CN104072645B - A kind of method that residual metal catalyst is removed in the glue from hydrogenated polymers - Google Patents
A kind of method that residual metal catalyst is removed in the glue from hydrogenated polymers Download PDFInfo
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Abstract
The invention discloses a kind of method that residual metal catalyst is removed in glue from hydrogenated polymers, this method is in the glue formed by unsaturated polymer made from anionic polymerisation after catalytic hydrogenation reaction, oxidant is first added to occur to add carbon dioxide generation neutralization reaction after the completion of oxidation reaction, oxidation reaction；Or oxidant generation oxidation reaction is added in above-mentioned glue, while adding carbon dioxide occurs neutralization reaction；Finally centrifuge out precipitation；Or in the glue that unsaturated polymer made from free radical or cationic polymerization is formed after catalytic hydrogenation reaction, first add after organolithium, add oxidant and occur to add carbon dioxide generation neutralization reaction after the completion of oxidation reaction, oxidation reaction；Or after in above-mentioned glue first adding organolithium, add oxidant and occur oxidation reaction, while adding carbon dioxide occurs neutralization reaction；Finally centrifuge out precipitation；This method removing metallic catalyst residue is more thorough, more environmentally friendly, safer, be more easy to industrialization；Aluminum ions removing is particularly suitable for use in polymer.
Description
Technical field
The present invention relates to a kind of method that residual metal catalyst is removed in glue from hydrogenated polymers, belong to polymer pure
Change field.
Background technology
The homopolymer or conjugated diene and the copolymer of vinyl-arene of some polymer, such as conjugated diene, in molecule knot
The unsaturated bond existed in structure in unsaturated double-bond, polymer has intolerance to environmental factors such as light, heat, oxygen, ozone, because
This makes unsaturated bond saturation frequently with the method for hydrogenation, makes it have more preferable environmental stability and heat endurance.Polymer adds
Hydrogen methods in the prior art, are carried out, used catalyst is usually group VIII metal generally in the presence of heavy metal catalyst
（Cobalt, nickel, iron）Organo-metallic compound and reducing agent（Organo-aluminium, organo-lithium compound）.Metallic catalyst residue not only shadow
Weather-proof, heat-resisting polymer, oxytolerant, ageing-resistant performance are rung, and has certain harm to human body, it is therefore necessary to is removed in polymer
A small amount of metallic residue.
Remove catalyst metals residue a kind of typical method used in the prior art be polymer solution or
In emulsion, oxidant and the aqueous solution of organic acid are used.United States Patent (USP) U.S.3780138 discloses a kind of removing residual metal and urged
The method of agent, the metal ion in polymerizate is extracted using oxidant and dilute aqueous citric acid solution and lower aliphatic alcohols.
This method needs a large amount of extractants, and extraction time is long, is separated difficult, treatment process is complicated, long flow path, easily causes environment dirty
Dye.
A kind of method that metallic catalyst is removed during glue from polymer is disclosed in United States Patent (USP) U.S.4595749, is adopted
With oxidant and dicarboxylic acids, lower aliphatic alcohols（Carbon number is less than 4）Or toluene is used as the solvent of dicarboxylic acids.Using oxidant and
The dicarboxylic acid solution dissolved in advance with solution handles polymer glue, makes wherein residual metal catalyst formation insoluble petal
Compound, is isolated, so as to reach the purpose of removing residual metal catalyst.It is higher to polymer latex fluid viscosity using this method
When, removal effect is undesirable.And this method introduces other solvents, adds solvent recovery step.
A kind of removing of unsaturated polymer residure after hydrogenation treatment metallic catalyst is disclosed in Chinese patent 92105370.3
Method, using oxidant and dicarboxylic acids, dicarboxylic acids is with many alkyl diol ether compounds as solubilizer, and many alkyl diol etherificates are closed
The formula of thing is R1-O-[R2-O]-nR3Wherein n is 1,2,3 or 4；R1For H or alkyl, carbon number is 1-8 when being alkyl；R2
It is the alkyl of carbon number 2-5；R3It is the alkyl of carbon number 1-8.The consumption and metal ion of dicarboxylic acids in this method
Mol ratio be 1-20, make aqueous phase in glue in acidity, equipment corrosion be used for a long time serious.
