CN1884340A - Process for ultrafiltration and purification of polyether glycol - Google Patents
Process for ultrafiltration and purification of polyether glycol Download PDFInfo
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- CN1884340A CN1884340A CN 200610040557 CN200610040557A CN1884340A CN 1884340 A CN1884340 A CN 1884340A CN 200610040557 CN200610040557 CN 200610040557 CN 200610040557 A CN200610040557 A CN 200610040557A CN 1884340 A CN1884340 A CN 1884340A
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Abstract
The invention discloses a method for purifying crude polyether polyol through hyperfiltration, comprising following steps: feeding crude polyether polyol containing catalyst into crude storage tank, then feeding it to hyperfiltration device at 50-220 Deg. C, discharging a part of polyether polyol through separating membrane, inputting filtered liquid which is purified polyether polyol to final product tank, feeding polyether polyol which is not penetrated through separating membrane and catalyst back to crude storage tank, recycling, and the concentration of catalyst in crude storage tank is increased continuously and when it amounts to a certain value, closing valve of crude storage tank to hyperfiltration device and opening valve to synthesis device, reclaiming catalyst for reuse. The invention can purify crude containing 30-1000 ppm of DMC catalyst to polyether polyol (total content of zinc ion and cobalt ion less than 2.0 ppm), the recovered DMC can be directly used for polyether polyol synthesis.
Description
Technical field
The present invention relates to the purifying of the polyether glycol of bimetallic catalyst catalytic preparation.
Background technology
With low-molecular-weight polyether glycol is initiator, with epoxy compounds (comprising propylene oxide, ethylene oxide or oxybutylene etc.) is raw material, in the presence of bimetallic catalyst, are the main method that prepare high molecular weight polyether at present at 90～150 ℃ of synthetic higher polyether glycols of relative molecular weight of reaction.
With bimetallic cyaniding complex (DMC) is that the method for Preparation of Catalyst polyether glycol is comparatively ripe, its catalyst activity height, low, the narrow molecular weight distribution of synthetic polyether glycol degree of unsaturation, and existing a large amount of patent reports.Preparation during polyether glycol if the dmc catalyst consumption is less, inductive condition harshness then.Can relax inductive condition by strengthening catalyst consumption, and reacting balance is rapid, can improve the quality of polyether glycol, but the dmc catalyst residue must be removed from the polyether glycol finished product as much as possible, because of the existence of dmc catalyst can make polyether glycol follow-up, undesirable side reaction taking place, has shortened the storage time of polyether glycol; And residual dmc catalyst has considerable influence to the application of polyether glycol.The dmc catalyst particle that suspends in the polyether glycol crude product without purification process tiny (between 50～2000nm), be difficult to pass through conventional filtration means or centrifugation means with its direct separation, therefore need a kind of separation means efficiently come the purifying polyether glycol.
U.S. Pat 2004/0267056 has been reported the method that adopts ultrafiltration or micro-filtration means to come the purifying polyether glycol, utilizes ceramic membrane or polyvinylidene fluoride film (PVDF) etc. to remove by filter dmc catalyst in the polyether glycol crude product for separatory membrane.The polyether glycol product dmc catalyst residual quantity that obtains is lower, appearance transparent.But this method is along with the continuous operation of purge process, and dmc catalyst concentration constantly increases in the polyether glycol, and the flux of separatory membrane will successively decrease gradually, thereby has reduced separation efficiency, and isolated dmc catalyst can not directly be continued to use.
Summary of the invention
The flux rate of decline that the object of the present invention is to provide a kind of separatory membrane is slow, dmc catalyst is recyclable and the method for the ultrafiltration and purification of polyether glycol crude product that direct continuation is used.
