CN106495382B - A kind of processing method of sugar water - Google Patents
A kind of processing method of sugar water Download PDFInfo
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- CN106495382B CN106495382B CN201610863644.2A CN201610863644A CN106495382B CN 106495382 B CN106495382 B CN 106495382B CN 201610863644 A CN201610863644 A CN 201610863644A CN 106495382 B CN106495382 B CN 106495382B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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Abstract
The invention discloses a kind of processing methods of sugar water, include the steps that preheating filtering, doughnut nanofiltration and membrane distillation.The sugar water that present invention is specifically directed to generate in fatty acid production process, it can remove the coloration in sugar water, step by step, remaining fatty acid, crude product glycerol and distilled water in sugar water are targetedly separated and recovered, process flow can continuous and automatic, reaction condition it is mild, it is easy to operate, effect is obvious, has certain economic benefit.
Description
Technical field
The present invention relates to Treating Industrial Wastewater fields, and in particular to a kind of processing method of sugar water.
Background technique
Sugar water is generated in the technique of fatty acid manufacture: a large amount of water being added in grease under conditions of high temperature, makes
Grease hydrolysis becomes fatty acid and glycerol, the glycerol, a small amount of rouge after a large amount of fatty acid is removed from surface, in water containing 2 ~ 9%
Fat acid and pigment, here it is so-called sugar water.
The technique of traditional processing sugar water is to use the way of distillation, and the glycerol of concentration 2 ~ 9% is to 60-80%, wherein still containing pigment
And fatty acid, a kind of burgundy crude glycerine is obtained, for the purification of glycerol.
Film concentration is operation at normal temperature, without phase-change and heat-sensitive ingredients can be protected, equipment scale is small, low energy consumption,
Separative efficiency is high, is a kind of non-thermal concentration technology and technology with development prospect.Film be divided into reverse osmosis, nanofiltration,
Ultrafiltration, micro-filtration, membrane distillation, osmotic distillation, joint membrane technology etc..
Nanofiltration membrane is a kind of special and up-and-coming seperation film kind, it is about nanometer because of the size that can retain substance
And gain the name, the ability of dissolubility salt is retained between 2-98%, and high-valence anion is lower than to the desalination of monovalent anion salting liquid
Salting liquid.It is used to remove the organic matter and coloration of surface water, removes the hardness of underground water, part removes dissolubility salt, concentration
Utility etc. in fruit juice and separation drug.The form of membrane module has doughnut, rolling, plate and frame and tubular type etc..In
The packed density of empty fiber membrane component is high, low cost, and hydrodynamic conditions are good in component, but want to the manufacturing technology of membrane module
Ask high, sealing is difficult, and contamination resistance is poor in use, high to feed liquid pre-processing requirements.The research of film distillation starts from 20 generation
It records the eighties, compared with traditional way of distillation, having can overcome way of distillation equipment huge, high, the shortcomings that energy consumption is high is invested,
With low, the small advantage of energy consumption is invested, since low temperature distillation can be with applicable industry waste heat, solar energy etc., in certain special necks
Domain such as food industry, pharmaceutical industries, the purification such as chemical industry, concentration, reverse osmosis concentration salt water be concentrated again etc. show it is greatly excellent
More property.
In existing research, chemical, physical method (Qi Lin, Yang Jun, the pollution and its processing of fatty acid wastewater, Chinese oil,
1989 (1): 52-54.), contact oxidation method (Qin Linyuan, Liu Jinzhu, Zhu Pingsheng, the research of fatty acid wastewater treatment process selection,
Environmental Pollution and Control, 1986 (6)), (Cao Enwei, Liu Yuchuan, Chen Kuizhang, SBR technique is in fatty acid wastewater for anaerobism-SBR method
Handle the application in engineering, Jiangsu environmental science and technology, 16.4 (2003): 22-23.) and multi-method combination (Zhang Guobing, Sui Haibo,
A kind of waste water treatment system of fatty acid, CN203451332U [P] .2014.) all there are certain decoloration, drop to fatty acid wastewater
The effect of low COD.But several method requires additionally to add medicament, takes up a large area, can automate, poor continuity.
