CN105683092A - Combined membrane separation process for concentrating IPA from wastewater containing IPA and treating wastewater - Google Patents

Combined membrane separation process for concentrating IPA from wastewater containing IPA and treating wastewater Download PDF

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Publication number
CN105683092A
CN105683092A CN201480055455.1A CN201480055455A CN105683092A CN 105683092 A CN105683092 A CN 105683092A CN 201480055455 A CN201480055455 A CN 201480055455A CN 105683092 A CN105683092 A CN 105683092A
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CN
China
Prior art keywords
ipa
membrane separation
waste water
composite membrane
reverse osmosis
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CN201480055455.1A
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Chinese (zh)
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CN105683092B (en
Inventor
河成龙
高亨澈
季忠变
裴恩石
林采成
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ENERENVI-TECH Co Ltd
Airrane Co Ltd
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ENERENVI-TECH Co Ltd
Airrane Co Ltd
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Classifications

    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/02Treatment of water, waste water, or sewage by heating
    • C02F1/04Treatment of water, waste water, or sewage by heating by distillation or evaporation
    • C02F1/08Thin film evaporation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/44Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/448Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by pervaporation
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D61/00Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/58Multistep processes
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/44Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/44Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/441Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D61/00Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/025Reverse osmosis; Hyperfiltration
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D61/00Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/36Pervaporation; Membrane distillation; Liquid permeation
    • B01D61/362Pervaporation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • C02F2101/34Organic compounds containing oxygen

Abstract

The present invention relates to a combined membrane separation process for concentrating IPA from wastewater containing IPA and treating wastewater, and more specifically, to a combined membrane separation process capable of separating and concentrating IPA from wastewater containing IPA and simultaneously treating wastewater by combining a pervaporation membrane separation process and a reverse osmosis membrane separation process. According to the combined membrane separation process of the present invention, IPA can be selectively separated from IPA washing wastewater and concentrated to 30 wt% or more, thereby recycling the same, and simultaneously, IPA washing wastewater having a low concentration of 0.5 wt% or less can be treated, as is, in a conventional wastewater treatment plant without separate dilution.