Technical scheme of the present invention is as follows:
A kind of method of ultrafiltration and purification of polyether glycol crude product, it is made up of the following step basically:
Step 1. contains synthetic the polyether glycol crude product of bimetallic cyaniding complex (DMC) catalyzer through interchanger heat exchange input crude product storage tank, makes the polyether glycol crude product remain on 50～220 ℃.The purpose that makes the polyether glycol crude product remain on 50～220 ℃ is in order to make viscosity of polyether drop to 80.0mm
2Below/the s, at the flux that can improve separating effect and separatory membrane (mineral membrane or sintering metal micropore tubular membrane) than the catalyzer in the separation polyether glycol crude product under the low-viscosity;
When step 3. is increased to 500～30000ppm when the catalyst concn of the polyether glycol in the crude product storage tank, close the valve that the crude product storage tank leads to ultrafiltration apparatus, open the valve that the crude product storage tank leads to synthesizer, catalyzer is recovered direct continuation and uses.
The method of above-mentioned purifying polyether glycol crude product, the described separatory membrane of step 2 are ultra-filtration membrane or the microfiltration membrane that contains single or several passages, and material is mineral membrane or sintering metal micropore tubular membrane, and the aperture is 0.05～1.2 μ m.
The method of above-mentioned purifying polyether glycol crude product, pipe pressure is in 0.02～4.0MPa (gauge pressure in the separatory membrane passage, down together), separatory membrane pipe pressure at two ends difference can be by the operating pressure of valve regulated fluid in separatory membrane at described ultrafiltration apparatus two ends between 0.002～1.0MPa.
The method of above-mentioned purifying polyether glycol crude product, in the new equipment entry into service stage, catalyst content in the described filtrate of step 2 may overshoot amount (in the polyether glycol finished product under the catalyzer metal ion total content be no more than 2.0ppm), can fail back filtrate the crude product storage tank this moment, after running for some time, the micropore that the part of described separatory membrane is bigger can be stopped up by catalyzer, and after this catalyst content in the filtrate will reach requirement.
The method of above-mentioned purifying polyether glycol crude product, described ultrafiltration apparatus is connected with back-purge system, described separatory membrane is after running after a while, the part micropore of separatory membrane is stopped up by catalyzer, the flux of separatory membrane descends, can recoil to separatory membrane by back-purge system this moment with the polyether glycol that contains dmc catalyst hardly, the temperature of pure polyether glycol backwash liquid remains between 50～220 ℃, recoil pressure reaches between 0.2～10MPa fast in this recoil system, time length of once recoiling is 1～180 second, and its frequency remains on 1 * 10
-3Between～the 0.1Hz, the fine and close dirty layered catalyst that is attached on separation membrane surface becomes loose under the recoil effect of the quick backwash liquid of high pressure, is brought into the material circulation by high-velocity fluid, makes separatory membrane return to bigger flux.
The inventive method can (wherein the Zn ion content be 6.24～207.8ppm with containing dmc catalyst 30～1000ppm, the Co ion content is that 1.57～52.25ppm) polyether glycol crude product is treated to ultrapure polyether glycol product (Zn ion and Co ion total content are lower than 2.00ppm), and the dmc catalyst of recovery can directly continue on for synthesizing polyether glycol.Constant basically with its character of dmc catalyst synthetic polyether glycol that reclaims.
Description of drawings
Fig. 1 is the skeleton diagram of polyether glycol purification system flow process;
Fig. 2 is the The decline of membrane flux situation map that embodiment 1 separatory membrane is handled polyether glycol crude product A;
Fig. 3 is the The decline of membrane flux situation map that embodiment 2 separatory membranes are handled polyether glycol crude product B.
Embodiment
The experiment condition of embodiment:
The flow process of the method for ultrafiltration and purification of polyether glycol of the present invention as shown in Figure 1;
Ultrafiltration purification system: tightness system;
Polyether glycol crude product: 1000～8000Da, pH:5～8;
Treatment temp: 50～220 ℃;
Pipe pressure is between 0.02～4.0MPa in the separatory membrane passage, and separatory membrane pipe pressure at two ends difference is between 0.002～1.0MPa;
The pressure of (the separatory membrane pipe is outer) is between 0.001～0.2MPa in the ultrafiltration apparatus shell.
Recoil pressure between 0.2～10MPa,
Once recoil the time length between 1～180 second,
The recoil frequency remains on 1 * 10
-3Between～the 0.1Hz,
Separatory membrane is recoiled by back-purge system with the polyether glycol that is substantially free of catalyzer, the temperature of pure polyether glycol backwash liquid remains between 50～220 ℃.