The Chinese literature of 103420533 B of Publication No. CN discloses a kind of processing method of high concentrated organic wastewater, benefit
With film integrated combination technique, high concentrated organic wastewater is first passed through into conditioning tank, then successively with micro- ultra filtration hollow fiber membrane device, receive
The group technology processing treating high-concentration saline organic wastewater for filtering hollow fiber membrane device, distillation device, realizes the portion of utility
Divide recycling or high concentrated organic wastewater is made to reach discharge standard.The technique generates without phase-change, and treatment temperature is low, less energy consumption,
Steam consumption is few, though having collected the utility in high concentrated organic wastewater, but still has waste water discharge.
Summary of the invention
In order to overcome the defects of the prior art, the present invention provides one kind with " preheating filtering-doughnut nanofiltration-film
The sugar water treatment process that distillation " is served as theme removes the color in sugar water specifically for the sugar water generated in fatty acid production process
Degree step by step, targetedly separates and recovers remaining fatty acid, crude product glycerol and water in sugar water, and process flow can continuously certainly
Dynamicization, reaction condition are mild, easy to operate, and effect is obvious, have certain economic benefit.
A kind for the treatment of process of sugar water, includes the following steps:
(1) preheating filtering: using industrial waste heat by sugar water heating and filtering, filtrate 1 is obtained, filter residue is burned into incinerator；
(2) doughnut nanofiltration: filtrate 1 is handled through hollow fiber nanofiltration membrane, is removed fatty acid, is obtained treatment fluid 2；It is described
Hollow fiber nanofiltration membrane aperture is 1.1 ~ 1.9 nm, can retain the substance of 120 ~ 480 dalton；
(3) membrane distillation: treatment fluid 2 enters distillation device and is concentrated by evaporation, and obtains crude product glycerol and water；Distillation device
Distilling film thickness is 70-590 μm, and aperture is 0.2 ~ 0.4 μm, distills the film both sides temperature difference at 20 ~ 40 DEG C.
Sugar water refers to the sugar water generated in fatty acid production process in the present invention, the glycerol containing 8% wt or so, a small amount of rouge
Fat acid and pigment, color is in faint yellow.
Preferably, the temperature of heating is 60 ~ 90 DEG C in step (1).Sugar water is heated to 60 ~ 90 DEG C, is had good
Mobility filters while hot, filters out pigment and bulky grain insoluble matter in sugar water, and the doughnut that can avoid blocking subsequent processing is received
Filter membrane.
Preferably, operating pressure is 0.8 ~ 1.0 MPa in step (2).
The hollow fiber nanofiltration membrane is hydrophilic film, and material is polyamide, polypropylene is fine, polyvinyl alcohol, diacetate fiber
One or more of element, Triafol T.
Further preferably, the hollow fiber nanofiltration membrane is by applying in aperture for 0.05-0.1 μm of ultrafiltration membrane surface
The composite membrane that polyamide, polypropylene be fine, polyvinyl alcohol, cellulose diacetate or Triafol T are prepared.Doughnut
Nanofiltration membrane is with a thickness of 50 ~ 750 μm, wherein ultra-thin dense layer thickness is 0.01 ~ 0.1 μm.
The hollow fiber nanofiltration membrane is high to organic matter separation rate, is 90%, 1000 to 300 dalton interception of molecular weight
Dalton interception is 100%, higher for divalent salt rejection rate, but low for monovalence salt rejection rate, only 10%.The present invention
The fatty acid molecule amount contained in related sugar water is between the hollow fiber nanofiltration membrane molecular cut off range, and
It is practically free of salt in sugar water, is suitble to handle using hollow fiber nanofiltration membrane of the present invention.
The common form of membrane module has doughnut, rolling, plate and frame and tubular type etc..Wherein, doughnut and rolled film
The packed density of component is high, low cost, and hydrodynamic conditions are good in component；But the manufacturing technology of both membrane modules requirement
Height, sealing is difficult, and contamination resistance is poor in use, high to feed liquid pre-processing requirements.Although and plate and frame and tubular membrane component are clear
Convenience, anti-pollution are washed, but the packed density of film is low, cost is high.
