CN114316094B - Method for removing residual catalyst after polymer hydrogenation - Google Patents
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Abstract
The invention relates to the technical field of catalyst removal after hydrogenation of unsaturated polymers, in particular to a method for removing residual catalyst after hydrogenation of polymers by using a countercurrent continuous extraction technology. The glue solution and the extract liquid after the polymer to be treated is hydrogenated are subjected to countercurrent continuous extraction, so that the glue solution and the extract liquid are in high-speed inverse mixing contact and are rapidly centrifugally separated under the drive of a centrifuge drum, and the residual catalyst in the glue solution is removed. Compared with the existing removal method, the method is simpler and more efficient, the annular gap type countercurrent extractor is driven by the rotary drum to complete rapid and efficient separation, and can be connected in series in multiple stages to realize continuous removal, reduce the waste water amount and improve the removal rate, so that the nickel content in the hydrogenated styrene-conjugated diene copolymer glue solution is reduced to below 10 ppm.
Description
Technical Field
The invention relates to the technical field of catalyst removal after hydrogenation of unsaturated polymers, in particular to a method for removing residual catalyst after hydrogenation of polymers by using a countercurrent continuous extraction technology.
Background
Unsaturated polymers are active in chemical properties and poor in thermal, oxygen stability and ageing resistance, so that unsaturated bonds are saturated by a hydrogenation method, and environmental stability is improved. The hydrogenation method of the homogeneous solution catalyst represented by nickel, aluminum, cobalt and metallocene is a method commonly used in the industry at present, and has the advantages of high hydrogenation selectivity, mild reaction conditions, low catalyst dosage, simple synthesis and low cost, but compared with a heterogeneous catalyst, the homogeneous catalyst has the defect of difficult separation and removal. The residual metal catalyst after hydrogenation not only affects the appearance of the product, but also affects the physical and chemical properties of the product such as weather resistance, thermo-oxidation resistance, aging resistance and the like.
The nickel/aluminum catalytic hydrogenation system is widely applied to the hydrogenation reaction of the polymer due to the advantages of high selectivity, low price, high hydrogenation efficiency and the like. The removal of metal residues in the system is mainly divided into wet and dry methods. U.S. patent No. 3780138 discloses a method for removing metal residues by a wet method using citric acid, firstly oxidizing a glue solution by using an oxidant such as oxygen, hydrogen peroxide or acyl peroxide, dissolving metals by using a citric acid aqueous solution containing lower alcohol, standing and separating an organic phase and a water phase to realize metal separation, firstly adding the oxidant and then adding citric acid, wherein the removal rate of a metal nickel catalyst in the glue solution with the mass fraction of 12% is 98%, and although the removal rate meets the requirement, emulsification easily occurs, and the two phases cannot be thoroughly separated by standing and sedimentation. Another typical wet removal is a dicarboxylic acid method, wherein firstly an oxidizing agent is added, the metal is oxidized to a high valence state, then dicarboxylic acid is added to react with metal ions to generate a precipitate, and finally metal residues are removed by centrifugal separation. US patent 4595749 uses lower aliphatic alcohols such as methanol, ethanol, isopropanol as solubilizer, chinese patent CN106749782a adds hydrochloric acid during the polymer oxidation stage, but the removal rate of the corresponding scheme is not obvious or the concentration of the treated object is low.
Dry separation is the addition of a reagent to the hydrogenated polymer solution that contains no or only a small amount of water, which reagent reacts with the metal ions in the polymer solution to form a precipitate that is insoluble in the polymer solution, and the precipitate containing the metal residues is separated by separation means. US patent US5089541 incorporates acid washed lignite-based activated carbon and US5104972 employs diatomaceous earth. The metal ions were removed by using activated clay from Kuraray corporation of japan. The reaction process shows that the residual book ions in the polymer solution are further removed after centrifugal separation, but when the oxidized and acid-washed military solution is continuously treated by a centrifugal machine, the requirement on equipment of the centrifugal machine is higher and the investment is correspondingly larger because the density difference between the metal ions in the polymer solution and the polymer solution is smaller.
However, wet separation has the problems of easy emulsification, small density difference between precipitation and glue solution and poor phase separation. The dry separation has the problems of long precipitation time and unsatisfactory removal effect on the glue solution with larger viscosity. And both the two require a centrifuge to realize phase separation, and can only realize one-time separation, and particularly when the polymer viscosity is higher, the density difference between metal ions in the polymer solution and the polymer solution is smaller, the requirement on centrifuge equipment is higher, and the equipment investment cost is increased.