The separatory membrane structure:
Multichannel micro-pore-film filtration precision: between 0.05～1.2um, port number has 19,
Separatory membrane external diameter: 31mm, separatory membrane internal diameter: 3.6mm,
Filtration area: 0.1m
2,
The internal diameter of ultrafiltration apparatus separating film module shell: 38mm.
Separatory membrane material and preparation method
Use mineral membrane or metallic membrane to come purifying polyether glycol crude product among the present invention
1, the supporter of mineral membrane is α-Al
2O
3Class coating material is Al
2O
3, ZrO
2The general preparation method of mineral membrane: the coating liquid that intermediate product-the nucleus particle suspension liquid is made (comprising dispersion agent, thickening material, defoamer and sanitas etc.) that wet chemistry method is prepared superfine powder technology is filmed or is sticked on porous metal or the porous ceramic support.Wet film is after drying oven dry, in specified temp (600～800 ℃) roasting moulding down.Its preparation method can be with reference to patent CN1443597.
2, the supporter of metallic membrane is a Porous Stainless Steel; Class coating material is TiO
2(the sintering metal micropore tubular membrane that used metallic membrane provides for baud mineral membrane separating device company limited)
Embodiment 1:
The polyether glycol crude product A[number-average molecular weight of synthetic 50Kg is 3000 ± 100, (Mn), down with], wherein dmc catalyst content 200ppm (handle raw material ions content: Zn:41.56ppm, Co:10.45ppm),
Fluid temperature (F.T.): 120 ℃, viscosity: 32.20mm
2/ s,
Mineral membrane: 0.13um,
Separatory membrane passage pressure at two ends difference: 0.5MPa, 0.4MPa,
The pressure that the separatory membrane pipe is outer: 0.001MPa,
Metal ion content in the filtrate: Zn:1.02ppm Co:＜0.20ppm,
The content of the metallic element in the polyether glycol (Zn and Co) all uses atomic absorption spectrophotometer (AA) to measure (down together),
The flux of separatory membrane drops to 17.2Lh behind the lasting 1.0h of filtration
-1M
-2, therefore recoil.Use pure polyether glycol to recoil, recoil pressure reaches 1.0MPa fast, once recoils 20 seconds time length; The recoil frequency remains on 1 * 10
-2Hz, the temperature of pure polyether glycol backwash liquid remains on 120 ℃.After the recoil, the flux of separatory membrane returns to 19.1Lh
-1M
-2
Embodiment 2:
The polyether glycol crude product B (number-average molecular weight is 2000 ± 100) of synthetic 50Kg, wherein dmc catalyst content 200ppm (handle raw material ions content: Zn:41.56ppm, Co:10.45ppm),
Fluid temperature (F.T.): 120 ℃, viscosity: 20.00mm
2/ s,
Mineral membrane: 0.13um,
Separatory membrane passage pressure at two ends difference: 0.5MPa, 0.4MPa,
The pressure that the separatory membrane pipe is outer: 0.001MPa,
Metal ion content in the filtrate: Zn:0.80ppm, Co:＜0.20ppm,
The flux of separatory membrane drops to 19.4Lh behind the lasting 1.0h of filtration
-1M
-2, therefore recoil.Use pure polyether glycol to recoil, recoil pressure reaches 1.0MPa fast, and the time length of once recoiling is 20 seconds; The recoil frequency remains on 1 * 10
-2Hz, the temperature of pure polyether glycol backwash liquid remains on 120 ℃.After the recoil, the flux of separatory membrane returns to 22.0Lh
-1M
-2
Embodiment 3:
The polyether glycol crude product C (number-average molecular weight is 8000 ± 100) of synthetic 50Kg, wherein dmc catalyst content 200ppm (handle raw material ions content: Zn:41.56ppm, Co:10.45ppm),
Fluid temperature (F.T.): 220 ℃, viscosity: 74.42mm
2/ s,
Mineral membrane: 0.13um,
Separatory membrane passage pressure at two ends difference: 4.0MPa, 3.0MPa,