Description

The composite membrane separation method of concentration and wastewater treatment for the waste water containing IPA being carried out IPA
Technical field
The present invention relates to the composite membrane separation method for the concentration and wastewater treatment that the waste water containing IPA is carried out IPA, it is more particularly to combine osmotic evaporation film separation circuit and reverse osmosis membrane separation operation, it is possible to from the waste water containing IPA, separate and concentrate IPA and process the composite membrane separation method of waste water simultaneously.
Background technology
IPA (isopropanol) is many in industry workshop particularly semiconductor fabrication sequence and LCD manufacturing process etc. to be used as cleaning solution, usually contains the IPA of 5 weight %~15 weight % in the cleaning waste water after this use. About the waste water so produced, from the viewpoint of the recovery of organic compound especially alcohol, because the concentration of IPA is non-normally low, so there is no economy when using common distillation process to be easily separated, concentrating, therefore there is currently the problem that it is all carried out wastewater treatment.
On the other hand, clean waste water about such IPA, from the viewpoint of wastewater treatment, because the excessive concentration of IPA, diluting so there is use water, making the concentration of IPA be reduced to 1% other problem being carried out below wastewater treatment.
The existing formerly research (patent documentation 1,2) about osmotic evaporation film separation circuit, this osmotic evaporation film separation circuit is for using osmotic evaporation film be optionally sequestered water from the mixed solution of the alcohol/water such as IPA or be optionally sequestered organic compound from organic compound aqueous solution, and use the technology that reverse osmosis membrane separation operation processes waste water to be also widely known by the people (patent documentation 3,4), but osmotic evaporation film separation circuit and reverse osmosis membrane separation operation carry out respectively as different operations according to purposes and characteristic.
Therefore, IPA for being unsuitable for carrying out concentrating the concentration recycling or carrying out wastewater treatment cleans waste water, if while using osmotic evaporation film separation circuit to concentrate IPA, reverse osmosis membrane separation operation is used to separate IPA and make IPA concentration become suitable for the concentration of wastewater treatment in the lump, then can be optionally sequestered and concentrate IPA from the IPA cleaning waste water all carrying out wastewater treatment in the past to recycle, and, the IPA of low concentration cleans waste water can not carry out other dilution and be made directly process in existing waste water treatment plant, present inventor is conceived to above-mentioned situation, complete the present invention.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Laid-Open Patent Publication the 10-2011-0083077th;
Patent documentation 2: Japanese Laid-Open Patent Publication the 10-2000-0067454th;
Patent documentation 3: Japanese Laid-Open Patent Publication the 10-2013-0032294th;
Patent documentation 4: Japanese Laid-Open Patent Publication the 10-2005-0026294th.
Summary of the invention
The problem that invention to solve
The present invention makes in view of the above-mentioned problems, its object is to provide a kind of composite membrane separation method combining osmotic evaporation film separation circuit and reverse osmosis membrane separation operation, can clean from IPA waste water to be optionally sequestered IPA and is concentrated into more than 30 weight % and recycle, and the IPA of the low concentration of below 0.5 weight % cleans waste water and can not carry out other dilution and be made directly process in existing waste water treatment plant.
For solving the scheme of problem
In order to realize described purpose, the present invention provides a kind of composite membrane separation method, including: from the waste water containing IPA, the step of IPA I) is concentrated by osmotic evaporation film separation circuit; And II) by the reverse osmosis membrane separation operation step from the wastewater treatment waste water containing IPA.
It is characterized in that, described I) the osmotic evaporation film separation circuit of step includes: the waste water containing IPA that i) will heat up is supplied to the step of pervaporation film module; Ii) IPA having penetrated pervaporation film module is condensed into the step of liquid phase; And iii) curdy IPA is transplanted on the step of percolating solution case.
It is characterized in that, the described waste water containing IPA heated up is maintained 30 DEG C~60 DEG C by heater.
It is characterized in that, be supplied to more than supply flow rate is seepage discharge 5 times of waste water containing IPA of described pervaporation film module.
It is characterized in that, described II) the reverse osmosis membrane separation operation of step includes: a) waste water containing IPA boosted is supplied to the step of reverse osmosis membrane module; And b) move wastewater of the reverse osmosis membrane module step to infiltration water tank will have been penetrated.
It is characterized in that, the described waste water containing IPA boosted is maintained 10bar~70bar by high-pressure pump.
It is characterized in that, be supplied to more than supply flow rate is seepage discharge 3 times of waste water containing IPA of described reverse osmosis membrane module.
Invention effect
Composite membrane separation method according to the present invention, can clean from IPA and waste water is optionally sequestered IPA, it is concentrated into more than 30 weight % to recycle, and the IPA cleaning waste water of the low concentration of below 0.5 weight % can not carried out other dilution and be made directly process in existing waste water treatment plant simultaneously.
Accompanying drawing explanation
Fig. 1 is the block diagram of continuous way (continuous) the composite membrane separation method illustrating the present invention;