Patent CN 108341898A discloses a process for removing the catalyst after hydrogenation of unsaturated polymers comprising: standing and layering the hydrogenated polymer solution to obtain a water phase and an oil phase respectively; and then the oil phase is further separated from the material inlet pipe into the hydrocyclone, the hydrogenated polymer obtained by separation is led out from the overflow pipe, part of the obtained hydrogenated polymer is circularly led into the hydrocyclone, and the mass flow rate ratio of the residual hydrogenated polymer as qualified hydrogenated polymer is (1.2-1.6): 1. The method has the advantages that the glue solution is easy to emulsify after oxidation and acid washing, the standing layering phase separation effect is poor, the method belongs to intermittent operation, continuous removal cannot be realized, and the removal effect of the glue solution with higher viscosity can be influenced.
Disclosure of Invention
The invention provides a method for removing residual catalyst after polymer hydrogenation by using a countercurrent continuous extraction technology in order to make up for the defects in the prior art.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the method for removing residual catalyst after polymer hydrogenation is characterized by that the glue solution after polymer hydrogenation to be treated and extract liquor are passed through the countercurrent continuous extraction mode, and passed through the high-speed countercurrent mixing contact and quick centrifugal separation so as to remove residual catalyst in the glue solution.
The countercurrent continuous extraction mode is to treat the glue solution by adopting at least one annular space type centrifugal extractor.
The countercurrent continuous extraction mode is to improve the extraction efficiency through multistage series connection, wherein the number of stages is 1-20 stages, preferably 3-8 stages.
The glue solution and the extract are pumped into the annular centrifugal extractor from the feed inlets at two ends of the annular centrifugal extractor respectively, and are in high-speed inverse mixing contact and quick centrifugal separation under the drive of the centrifugal drum, so that the glue solution and the extract are discharged from the corresponding light and heavy two-phase discharge ports respectively, and further the removal of residual catalyst in the glue solution is realized.
The extract is water or acid solution; wherein the concentration of the acid solution is 0.1-10%; the acid is an aqueous solution of inorganic acid or organic acid which is easy to dissolve in water, and the inorganic acid is hydrochloric acid, sulfuric acid or phosphoric acid; the organic acid which is easily soluble in water is citric acid.
The feeding port glue solution and the extraction liquid are pumped at the flow rate of 1-50mL/min, and more preferably 5-30mL/min.
The ratio of the flow rate of the extract to the hydrogenated styrene-conjugated diene copolymer gum solution is 1:0.5-5, preferably 1:0.5-1.5.
The annular space centrifugal extractor has a centrifugal rate of 1500-10000rpm, more preferably 4000-8000rpm. The extraction temperature is 20-90 ℃, preferably 50-80 ℃. The mass fraction of the glue solution is 1-20 wt%, preferably 5-15 wt%. The single stage residence time is 1 to 10min, preferably 2 to 5min.
The invention has the advantages that:
the invention overcomes the technical defects of high cost and low efficiency of the prior art that a centrifuge is needed to treat oxidized and pickled polymer solution when the residual catalyst after the unsaturated polymer hydrogenation is removed, and further provides a method for removing the residual catalyst after the unsaturated polymer hydrogenation, which has simple operation, low cost and high efficiency; the method is characterized in that the countercurrent continuous extractor is driven by a high-speed rotary drum of the annular gap countercurrent extractor to realize high-efficiency and rapid mixing of the hydrogenated polymer glue solution and the extraction liquid, so that emulsification is avoided, the contact quantity and the residence time of the glue solution and the extraction liquid are controlled by adjusting the flow velocity and the two-phase flow velocity ratio of the glue solution and the extraction liquid, and the waste water quantity is reduced. Meanwhile, the series connection of the extractors can realize multistage countercurrent extraction, improve the removal rate and realize continuous removal.
Detailed Description
The following examples are intended to further illustrate the invention, but not to limit it. The embodiments described below are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to fall within the scope of the invention.
The method pumps the oxidized styrene-conjugated diene copolymer glue solution and the extract solution into an annular space type centrifugal extractor from feed inlets at two ends respectively at a certain flow rate, and the two are reversely mixed and contacted at high speed and are rapidly centrifugally separated under the drive of a centrifugal drum, and the obtained hydrogenated styrene-conjugated diene copolymer glue solution and the extract solution are discharged from corresponding light and heavy two-phase discharge outlets respectively after catalyst removal. According to the invention, the annular gap type countercurrent extractor is driven by the rotary drum to enable the styrene-conjugated diene copolymer glue solution to be rapidly, simply, conveniently and efficiently separated, countercurrent continuous extraction is carried out to enable the glue solution and the extract to be efficiently and rapidly mixed and then separated at a certain flow rate, emulsification can be avoided, and meanwhile, continuous operation is carried out. And a plurality of devices can be connected in series in multiple stages according to the treatment requirement, so that continuous removal is realized, the waste water amount is reduced, the removal rate is improved, and the nickel content in the hydrogenated styrene-conjugated diene copolymer glue solution can be further reduced to below 10 ppm.