Chinese patent 201110195915.9 discloses a kind of method for removing metal in hydrogenated polymers, including following step
Suddenly：Organic base is added into the hydrogenated polymers glue containing metallic residue, deionized water is added after adding oxidant, reaction
Washing, is centrifuged.Organic base in this method makes the water phase basic in glue, particularly in the presence of having Al,
Al under alkalescence condition（OH）3In colloidal state, it is extremely difficult to separate.
The content of the invention
The present invention is removed for metal ion in metal ion subtractive process in hydrogenation catalyst post-consumer polymer in the prior art
Not thoroughly, it is separated difficult, treatment process is complicated, easily causes environmental pollution, acid-base balance is easily lacked of proper care and etching apparatus, particularly
In the presence of having an aluminium ion, the abnormal troublesome defect of removing, it is therefore an objective to be to propose it is a kind of it is more thorough, more environmentally friendly, safer, be more easy to
Industrialize the method that metallic catalyst residue is removed from polymer glue；Aluminum ions removing is particularly suitable for use in polymer.
The invention provides a kind of method that residual metal catalyst is removed in glue from hydrogenated polymers, this method is：
1）In the glue formed by unsaturated polymer made from anionic polymerisation after catalytic hydrogenation reaction, first add
Enter oxidant to occur to add carbon dioxide generation neutralization reaction after the completion of oxidation reaction, oxidation reaction；Or in above-mentioned glue
Add oxidant and occur oxidation reaction, while adding carbon dioxide occurs neutralization reaction；Finally centrifuge out precipitation；
2）Or the glue formed in unsaturated polymer made from free radical or cationic polymerization after catalytic hydrogenation reaction
In liquid, first add after organolithium, add oxidant and occur to add in carbon dioxide generation after the completion of oxidation reaction, oxidation reaction
And reaction；Or after in above-mentioned glue first adding organolithium, add oxidant and occur oxidation reaction, while adding titanium dioxide
Neutralization reaction occurs for carbon；Finally centrifuge out precipitation；
The minimum amount of described carbon dioxide is 0.5 times of aluminium ion mole in glue, and research on maximum utilized quantity is water-soluble to make
The pH value of liquid is neutrality.
Catalytic hydrogenation catalyst in described catalyst hydrogenation reaction is mainly the organo-metallic compound of cobalt, nickel, iron
Middle one or more of combinations with organo-aluminium.
Described addition carbon dioxide can be passed through carbon dioxide, or add carbon dioxide saturated aqueous solution,
Or two kinds of progress simultaneously.
The mole dosage of described oxidant is the one or more and aluminium in iron ion, cobalt ions, nickel ion in glue
1.0~7.0 times of the total mole number of ion；Preferably 1.2~3 times.
Described oxidant is one or more in oxygen, air, hydrogen peroxide or alkyl peroxide；Preferably peroxidating
Hydrogen.
The oxidant addition of the present invention is too low, and metallic residue oxidation is insufficient, it is difficult to form precipitation, metal ion removing
Effect is bad.
When the inventive method selects hydrogen peroxide, if hydrogen peroxide addition is too high, there is potential safety hazard in reaction.
In the inventive method, if free radical or cation trigger the obtained unsaturated polymer of polymerization through catalytic hydrogenation
The glue formed after reaction, in order that metal ion, particularly aluminium ion are oxidized to after high price, forms molten in alkaline solution
Glue, adds organolithium in glue, it is ensured that glue is into alkalescent；If the unsaturated polymerization as made from anion initiated polymerization
The glue that thing is formed after catalytic hydrogenation reaction, the inside generally there are a small amount of initiator and organic metal residue, can guarantee that molten
Liquid is in alkalescent；If not in alkalescent, a small amount of organolithium can also be added again to adjust.