The pressure that the separatory membrane pipe is outer: 0.2MPa,
Metal ion content in the filtrate: Zn:1.18ppm, Co:＜0.20ppm,
The flux of separatory membrane drops to 20.6Lh behind the lasting 0.5h of filtration
-1M
-2, therefore recoil.Use pure polyether glycol to recoil, recoil pressure reaches 10.0MPa fast, and the time length of once recoiling is 180 seconds; The recoil frequency remains on 1 * 10
-3Hz, the temperature of pure polyether glycol backwash liquid remains on 220 ℃.After the recoil, the flux of separatory membrane returns to 24.0Lh
-1M
-2
Embodiment 4:
The polyether glycol crude product A (number-average molecular weight is 2000 ± 100) of synthetic 50Kg, wherein dmc catalyst content 200ppm (handle raw material ions content: Zn:41.56ppm, Co:10.45ppm),
Fluid temperature (F.T.): 50 ℃, viscosity: 79.5mm
2/ s,
Mineral membrane: 0.13um,
Separatory membrane passage pressure at two ends difference: 1.0MPa, 0.8MPa,
The pressure that the separatory membrane pipe is outer: 0.01MPa;
Metal ion content in the filtrate: Zn:1.10ppm, Co:＜0.20ppm,
The flux of separatory membrane drops to 9.5Lh behind the lasting 1.0h of filtration
-1M
-2, therefore recoil.Use pure polyether glycol to recoil, recoil pressure reaches 2.0MPa fast, and the time length of once recoiling is 1 second; The recoil frequency remains on 0.1Hz, and the temperature of pure polyether glycol backwash liquid remains on 50 ℃.After the recoil, the flux of separatory membrane returns to 11.0Lh
-1M
-2
Embodiment 5:
The polyether glycol crude product A (number-average molecular weight is 3000 ± 100) of synthetic 50Kg, wherein dmc catalyst content 200ppm (handle raw material ions content: Zn:41.56ppm, Co:10.45ppm),
Fluid temperature (F.T.): 180 ℃, viscosity: 16.40mm
2/ s,
Mineral membrane: 0.13um,
Separatory membrane passage pressure at two ends difference: 0.5MPa, 0.4MPa,
The pressure that the separatory membrane pipe is outer: 0.05MPa,
Metal ion content in the filtrate: Zn:0.85ppm, Co:＜0.20ppm,
The flux of separatory membrane drops to 21.5Lh behind the lasting 1.0h of filtration
-1M
-2, therefore recoil.Use pure polyether glycol to recoil, recoil pressure reaches 0.8MPa fast, and the time length of once recoiling kept 150 seconds; The recoil frequency remains on 1 * 10
-3Hz, the temperature of pure polyether glycol backwash liquid remains on 180 ℃.After the recoil, the flux of separatory membrane returns to 24.3Lh
-1M
-2
Embodiment 6:
The polyether glycol crude product D (number-average molecular weight is 1000 ± 100) of synthetic 50Kg, wherein dmc catalyst content 200ppm (handle raw material ions content: Zn:41.56ppm, Co:10.45ppm),
Fluid temperature (F.T.): 80 ℃, viscosity: 20.05mm
2/ s,
Mineral membrane: 0.13um,
Separatory membrane passage pressure at two ends difference: 0.022MPa, 0.02MPa,
The pressure that the separatory membrane pipe is outer: 0.001MPa,
Metal ion content in the filtrate: Zn:1.02ppm, Co:＜0.20ppm,
The flux of separatory membrane drops to 1.20Lh behind the lasting 3.0h of filtration
-1M
-2, therefore recoil.Use pure polyether glycol to recoil, recoil pressure reaches 0.2MPa fast, and the time length of once recoiling kept 60 seconds; The recoil frequency remains on 1 * 10
-3Hz, the temperature of pure polyether glycol backwash liquid remains on 80 ℃.After the recoil, the flux of separatory membrane recovers 1.27Lh
-1M
-2
Embodiment 7:
The polyether glycol crude product A (number-average molecular weight is 3000 ± 100) of synthetic 50Kg, wherein dmc catalyst content 200ppm (handle raw material ions content: Zn:41.56ppm, Co:10.45ppm),
Fluid temperature (F.T.): 180 ℃, viscosity: 16.40mm
2/ s,
Mineral membrane: 0.13um,
Separatory membrane passage pressure at two ends difference: 0.5MPa, 0.4MPa,
The pressure that the separatory membrane pipe is outer: 0.05MPa,