Example 1
The base gum before hydrogenation is SIBR copolymer. The unsaturated copolymer is prepared in cyclohexane solution, and a star polymer is synthesized by using n-butyllithium as an initiator, styrene, isoprene and butadiene as polymerization monomers and divinylbenzene as a coupling agent. After polymerization, hydrogenation is carried out by using a nickel catalyst, the catalyst dosage is 0.1gNi/100g of polymer, the reaction temperature is 60 ℃, the hydrogenation pressure is 2.5MPa, and the stirring speed is 800rpm/min for 2 hours. The degree of hydrogenation of the hydrogenated polymer was 99.3% as measured by the iodometry method.
Oxidizing the hydrotreated glue solution under the following conditions: taking 500mL of hydrogenated styrene-conjugated diene copolymer glue solution, the concentration is 5.0% (wt), the reaction temperature is 60 ℃, the rotating speed is 1000rpm/min, the normal pressure is adopted, and 30wt% of H is added 2 O 2 25mL, oxidized for 30min.
After oxidation, adopting countercurrent extraction, connecting 4 annular gap countercurrent extractors in series to realize countercurrent continuous extraction of oxidized glue solution, taking 5.0% (wt) hydrogenated styrene-conjugated diene copolymer glue solution with the concentration of oxidized glue solution as a light phase, 2.0wt% citric acid aqueous solution extractant as a heavy phase, pumping the glue solution into a feed inlet at the flow rate of 10mL/min, the flow rate ratio of the extractant to the hydrogenated styrene-conjugated diene copolymer glue solution is 1:1, the centrifugal speed is 5000rpm, the extraction temperature is 60 ℃, the reaction stage number is 4, and the single-stage residence time is 2min. And (5) carrying out countercurrent extraction to obtain a glue solution, precipitating the glue solution with ethanol, and carrying out vacuum drying. The dry gel samples were tested by plasma emission spectroscopy and the residual nickel and aluminum contents are shown in table 1.
Example 2
This example was conducted in a similar manner to example 1 except that the concentration of the hydrogenated styrene-conjugated diene copolymer gum solution in this example was 8.0% by weight. And (5) carrying out countercurrent extraction to obtain a glue solution, precipitating the glue solution with ethanol, and carrying out vacuum drying. The dry gel samples were tested by plasma emission spectroscopy and the residual nickel and aluminum contents are shown in table 1.
Example 3
This example was conducted in a similar manner to example 1 except that the concentration of the hydrogenated styrene-conjugated diene copolymer gum solution in this example was 10.0% by weight. And (5) carrying out countercurrent extraction to obtain a glue solution, precipitating the glue solution with ethanol, and carrying out vacuum drying. The dry gel samples were tested by plasma emission spectroscopy and the residual nickel and aluminum contents are shown in table 1.
Example 4
This example was conducted in a similar manner to example 1 except that the concentration of the hydrogenated styrene-conjugated diene copolymer gum solution in this example was 12.0% by weight. And (5) carrying out countercurrent extraction to obtain a glue solution, precipitating the glue solution with ethanol, and carrying out vacuum drying. The dry gel samples were tested by plasma emission spectroscopy and the residual nickel and aluminum contents are shown in table 1.
Example 5
This example was conducted in a similar manner to example 1 except that the concentration of the hydrogenated styrene-conjugated diene copolymer gum solution in this example was 15.0% by weight. And (5) carrying out countercurrent extraction to obtain a glue solution, precipitating the glue solution with ethanol, and carrying out vacuum drying. The dry gel samples were tested by plasma emission spectroscopy and the residual nickel and aluminum contents are shown in table 1.
Table 1 shows the effect of examples 1-5 on the separation effect by treating different polymer concentrations (or viscosities)
| Polymer gum solution concentration after hydrogenation (%) | 5.0 | 8.0 | 10.0 | 12.0 | 15.0 |
| Viscosity (cps) of hydrogenated polymer gum | 136.0 | 180.0 | 270.5 | 366.4 | 510.0 |
| Residual Ni (ppm) | 1.5 | 3.0 | 8.0 | 9.0 | 9.6 |
| Residual Al (ppm) | 5.0 | 7.0 | 16.0 | 30.0 | 35.0 |
| Nickel removal Rate (%) | 99.9 | 99.7 | 99.2 | 99.1 | 99.0 |
As can be seen from the results in Table 1, the process according to the invention is suitable for polymer cement solutions of different viscosities. The glue solution and the extractant can be continuously pumped into the annular space type centrifugal extractor at a certain flow rate, and the glue solution and the extractant are reversely mixed at a high speed under the drive of a centrifugal drum, fully contact and are rapidly centrifugally separated, and a plurality of devices can be connected in series in multiple stages according to different viscosities of the glue solution, so that continuous removal is realized, and the removal rate is further improved; meanwhile, the method has a good removal effect on the high-viscosity polymer glue solution.
