色反渗透浓水内COD的操作后，对使用后的活性炭进行再生处理；和/或，所述澄清处理中采用的澄清池为耐酸水池，所述澄清池底部设置有刮泥机，用于将池底沉淀物及时收集至池底部中心，并且所述澄清池是间歇操作或连续操作的。7. The treatment method for the resource utilization of viscose fiber acidic wastewater according to claim 5, wherein the membrane concentration step further comprises: adding activated carbon to the orange-yellow reverse osmosis concentrated water for adsorption, and the adsorption time ≥0.25h, so as to remove the COD therein; and/or, after the operation of adsorbing COD in the orange-yellow reverse osmosis concentrated water with activated carbon is completed, the activated carbon after use is regenerated; and/or, the clarification treatment The clarifier used in the clarifier is an acid-resistant water pond, and a mud scraper is arranged at the bottom of the clarifier to collect the sediment at the bottom of the pond to the center of the bottom of the pond in time, and the clarifier is operated intermittently or continuously. 8.根据权利要求1所述粘胶纤维酸性废水资源化利用的处理方法，其特征在于还包括：在预处理步骤、膜浓缩步骤和蒸发结晶步骤中的任一者中采用活性炭吸附酸性废水中的COD。8. The treatment method for resource utilization of viscose fiber acidic wastewater according to claim 1, characterized in that it further comprises: using activated carbon to adsorb the acidic wastewater in any one of the pretreatment step, the membrane concentration step and the evaporative crystallization step COD. 9.根据权利要求1所述粘胶纤维酸性废水资源化利用的处理方法，其特征在于，所述的蒸发结晶步骤包括：采用热结晶法或冷结晶法对无色酸性浓水进行蒸发结晶处理，从而提取出其中的硫酸钠；所述热结晶法的温度控制在32.8℃以上，硫酸钠以无结晶水形式析出，所述冷结晶法的温度控制在32.8℃以下，硫酸钠以芒硝形式析出。9. The treatment method for resource utilization of viscose fiber acidic wastewater according to claim 1, wherein the evaporative crystallization step comprises: adopting a thermal crystallization method or a cold crystallization method to carry out evaporative crystallization treatment on the colorless acidic concentrated water , thereby extracting the sodium sulfate therein; the temperature of the thermal crystallization method is controlled above 32.8 ° C, the sodium sulfate is separated out in the form of no crystal water, the temperature of the cold crystallization method is controlled below 32.8 ° C, and the sodium sulfate is separated out in the form of mirabilite . 10.根据权利要求1所述粘胶纤维酸性废水资源化利用的处理方法，其特征在于：所述蒸发结晶处理的方式包括MVR蒸发、多效蒸发或多级真空闪蒸。10 . The method for treating viscose fiber acidic wastewater as a resource according to claim 1 , wherein the evaporative crystallization treatment method comprises MVR evaporation, multi-effect evaporation or multi-stage vacuum flash evaporation. 11 .
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