Sugar water after heat filtering is filtered by hollow fiber nanofiltration membrane, and 95% fatty acid is trapped, and fatty acid is concentrated 40
~ 45 times, recoverable improves fatty acid yield.The crude glycerine of transmission is practically free of fatty acid and volatile substances.
Preferably, distillation film described in step (3) is hydrophobic membrane.Since the hydrophobicity of distillation film lead to liquid water can not
It crosses, and water vapour can penetrate film under the driving of the temperature difference, add condensing condition in the film other side, and water vapour is made to be changed into water.Into
The crude glycerine temperature of row membrane distillation is higher, film is penetrated using film two sides temperature official post vapor, using compressed air by vapor
It brings condenser system condensation into, obtains condensed water.Glycerol is concentrated 10 ~ 12 times, and color is compared with the crude glycerine face that conventional distillation obtains
Color is shallow.
Thus the thickness of film and the size of the temperature difference are to determine the principal element of transmitance.Distill the thickness effect pure water of film
Flux, the thickness for increasing film can reduce flux, and the thickness for reducing film can reduce mechanical strength.So preferably, step (3)
In, the film both sides temperature difference is distilled at 20 ~ 40 DEG C, the distillation film is by polypropylene, Kynoar, polytetrafluoroethylene (PTFE), polysiloxanes,
Polysulfones or combinations thereof is made.
Compared with prior art, the present invention has the following advantages:
1, process is succinct, easy to operate, mild condition, and unused high energy consumption evaporates to obtain second-rate crude glycerine, subtracts
Few energy consumption pollution；
2, with doughnut nanofiltration, concentrating and purifying process can carry out at normal temperature, without phase-change, no chemical reaction,
It does not bring other impurities into, does not cause product to decompose denaturation, product salinity can be removed, simple and compact equipment structure, occupied area is small,
Low energy consumption, easy to maintain；
3, film distillation technology is applied in process, can be carried out under normal pressure, it is easy to operate, it is not necessary that solution is heated to boiling point,
The appropriate temperature difference in film two sides need to only be maintained；
4, the fatty acid and crude product glycerol obtained by this technique can recycle, and improve yield, and obtained condensed water reaches
It to national tertiary effluent GB/T6682-2008 requirement, can be used for producing washing water or reaction water, increase economic benefit.
Detailed description of the invention
Fig. 1 is the processing technological flow of sugar water waste water of the invention.
Specific embodiment
Embodiment 1
The sugar water that fatty acid generates is produced, measures 0.69 g/L of fatty acid, glycerol 8.6%wt, color is transparent dark yellow.
(1) preheating filtering: sugar water is heated to 70 DEG C using industrial waste heat, filtering obtains glassy yellow clear filtrate I.
(2) doughnut nanofiltration: filtrate I is entered in hollow fiber nanofiltration membrane component at 0.8 MPa by constant flow pump
Fractionation of fatty acid and crude glycerine, used nanofiltration membrane is by polyamide, polypropylene is fine, polyvinyl alcohol, cellulose diacetate, three vinegar
Acid cellulose is made, aperture be 1.3 nm, 50 μm of film thickness.It is detected, obtained fatty acid is 28.56 g/L.
(3) membrane distillation: the crude glycerine by doughnut nanofiltration enters membrane component concentration, is carried using compressed air
Vapor enter condenser system condensation, used distillation film by polypropylene, Kynoar, polytetrafluoroethylene (PTFE), polysiloxanes,
Polysulfones is made, and aperture is 0.4 μm, 85 μm of film thickness.Through detecting, gained glycerol is 84%wt, light yellow transparent liquid, gained condensation
Water meets National Laboratory three-level water supply standard GB/T6682-2008.