Example 6
This example was conducted in a similar manner to example 3 except that the feed dope was pumped at a flow rate of 5mL/min. And (5) carrying out countercurrent extraction to obtain a glue solution, precipitating the glue solution with ethanol, and carrying out vacuum drying. The dry gel sample was tested by plasma emission spectroscopy, and the residual nickel content of the sample was 2.0ppm and the residual aluminum content was 6.0ppm.
Example 7
This example was conducted in a similar manner to example 3 except that the feed dope was pumped at a flow rate of 20mL/min. And (5) carrying out countercurrent extraction to obtain a glue solution, precipitating the glue solution with ethanol, and carrying out vacuum drying. The dry gel sample was tested by plasma emission spectroscopy, and the residual nickel content of the sample was 8.0ppm and the residual aluminum content was 20.0ppm.
Example 8
This example was conducted in a similar manner to example 3 except that the ratio of the flow rates of the extract solution to that of the hydrogenated styrene-conjugated diene copolymer gum solution in this example was 1:1.2, and that the dry gum sample was tested by plasma emission spectroscopy, and the residual nickel content of the above sample was 7.0ppm and the residual aluminum content was 13.0ppm.
Example 9
This example was conducted in a similar manner to example 3 except that the ratio of the flow rates of the extract solution to that of the hydrogenated styrene-conjugated diene copolymer gum solution in this example was 1:3, and that the dry gum sample was tested by plasma emission spectroscopy, which had a residual nickel content of 8.7ppm and a residual aluminum content of 15.0ppm.
Example 10
Taking 500mL of hydrogenated styrene-conjugated diene copolymer glue solution, the concentration is 12.0% (wt), the reaction temperature is 60 ℃, the rotating speed is 1000rpm/min, the normal pressure is adopted, and 30wt% of H is added 2 O 2 25mL, oxidized for 30min.
After oxidation, adopting countercurrent extraction, connecting 4 annular gap countercurrent extractors in series to realize countercurrent continuous extraction of oxidized glue solution, taking 12.0% (wt) hydrogenated styrene-conjugated diene copolymer glue solution with the concentration of 12.0% (wt) after oxidation as a light phase, 2.0% citric acid aqueous solution extractant as a heavy phase, pumping the glue solution into a feed inlet at a flow rate of 5mL/min, the flow rate ratio of the extractant to the hydrogenated styrene-conjugated diene copolymer glue solution is 1:0.5, the centrifugal speed is 5000rpm, the extraction temperature is 60 ℃, the reaction stage number is 4, and the single-stage residence time is 5min. And (5) carrying out countercurrent extraction to obtain a glue solution, precipitating the glue solution with ethanol, and carrying out vacuum drying. The above sample had a residual nickel content of 9.8ppm and a residual aluminum content of 25.0ppm.
Example 9
This example was conducted in a similar manner to example 2 except that the countercurrent continuous extraction apparatus in this example was changed from 4-stage series to 8-stage series, and the plasma emission spectrum was conducted to test a dry gel sample having a residual nickel content of 1.0ppm and a residual aluminum content of 5.0ppm.
Example 10
This example was conducted in a similar manner to example 2 except that the single-stage residence time in this example was 5 minutes, and the plasma emission spectrum was conducted to test a dry gel sample having a residual nickel content of 1.0ppm and a residual aluminum content of 3.0ppm.
Example 11
This example was conducted in a similar manner to example 2 except that the dry gel sample was tested by plasma emission spectroscopy at a centrifugal speed of 8000rpm, and the residual nickel content of the above sample was 2.0ppm and the residual aluminum content was 5.0ppm.
Example 12
This example was conducted in a similar manner to example 2 except that the extraction temperature in this example was 80℃and the plasma emission spectrum was conducted to test a dry gel sample having a residual nickel content of 3.5ppm and a residual aluminum content of 8.5ppm.
Example 13
This example was conducted in a similar manner to example 1 except that the extract in this example was a 2.0wt% aqueous sulfuric acid solution, and the plasma emission spectrum was conducted to test a dry gel sample having a residual nickel content of 9.5ppm and a residual aluminum content of 32.0ppm.