The addition mole of the organolithium:One or more of and aluminium ion in iron ion, cobalt ions, nickel ion in glue
Integral molar quantity be 1:0.5~5；Preferably 1:2.0~3.5.
The metal ion contained in glue of the present invention derives from the catalyst residue added in hydrogenation reaction；Lithium from
The organolithium that son is added in initiator organolithium and removing glue during metal.
The organolithium includes the one or more in n-BuLi, s-butyl lithium, phenyl lithium, ethyl-lithium.
Described oxidation reaction be temperature be 10~150 DEG C, pressure be 0.01~1MPa under conditions of, reaction 0.1~
10h；Preferably temperature be 30~90 DEG C when, pressure be 0.1~0.5MPa under conditions of, react 0.1~2h.
Described neutralization reaction be temperature be 10~150 DEG C, pressure be 0.01~1MPa under conditions of, reaction 0.1~
10h；Preferably temperature be 30~90 DEG C when, pressure be 0.1~0.5MPa under conditions of, react 0.1~2h.
The present invention, as the medium of separating metal ions, makes the metal ion after oxidation, organic base in the aqueous solution using water
In react；Water includes the water of the water and dissolved carbon dioxide in oxidants hydrogen peroxide solution；If using other oxidations
Agent and when being passed directly into carbon dioxide neutralization reaction, need to add water, and it with the volume proportion of glue total amount is 1 that the consumption of water, which is,:
10~100, preferably 1:40~60.
The technical principle of the present invention：The difficulties such as iron, cobalt, nickel, aluminium are primarily present in the glue of the hydrogenation reaction formation of polymer
The metal ion removed；The present inventor had found by substantial amounts of experiment, in the presence of having aluminium ion in polymer, metal ion
Removing is difficult, and generally using organo-aluminium as reducing agent in hydrogenation catalyst；Aluminium ion is mainly oxidized to Al3+, in alkalescence
Amorphous [the Al (OH) of gel is formed in environment4]-, the actually mainly indefinite hydrated alumina Al of water content2O3.xH2O；
Alumine hydroxide colloid adsorbs other metal oxides, is formed and includes a large amount of water and the floccule body smaller than water density, hydrogenation glue from
Glue is on upper strata after heart separation, and metal floccule body is in middle level, and water causes difficult with hydrogenation glue layering in lower floor, in order to thorough
Metallic residue is isolated at bottom can take substantial amounts of glue out of；When removing is hydrogenated with residual metal ions in glue containing aluminium element, destruction
Alumine hydroxide colloid is the key for removing metal ion；Gel aluminum hydroxide can be destroyed by the pH value for adjusting water, when water
PH value>When 5.5, alumine hydroxide colloid destruction, but the dissolving of other metal ions is in aqueous, it is difficult to reclaim, and cause
Discharge the pollution of water body；Inventor is passed through CO by substantial amounts of experiment, discovery2Gel aluminum hydroxide can be not only destroyed, is precipitated
Out aluminium hydroxide white crystal, and make other heavy metal ion generation metal precipitates be deposited in the bottom simultaneously, through centrifugation
After machine separation, the beds of precipitation are in bottom, and water is in intermediate layer, and glue can be directly separated plastic emitting liquid layer, glue layer purity on upper strata
Height, separation is thorough.
Beneficial effects of the present invention：The inventive method can remove the metal residue in polymer glue well, especially
It is the presence of the aluminium element it is difficult to be removed from polymer, in the case that gelatin viscosity is higher, the clearance of metallic residue
Also up to more than 98%；Other heavy metal ion are with Precipitation simultaneously, and the almost noresidue in discharge water does not result in pollution；Together
When avoid using other acid-base reagents, the equipment corrosion caused；Do not have during polymer glue removing metal impurities
Introduce any impurity, it is adaptable to industrialized production.
Embodiment
The present invention is illustrated with embodiment below, is not intended to limit the present invention.