Metal ion content in the filtrate: Zn:0.97ppm, Co:＜0.20ppm,
The flux of separatory membrane drops to 21.5Lh behind the lasting 1.0h of filtration
-1M
-2, therefore recoil.Use pure polyether glycol to recoil, recoil pressure reaches 2.0MPa fast, and the time length of once recoiling kept 40 seconds; The recoil frequency remains on 1 * 10
-3Hz, the temperature of pure polyether glycol backwash liquid remains on 180 ℃.After the recoil, the flux of separatory membrane returns to 24.5Lh
-1M
-2
Embodiment 8:
The polyether glycol crude product A (number-average molecular weight is 3000 ± 100) of synthetic 50Kg, wherein dmc catalyst content 200ppm (handle raw material ions content: Zn:41.56ppm, Co:10.45ppm),
Fluid temperature (F.T.): 120 ℃, viscosity: 32.20mm
2/ s,
Sintering metal micropore tubular membrane: 0.3um,
Separatory membrane passage pressure at two ends difference: 0.5MPa, 0.4MPa,
The pressure that the separatory membrane pipe is outer: 0.001MPa,
Metal ion content in the filtrate: Zn:1.22ppm, Co:0.40ppm,
The flux of separatory membrane drops to 20.2Lh behind the lasting 2.5h of filtration
-1M
-2, therefore recoil.Use pure polyether glycol to recoil, recoil pressure reaches 1.0MPa fast, and the time length of once recoiling kept 60 seconds; The recoil frequency remains on 1 * 10
-3Hz, the temperature of pure polyether glycol backwash liquid remains on 120 ℃.After the recoil, the flux of separatory membrane returns to 22.5Lh
-1M
-2
Catalyzer is used to polyreaction synthetic polyether glycol physical data once more
| PPG | Initiator | Temperature of reaction (℃) | Induction time (min) | Double bond content (molkg -1) | Viscosity (25 ℃) (mpaS) | Mw/Mn |
| A B | A 1 B 1 | 145 145 | 1.5 1.0 | 0.0050 0.0045 | 580-600 380-400 | 1.15～1.17 1.11～1.12 |
Annotate: the Mw-weight-average molecular weight
The Mn-number-average molecular weight
Feed ratio:
B (containing dmc catalyst 1000ppm)/B
1(molecular weight is 400)=5/4;
A (containing dmc catalyst 1000ppm)/A
1(molecular weight is 500)=3/2.
Claims (8)
1. the method for a ultrafiltration and purification of polyether glycol crude product is characterized in that it is made up of the following step basically:
Step 1. contains synthetic the polyether glycol crude product of double metal cyanide catalyst through interchanger heat exchange input crude product storage tank, makes the polyether glycol crude product remain on 50～220 ℃;
Step 2. is with the input of the polyether glycol crude product in crude product storage tank ultrafiltration apparatus, ultrafiltration apparatus is formed by the piped separatory membrane with the concentric tube-like envelope of tubular separation membrane, the polyether glycol crude product enters in the tubular separation membrane, the part polyether glycol sees through the micropore diameter of separatory membrane and discharges to cross-flow, enter the tube-like envelope of ultrafiltration apparatus, the filtrate that enters tube-like envelope is for containing the polyether glycol of double metal cyanide catalyst hardly, input finished product jar, the catalyzer that does not see through the polyether glycol of separatory membrane and wherein be retained down is then by being failed back the crude product storage tank behind the ultrafiltration apparatus, constantly circulation, the catalyst concn of the polyether glycol in the crude product storage tank constantly increases;
When step 3. is increased to 500～30000ppm when the double metal cyanide catalyst concentration of the polyether glycol in the crude product storage tank, close the crude product storage tank and lead to the valve of ultrafiltration apparatus, open the valve that the crude product storage tank leads to synthesizer, catalyzer is recovered direct continuation and uses.