Example 14
This example was conducted in a similar manner to example 1 except that the extract in this example was a 2.0wt% aqueous phosphoric acid solution, and the dry gel sample was tested by plasma emission spectroscopy for a residual nickel content of 9.0ppm and a residual aluminum content of 27.0ppm.
Comparative example 1
The base gum before hydrogenation is SIBR copolymer. The unsaturated copolymer is prepared in cyclohexane solution, and a star polymer is synthesized by using n-butyllithium as an initiator, styrene, isoprene and butadiene as polymerization monomers and divinylbenzene as a coupling agent. After polymerization, hydrogenation is carried out by using a nickel catalyst, the catalyst dosage is 0.1gNi/100g of polymer, the reaction temperature is 60 ℃, the hydrogenation pressure is 2.5MPa, and the stirring speed is 800rpm/min for 2 hours. The degree of hydrogenation of the hydrogenated polymer was 99.1% as measured by the iodometry method.
Taking 500mL of hydrogenated styrene-conjugated diene copolymer glue solution, the concentration is 10.0% (wt), the reaction temperature is 60 ℃, the rotating speed is 1000rpm/min, the normal pressure is adopted, and 30wt% of H is added 2 O 2 25mL, oxidized for 30min. The countercurrent continuous extraction technology treatment and the centrifugal treatment are not adopted, and only ethanol is adopted for gum precipitation and vacuum drying. The plasma emission spectrum tests a dry gel sample, containing 200ppm nickel ions and 384.6ppm aluminum ions.
As can be seen from the above examples and comparative examples, when the concentration of the hydrogenated polymer gum solution is 12%, the efficiency of removing residual nickel ions from the hydrogenated styrene-conjugated diene copolymer gum solution by the method of the invention can reach 99.1%, which is higher than the nickel ion removal rate 98% described in U.S. Pat. No. 3780138 described in the background art, and the nickel ion removal rate 80% described in comparative example 1, and the removal efficiency of the method for low-viscosity and high-viscosity gum solutions can reach more than 99%, thereby meeting the industry requirements, and the retention time is short, the removal rate is improved, continuous removal is realized, and the waste water is reduced.
Claims (3)
1. A process for removing residual catalyst after polymer hydrogenation, characterized by: the polymer to be treated is hydrogenated, then the glue solution is oxidized by hydrogen peroxide and is subjected to countercurrent continuous extraction with the extract, so that the polymer to be treated and the extract are in high-speed inverse mixing contact and are rapidly centrifugally separated under the drive of a centrifuge drum, and further, the residual catalyst in the glue solution is removed;
the countercurrent continuous extraction mode is to treat the glue solution by adopting at least one annular space type centrifugal extractor;
the extract is acid liquor;
the feeding port glue solution and the extract solution are pumped into the reactor at the flow rate of 1-50 mL/min;
the flow rate ratio of the extract liquid to the hydrogenated styrene-conjugated diene copolymer glue liquid is 1:0.5-5;
the centrifugal speed of the annular space type centrifugal extractor is 1500-10000 rpm;
the extraction temperature is 20-90 ℃;
the mass fraction of the glue solution is 1-20 wt%.
2. The process for removing residual catalyst from a hydrogenated polymer according to claim 1, wherein: the countercurrent continuous extraction mode is to improve the extraction efficiency through multistage series connection, and the number of stages is 1-20.
3. A process for removing residual catalyst after hydrogenation of polymers according to any one of claims 1-2, characterized in that: the glue solution and the extract are pumped into the annular centrifugal extractor from the feed inlets at two ends of the annular centrifugal extractor respectively, and are in high-speed inverse mixing contact and quick centrifugal separation under the drive of the centrifugal drum, so that the glue solution and the extract are discharged from the corresponding light and heavy two-phase discharge ports respectively, and further the residual catalyst in the glue solution is removed.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3780138A (en) * | 1971-09-14 | 1973-12-18 | Shell Oil Co | Method for separating metal contaminant from organic polymers |
| CN106337138A (en) * | 2016-11-03 | 2017-01-18 | 深圳市捷鑫资产管理有限公司 | Technology for preparing high-purity anhydrous lithium chloride through centrifugal extraction of salt lake brine |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3780138A (en) * | 1971-09-14 | 1973-12-18 | Shell Oil Co | Method for separating metal contaminant from organic polymers |
| CN106337138A (en) * | 2016-11-03 | 2017-01-18 | 深圳市捷鑫资产管理有限公司 | Technology for preparing high-purity anhydrous lithium chloride through centrifugal extraction of salt lake brine |
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