Fig. 2 is the block diagram of batch-type (batch) the composite membrane separation method illustrating the present invention.
Detailed description of the invention
Hereinafter, using osmotic evaporation film separation circuit concentration IPA and using reverse osmosis membrane separation operation to separate IPA so that IPA concentration is suitable to composite membrane separation method and the accompanying drawing of the concentration of wastewater treatment simultaneously of the present invention is described in detail.
The present invention provides a kind of composite membrane separation method, including: from the waste water containing IPA, the step of IPA I) is concentrated by osmotic evaporation film separation circuit; And II) by the reverse osmosis membrane separation operation step from the wastewater treatment waste water containing IPA.
Additionally, above-mentioned I) the osmotic evaporation film separation circuit of step includes: the waste water containing IPA that i) will heat up is supplied to the step of pervaporation film module; Ii) IPA having penetrated pervaporation film module is condensed into the step of liquid phase;And iii) curdy IPA is transplanted on the step of percolating solution case, as shown in continuous (continuous) operation block diagram of Fig. 1, first, waste water (IPA solution) containing IPA is stored in IPA liquor box 100, utilizes the common heating units such as heater 110 to make the IPA solution warms of IPA liquor box. Now, if the temperature of IPA solution is less than 30 DEG C, then the infiltration capacity of pervaporation film module is too small, if the temperature of IPA solution is more than 60 DEG C, then energy expenditure is excessive, it is therefore preferable that IPA solution is heated up by heater 110 and maintains 30 DEG C~60 DEG C.
Then, will heat up to the IPA solution of 30 DEG C~60 DEG C and be supplied to pervaporation film module 150, at this, along with the process sequentially passing through the molten fluid supply pump 120 of IPA, solution strainer 130 and IPA liquid inventory meter 140. Now, it is preferable that the supply flow rate being supplied to the IPA solution of pervaporation film module 150 is adjusted to more than 5 times of seepage discharge. If IPA solution is supplied to pervaporation film module 150 with less than 5 times of seepage discharge, then the concentration by the IPA of the percolating solution of pervaporation film module 150 infiltration is low, it is thus impossible to be easily separated swimmingly and concentrate.
The IPA solution being supplied to pervaporation film module 150 like this has IPA separating dissolving in film, at separation film internal diffusion with the mechanism of action of gas-phase permeation. According to this mechanism of action, one end of pervaporation film module 150 supplies solution with IPA and contact, and the other end contacts with the vapour pressure of low penetrant, and low vapour pressure condition can by evacuation or make inert carrier gas inflow and generate. Therefore, generally, the gradient of chemical potential energy in the propulsive force (drivingforce) being internally generated as osmotic evaporation film separation circuit of osmotic evaporation film, carry out the material infiltration via film, therefore, in the present invention, in order to maintain the propulsive force of osmotic evaporation film separation circuit, by using vacuum pump 170 to make osmosizing portion maintain vacuum.
Secondly, the IPA of the gas phase having penetrated pervaporation film module 150 is condensed into liquid phase at common coagulator 160, and the IPA of curdy liquid phase is shifted into percolating solution case 190 through percolating solution effusion meter 180. The IPA solution obtained by this osmotic evaporation film separation circuit is concentrated into more than 30%, therefore, it is possible to be recovered for re-use.
On the other hand, the composite membrane separation method of the present invention carrying out reverse osmosis membrane separation operation, above-mentioned II simultaneously) the reverse osmosis membrane separation operation of step includes: a) waste water containing IPA after boosting is supplied to the step of reverse osmosis membrane module; And b) move wastewater of the reverse osmosis membrane module step to infiltration water tank will have been penetrated, as shown in the series-operation block diagram of Fig. 1, first, from IPA liquor box 100, the waste water containing IPA is transplanted on IPA solution high-pressure pump 220 through solution strainer 210, IPA solution is boosted. Now, the supply pressure of preferred high-pressure pump 220 maintains 10bar~70bar, if to run less than 10bar, then propulsive force is low, therefore the infiltration capacity of reverse osmosis membrane is greatly reduced, if it exceeds 70bar, then the long-time stability of reverse osmosis membrane reduce, therefore, it is adjusted to IPA solution to be boosted by high-pressure pump 220 and maintain 10bar~70bar.
Then, through liquid inventory meter 230, the IPA solution boosting to 10bar~70bar being supplied to reverse osmosis membrane module 240, the waste water having penetrated reverse osmosis membrane module 240 is shifted into infiltration water tank 260 through infiltration water ga(u)ge 250.The waste water (infiltration water) permeated by this reverse osmosis membrane separation operation is less than 0.5% due to the concentration of IPA, so not carrying out other dilution and directly carrying out processing in waste water treatment plant.
As described above, in actual continuous (continuous) composite membrane separation method carried out shown in Fig. 1, the waste water (IPA solution) containing IPA of fixed amount is filled into case 100, osmotic evaporation film separation circuit is used to be separated by IPA and concentration, also carry out reverse osmosis membrane separation operation together simultaneously, make water (waste water) infiltration be transplanted on infiltration water tank 260. Now, confirm the amount of the IPA concentrated solution of osmotic evaporation film separation circuit and the amount of the infiltration water of reverse osmosis membrane separation operation, IPA liquor box 100 is supplemented continuously, amount (continuous print waste water generation amount) according to process continuously designs osmotic evaporation film separation circuit and the capacity of reverse osmosis membrane separation operation, it is possible to run these operations continuously.