Comparative example 1
It is constant with operating procedures other in embodiment 1, step 1 is only removed, sugar water is filtered to remove depigmentation and bulky grain
Object is directly entered hollow fiber nanofiltration membrane component, obtains 28.54 g/L of fatty acid, glycerol 83.9%wt, and condensed water meets country
Laboratory three-level water supply standard GB/T6682-2008.Gained fatty acid, glycerol and condensed water and embodiment 1 are not much different, but in
The blocking of hollow fiber nanofiltration membrane component membrane aperture is serious, shortens the service life of film, increases the wash number of film.
Embodiment 2
The sugar water that fatty acid generates is produced, measures 0.68 g/L of fatty acid, glycerol 8.7%wt, color is transparent dark yellow.
(1) preheating filtering: sugar water is heated to 80 DEG C using industrial waste heat, filtering obtains glassy yellow clear filtrate I.
(2) doughnut nanofiltration: filtrate I is entered in hollow fiber nanofiltration membrane component at 0.9 MPa by constant flow pump
Fractionation of fatty acid and crude glycerine, used nanofiltration membrane is by polyamide, polyvinyl alcohol, cellulose diacetate, Triafol T
Be made, aperture be 1.2 nm, 50 μm of film thickness.It is detected, obtained fatty acid is 28.48 g/L.
(3) membrane distillation: the crude glycerine by doughnut nanofiltration enters membrane component concentration, is carried using compressed air
Vapor enters condenser system condensation, and used distillation film is by polypropylene, Kynoar, polytetrafluoroethylene (PTFE), polysiloxanes
It is made, aperture is 0.24 μm, 130 μm of film thickness.Through detecting, gained glycerol is 85%wt, light yellow transparent liquid, gained condensed water
Meet National Laboratory three-level water supply standard GB/T6682-2008.
Embodiment 3
The sugar water that fatty acid generates is produced, measures 0.67 g/L of fatty acid, glycerol 8.5%wt, color is transparent dark yellow.
(1) preheating filtering: sugar water is heated to 90 DEG C using industrial waste heat, filtering obtains glassy yellow clear filtrate I.
(2) doughnut nanofiltration: filtrate I is entered in hollow fiber nanofiltration membrane component at 0.95 MPa by constant flow pump
Fractionation of fatty acid and crude glycerine, used nanofiltration membrane is by polyamide, polypropylene is fine, polyvinyl alcohol, cellulose diacetate are made,
Aperture be 1.4 nm, 80 μm of film thickness.It is detected, obtained fatty acid is 28.33 g/L.
(3) membrane distillation: the crude glycerine by doughnut nanofiltration enters membrane component concentration, is carried using compressed air
Vapor enters condenser system condensation, and used distillation film is made of polypropylene, Kynoar, polysiloxanes, polysulfones, hole
Diameter is 0.33 μm, 150 μm of film thickness.Through detecting, gained glycerol is 81%wt, and light yellow transparent liquid, gained condensed water meets country
Laboratory three-level water supply standard GB/T6682-2008.
Embodiment 4
The sugar water that fatty acid generates is produced, measures 0.69 g/L of fatty acid, 7.8 %wt of glycerol, color is transparent dark yellow.
(1) preheating filtering: sugar water is heated to 85 DEG C using industrial waste heat, filtering obtains glassy yellow clear filtrate I.
(2) doughnut nanofiltration: filtrate I is entered in hollow fiber nanofiltration membrane component at 0.84 MPa by constant flow pump
Fractionation of fatty acid and crude glycerine, used nanofiltration membrane is by polyamide, polypropylene is fine, cellulose diacetate, Triafol T
Be made, aperture be 1.8 nm, 50 μm of film thickness.It is detected, obtained fatty acid is 28.54 g/L.
(3) membrane distillation: the crude glycerine by doughnut nanofiltration enters membrane component concentration, is carried using compressed air
Vapor enter condenser system condensation, used distillation film by polypropylene, Kynoar, polytetrafluoroethylene (PTFE), polysiloxanes,
Polysulfones is made, and aperture is 0.37 μm, 90 μm of film thickness.Through detecting, gained glycerol is 81%wt, light yellow transparent liquid, gained condensation
Water meets National Laboratory three-level water supply standard GB/T6682-2008.
Embodiment 5
The sugar water that fatty acid generates is produced, measures 0.69 g/L of fatty acid, glycerol 8.9%wt, color is transparent dark yellow.