2. the method for purifying polyether glycol crude product according to claim 1, it is characterized in that: the described separatory membrane of step 2 is ultra-filtration membrane or the microfiltration membrane that contains single or several passages, material is mineral membrane or sintering metal micropore tubular membrane, and the aperture is 0.05～1.2 μ m.
3. the method for purifying polyether glycol crude product according to claim 1 is characterized in that: the described polyether glycol crude product of step 1 remains on 80～180 ℃;
4. the method for purifying polyether glycol crude product according to claim 1, it is characterized in that: pipe pressure is between 0.02～4.0MPa in the separatory membrane passage, separatory membrane pipe pressure at two ends difference between 0.002～1.0MPa, the operating pressure of valve regulated fluid in separatory membrane at the two ends by described ultrafiltration apparatus.
5. the method for purifying polyether glycol crude product according to claim 1, it is characterized in that: pipe pressure is between 0.1～3.0MPa in the separatory membrane passage, separatory membrane pipe pressure at two ends difference between 0.01～0.3MPa, the operating pressure of valve regulated fluid in separatory membrane at the two ends by described ultrafiltration apparatus.
6. the method for purifying polyether glycol crude product according to claim 1, it is characterized in that: in the new equipment entry into service stage, the amount of the catalyst content meeting overshoot in the described filtrate of step 2, fail back crude product storage tank with filtrate this moment, after running for some time, the micropore that the part of described separatory membrane is bigger can be stopped up by catalyzer, and after this catalyst content in the filtrate will reach requirement, input finished product jar.
7. the method for purifying polyether glycol crude product according to claim 1, it is characterized in that: described ultrafiltration apparatus is connected with back-purge system, described separatory membrane is after running after a while, the part micropore of separatory membrane is stopped up by catalyzer, the flux of separatory membrane descends, to separatory membrane recoil by back-purge system with the polyether glycol that is substantially free of catalyzer this moment, the temperature of pure polyether glycol backwash liquid remains between 50～220 ℃, the fine and close dirty layered catalyst that is attached on separation membrane surface becomes loose under the effect of the quick backwash liquid recoil of high pressure, brought into the material circulation by high-velocity fluid, make separatory membrane return to bigger flux.
8. the method for purifying polyether glycol crude product according to claim 5 is characterized in that: recoil pressure can reach between 0.2～10MPa fast in the described recoil system, and the time length of once recoiling is 1～180 second, and its frequency remains on 1 * 10
-3Between～the 0.1Hz.
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|---|---|---|---|
| CN 200610040557 CN1884340A (en) | 2006-05-24 | 2006-05-24 | Process for ultrafiltration and purification of polyether glycol |
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|---|---|---|---|
| CN 200610040557 CN1884340A (en) | 2006-05-24 | 2006-05-24 | Process for ultrafiltration and purification of polyether glycol |
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ID=37582655
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102002155A (en) * | 2010-10-21 | 2011-04-06 | 句容宁武高新技术发展有限公司 | Device for removing low boiling point matters in polyether polyol |
| CN102286148A (en) * | 2011-06-10 | 2011-12-21 | 南京理工大学 | Method and device for refining polyether polyol by membrane separation |
-
2006
- 2006-05-24 CN CN 200610040557 patent/CN1884340A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102002155A (en) * | 2010-10-21 | 2011-04-06 | 句容宁武高新技术发展有限公司 | Device for removing low boiling point matters in polyether polyol |
| CN102286148A (en) * | 2011-06-10 | 2011-12-21 | 南京理工大学 | Method and device for refining polyether polyol by membrane separation |
| CN102286148B (en) * | 2011-06-10 | 2013-05-08 | 南京理工大学 | Method and device for refining polyether polyol by membrane separation |
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