On the other hand, example is run as other, it also is able to carry out the composite membrane separation method of (batch) the in batches formula shown in Fig. 2, the waste water (IPA solution) containing IPA of fixed amount is filled into case 100, using osmotic evaporation film separation circuit, IPA is separated and after concentration, when the concentration of the original waste water containing IPA is reduced to below finite concentration, the solution of IPA liquor box 100 is transplanted on another IPA liquor box 200, this waste water containing IPA transferred makes water penetration by reverse osmosis membrane separation operation and is stored in infiltration water tank 260, water is removed from the IPA solution of IPA liquor box 200, it is shifted into IPA liquor box 100 when IPA increases to finite concentration, again carry out osmotic evaporation film separation circuit, by reruning above-mentioned operation, the waste water containing IPA is all processed, the infiltration water of infiltration water tank 260 reduces due to the concentration of IPA, therefore, it is possible to process in waste water treatment plant.
And, although it is attached not illustrated in FIG., but the composite membrane separation method of following semi-batch (semi-batch) formula can also be carried out: the waste water (IPA solution) containing IPA of fixed amount is filled into case 100, using osmotic evaporation film separation circuit, IPA is separated and while concentration, also reverse osmosis membrane separation operation is carried out together, water (waste water) infiltration is made to be transplanted on infiltration water tank 260, continue to run with afterwards, when the level (level) of IPA liquor box 100 become a certain amount of below time, supplement the waste water containing IPA, the upper limit and threshold level according to IPA liquor box 100 to run with batch-type.
On the other hand, membrane material as the osmotic evaporation film separation circuit included by the composite membrane separation method of the present invention, it is preferably the silicone composite membrane being coated with the organopolysiloxanes such as polydimethylsiloxane (PDMS) at porous supporting masses such as Polyetherimide, but is not limited to this. It addition, as the membrane material of reverse osmosis membrane separation operation, it is preferable that it is coated with the polyamide-based composite membrane of polyamide at porous supporting masses such as polysulfones, but is not limited to this.
Detailed description of the invention
Hereinafter, specific embodiment is described in detail.
(embodiment 1)
The concentration of the IPA of the waste water containing IPA is fixed as 5.2 weight %, supply flow rate is fixed as 80LPM (literperminute, Liter Per Minute), the temperature making supply solution changes to 35 DEG C, 45 DEG C and 55 DEG C respectively, carrying out the continuous composite membrane separation method shown in Fig. 1, table 1 illustrates concentration and the seepage discharge of the IPA of the percolating solution of the temperature of the supply solution according to osmotic evaporation film separation circuit.
[table 1]
(embodiment 2)
Except the concentration of the IPA of the waste water containing IPA is fixed as 8.7 weight %, carrying out continuous composite membrane separation method in the same manner as in Example 1, table 2 illustrates concentration and the seepage discharge of the IPA of the percolating solution of the temperature of the supply solution according to osmotic evaporation film separation circuit.
[table 2]
(embodiment 3)
The temperature of supply solution is fixed as 35 DEG C, supply flow rate is fixed as 20LPM, the concentration making the IPA of the waste water containing IPA is changing into 5.2 weight %, 6.2 weight %, 7.3 weight % and 8.5 weight % respectively, carrying out the continuous composite membrane separation method shown in Fig. 1, table 3 illustrates concentration and the seepage discharge of the IPA of the percolating solution (infiltration water) of reverse osmosis membrane separation operation.
[table 3]
As shown in table 1 and table 2, the osmotic evaporation film separation circuit of the embodiment 1 and 2 of the composite membrane separation method according to the present invention, it is known when the temperature supplying solution is identical, the concentration of the IPA of the waste water containing IPA is more high, the concentration of the IPA of percolating solution and seepage discharge more increase, additionally, confirm in all cases, the concentration of the IPA of percolating solution shows that more than 38%, and percolating solution can be recovered for re-use.
And, as shown in table 3, the reverse osmosis membrane separation operation of the embodiment 3 of the composite membrane separation method according to the present invention, when the concentration (concentration of supply solution) of the IPA of the waste water containing IPA increases to 8.5 weight % from 5.2 weight %, the concentration of the IPA of percolating solution (infiltration water) somewhat increases, seepage discharge reduces, but in all cases, the concentration of the IPA of percolating solution (infiltration water) is equal to 0.5 weight %, it is thus identified that percolating solution (infiltration water) can be transplanted directly on waste water treatment plant to carry out wastewater treatment.
Industrial utilizability
Therefore, composite membrane separation method according to the present invention illustrates following significant effect, namely, IPA can be separated with cleaning waste water selective from IPA, concentrated is that more than 30 weight % recycle, further, the IPA cleaning waste water of the low concentration of below 0.5 weight % can not carry out other dilution and be made directly process in existing waste water treatment plant.