(1) preheating filtering: sugar water is heated to 75 DEG C using industrial waste heat, filtering obtains glassy yellow clear filtrate I.
(2) doughnut nanofiltration: filtrate I is entered in hollow fiber nanofiltration membrane component at 0.92 MPa by constant flow pump
Fractionation of fatty acid and crude glycerine, used nanofiltration membrane is by polyamide, polypropylene is fine, polyvinyl alcohol, cellulose diacetate, three vinegar
Acid cellulose is made, aperture be 1.9 nm, 50 μm of film thickness.It is detected, obtained fatty acid is 28.63 g/L.
(3) membrane distillation: the crude glycerine by doughnut nanofiltration enters membrane component concentration, is carried using compressed air
Vapor enters condenser system condensation, and used distillation film is by polypropylene, Kynoar, polytetrafluoroethylene (PTFE), polysiloxanes
It is made, aperture is 0.28 μm, 120 μm of film thickness.Through detecting, gained glycerol is 86%wt, light yellow transparent liquid, gained condensed water
Meet National Laboratory three-level water supply standard GB/T6682-2008.
Embodiment 6
The sugar water that fatty acid generates is produced, measures 0.69 g/L of fatty acid, glycerol 8.5%wt, color is transparent dark yellow.
(1) preheating filtering: sugar water is heated to 65 DEG C using industrial waste heat, filtering obtains glassy yellow clear filtrate I.
(2) doughnut nanofiltration: filtrate I is entered in hollow fiber nanofiltration membrane component at 1.0 MPa by constant flow pump
Fractionation of fatty acid and crude glycerine, used nanofiltration membrane is fine by polypropylene, polyvinyl alcohol, cellulose diacetate are made, and aperture is
1.3 nm, 75 μm of film thickness.It is detected, obtained fatty acid is 28.64 g/L.
(3) membrane distillation: the crude glycerine by doughnut nanofiltration enters membrane component concentration, is carried using compressed air
Vapor enters condenser system condensation, and used distillation film is made of polypropylene, polysiloxanes, polysulfones, and aperture is 0.33 μ
M, 75 μm of film thickness.Through detecting, gained glycerol is 83%wt, and light yellow transparent liquid, gained condensed water meets National Laboratory's three-level
Water supply standard GB/T6682-2008.
Embodiment 7
The sugar water that fatty acid generates is produced, measures 0.67 g/L of fatty acid, glycerol 8.9%wt, color is transparent dark yellow.
(1) preheating filtering: sugar water is heated to 90 DEG C using industrial waste heat, filtering obtains glassy yellow clear filtrate I.
(2) doughnut nanofiltration: filtrate I is entered in hollow fiber nanofiltration membrane component at 0.90 MPa by constant flow pump
Fractionation of fatty acid and crude glycerine, used nanofiltration membrane be made of polyamide, aperture be 1.9 nm, 350 μm of film thickness.Through detecting,
Obtained fatty acid is 28.33 g/L.
(3) membrane distillation: the crude glycerine by doughnut nanofiltration enters membrane component concentration, is carried using compressed air
Vapor enters condenser system condensation, and used distillation film is made of polypropylene, polysulfones, and aperture is 0.4 μm, 300 μm of film thickness.
Through detecting, gained glycerol is 82%wt, and light yellow transparent liquid, gained condensed water meets National Laboratory three-level water supply standard GB/
T6682-2008。
Embodiment 8
The sugar water that fatty acid generates is produced, measures 0.67 g/L of fatty acid, glycerol 8.5%wt, color is transparent dark yellow.
(1) preheating filtering: sugar water is heated to 75 DEG C using industrial waste heat, filtering obtains glassy yellow clear filtrate I.
(2) doughnut nanofiltration: filtrate I is entered in hollow fiber nanofiltration membrane component at 0.80 MPa by constant flow pump
Fractionation of fatty acid and crude glycerine, used nanofiltration membrane is fine by polypropylene, polyvinyl alcohol, cellulose diacetate are made, and aperture is
1.5 nm, 700 μm of film thickness.It is detected, obtained fatty acid is 28 g/L.
(3) membrane distillation: the crude glycerine by doughnut nanofiltration enters membrane component concentration, is carried using compressed air
Vapor enters condenser system condensation, and used distillation film is made of polypropylene, Kynoar, polysiloxanes, polysulfones, hole
Diameter is 0.37 μm, 550 μm of film thickness.Through detecting, gained glycerol is 83%wt, and light yellow transparent liquid, gained condensed water meets country
Laboratory three-level water supply standard GB/T6682-2008.
Claims (5)
1. a kind for the treatment of process of sugar water, which comprises the steps of:
(1) preheating filtering: using industrial waste heat by sugar water heating and filtering, heating temperature is 60~90 DEG C, obtains filtrate 1, filter residue into
Incinerator burns；
(2) doughnut nanofiltration: filtrate 1 is handled through hollow fiber nanofiltration membrane, is removed fatty acid, is obtained treatment fluid 2；It is described hollow
Fiber nano filtering membrane aperture is 1.1~1.9nm, can retain the substance of 120~480 dalton；
(3) membrane distillation: treatment fluid 2 enters distillation device and is concentrated by evaporation, and obtains crude product glycerol and water；The distillation of distillation device
Film is hydrophobic membrane, and by polypropylene, Kynoar, polytetrafluoroethylene (PTFE), polysiloxanes, polysulfones or combinations thereof is made, with a thickness of 70-
590 μm, aperture is 0.2~0.4 μm, distills the film both sides temperature difference at 20~40 DEG C.
2. treatment process according to claim 1, which is characterized in that in step (2), the work of the hollow fiber nanofiltration membrane
Making pressure is 0.8~1.0MPa.
3. treatment process according to claim 1, which is characterized in that in step (2), the hollow fiber nanofiltration membrane is parent
Moisture film, material are one or more of polyamide, polyacrylonitrile, polyvinyl alcohol, cellulose diacetate, Triafol T.
4. treatment process according to claim 1, which is characterized in that the hollow fiber nanofiltration membrane is by being in aperture
0.05-0.1 μm of ultrafiltration membrane surface coating polyamide, polyacrylonitrile, polyvinyl alcohol, cellulose diacetate or Triafol T
The composite membrane being prepared.
5. treatment process according to claim 4, it is characterised in that: the hollow fiber nanofiltration membrane is with a thickness of 50~750 μ
M, wherein ultra-thin dense layer thickness is 0.01~0.1 μm.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58126827A (en) * | 1982-01-25 | 1983-07-28 | Nippon Oil & Fats Co Ltd | Preparation of glycerol in high purity |
| CN101139255A (en) * | 2007-09-07 | 2008-03-12 | 浙江大学 | Hyperfiltration-distillation integration process for reclaiming glycerin from low-concentration sweet water |
| CN102887604A (en) * | 2012-10-29 | 2013-01-23 | 杭州油脂化工有限公司 | Method for hydrolyzing sweet water through processing grease by using dissolved air flotation |
| CN204058300U (en) * | 2014-06-20 | 2014-12-31 | 丰益油脂化学(东莞）有限公司 | A kind of high-temperature reflux hydrolysate oil is separated the device preparing glycerine |
-
2016
- 2016-09-29 CN CN201610863644.2A patent/CN106495382B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58126827A (en) * | 1982-01-25 | 1983-07-28 | Nippon Oil & Fats Co Ltd | Preparation of glycerol in high purity |
| CN101139255A (en) * | 2007-09-07 | 2008-03-12 | 浙江大学 | Hyperfiltration-distillation integration process for reclaiming glycerin from low-concentration sweet water |
| CN102887604A (en) * | 2012-10-29 | 2013-01-23 | 杭州油脂化工有限公司 | Method for hydrolyzing sweet water through processing grease by using dissolved air flotation |
| CN204058300U (en) * | 2014-06-20 | 2014-12-31 | 丰益油脂化学(东莞）有限公司 | A kind of high-temperature reflux hydrolysate oil is separated the device preparing glycerine |
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