Claims (9)

1. a composite membrane separation method, including:
I) from the waste water containing IPA, the step of IPA is concentrated by osmotic evaporation film separation circuit; And
II) by the reverse osmosis membrane separation operation step from the wastewater treatment waste water containing IPA.
2. composite membrane separation method as claimed in claim 1, it is characterised in that
Described I) the osmotic evaporation film separation circuit of step includes:
I) waste water containing IPA that will heat up is supplied to the step of pervaporation film module;
Ii) IPA having penetrated pervaporation film module is condensed into the step of liquid phase; And
Iii) curdy IPA is transplanted on the step of percolating solution case.
3. composite membrane separation method as claimed in claim 2, it is characterised in that
The described waste water containing IPA heated up is maintained 30 DEG C~60 DEG C by heater.
4. composite membrane separation method as claimed in claim 2, it is characterised in that
It is supplied to more than supply flow rate is seepage discharge 5 times of waste water containing IPA of described pervaporation film module.
5. composite membrane separation method as claimed in claim 1, it is characterised in that
Described II) the reverse osmosis membrane separation operation of step includes:
A) waste water containing IPA boosted is supplied to the step of reverse osmosis membrane module;And
B) move wastewater of the reverse osmosis membrane module step to infiltration water tank will have been penetrated.
6. composite membrane separation method as claimed in claim 5, it is characterised in that
The described waste water containing IPA boosted is maintained 10bar~70bar by high-pressure pump.
7. composite membrane separation method as claimed in claim 5, it is characterised in that
It is supplied to more than supply flow rate is seepage discharge 3 times of waste water containing IPA of described reverse osmosis membrane module.
8. composite membrane separation method as claimed in claim 1 or 2, it is characterised in that
The membrane material of described osmotic evaporation film separation circuit is silicone composite membrane.
9. the composite membrane separation method as described in claim 1 or 5, it is characterised in that
The membrane material of described reverse osmosis membrane separation operation is polyamide-based composite membrane.
CN201480055455.1A 2013-10-07 2014-09-04 For carrying out IPA concentration and the compound membrane separating method of wastewater treatment to the waste water containing IPA Active CN105683092B (en)

Applications Claiming Priority (3)

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KR10-2013-0118983 2013-10-07
KR1020130118983A KR101695215B1 (en) 2013-10-07 2013-10-07 Combined membrane separation process for concentration of IPA and treatment of wastewater from IPA-containing wastewater
PCT/KR2014/008334 WO2015053483A1 (en) 2013-10-07 2014-09-04 Combined membrane separation process for concentrating ipa from wastewater containing ipa and treating wastewater

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CN105683092B CN105683092B (en) 2018-04-03

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WO2015053483A1 (en) 2015-04-16
CN105683092B (en) 2018-04-03

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