Embodiment 1
Basic glue is SIS before hydrogenation, and gelatin concentration is 10%（wt）, take it
Contain Ni580mg/Kg in glue 3000mL after hydrogenation, polymer, containing Al1400mg/Kg, containing Li230mg/Kg, glue temperature 70
DEG C, gelatin viscosity is 212.8cp, temperature be 70 DEG C or so, pressure be 0.1~0.5MPa under conditions of, first add 1%
H2O2150mL is aoxidized after 40min, then be passed through CO as oxidant2It is separated off sinking through centrifuge after 0.04mol, reaction 40min
Form sediment.Pure glue, using Atomic Absorption Spectrometry examination wherein metal ion content, collects separation aqueous phase through gel, drying
And residue.
Comparative example 1
Basic glue is SIS before hydrogenation, and gelatin concentration is 10%（wt）, take it
Contain Ni580mg/Kg in glue 3000mL after hydrogenation, polymer, containing Al1400mg/Kg, containing Li230mg/Kg, glue temperature 70
DEG C, gelatin viscosity is 212.8cp, first adds 1%H2O2150mL is as oxidant, after the completion of oxidation, is directly removed through centrifuge separation
Go precipitation.Pure glue, using Atomic Absorption Spectrometry examination wherein metal ion content, collects separation through gel, drying
Aqueous phase and residue.
Comparative example 2
Basic glue is SIS before hydrogenation, and gelatin concentration is 10%（wt）, take it
Contain Ni580mg/Kg in glue 3000mL after hydrogenation, polymer, containing Al1400mg/Kg, containing Li230mg/Kg, glue temperature 70
DEG C, gelatin viscosity is 212.8cp, first adds 1%H2O2150mL is as oxidant, after the completion of oxidation, adds appropriate citric acid water
Solution, it is 7 to control pH value in aqueous phase, and precipitation is separated off through centrifuge.Pure glue is inhaled through gel, drying using atom
Spectroscopic methodology test wherein metal ion content is received, separation aqueous phase and residue is collected.
Comparative example 3
Basic glue is SIS before hydrogenation, and gelatin concentration is 10%（wt）, take it
Contain Ni580mg/Kg in glue 3000mL after hydrogenation, polymer, containing Al1400mg/Kg, containing Li230mg/Kg, glue temperature 70
DEG C, gelatin viscosity is 212.8cp, first adds 1%H2O2150mL is as oxidant, after the completion of oxidation, adds excessive citric acid water
Solution, it is 5-6 to control pH value in aqueous phase, and precipitation is separated off through centrifuge.Pure glue is through gel, drying, using atom
Absorption spectrometry test wherein metal ion content, collects separation aqueous phase and residue.
The contrast of the different demetalization ion methods of table 1
As shown in Table 1, the method for comparative example 1,2 produces a large amount of metallic residues containing polymer and solvent, it is necessary to further
Reclaim.Contain heavy metal ion in the method aqueous phase of comparative example 3, aqueous phase need to be handled.Embodiment 1 uses CO2Sedimentation,
Metal ion removing is thorough in polymer, and metallic residue amount is few and content is pure, and being not required to processing directly can reclaim or bury, and aqueous phase
Meet direct discharge standard, be a kind of method of removing metal in most easy-to-use polymer.
Embodiment 2
Basic glue is SIS, gelatin concentration 10% before hydrogenation（wt）, take it to add
Contain Ni580mg/Kg in glue 3000mL after hydrogen, polymer, containing Al1400mg/Kg, containing Li230mg/Kg, glue temperature 70
DEG C, gelatin viscosity is 212.8cp, temperature be 70 DEG C or so, pressure be 0.1~0.5MPa under conditions of, first add 3%
H2O250mL aoxidizes after 40min as oxidant, adds CO2Separated after saturated solution 250mL, reaction 40min through centrifuge
Remove precipitation.Pure glue, using Atomic Absorption Spectrometry examination wherein metal ion content, is collected and divided through gel, drying
From aqueous phase and residue.
Embodiment 3
Basic glue is SIS before hydrogenation, and gelatin concentration is 10%（wt）, take it
Contain Ni580mg/Kg in glue 3000mL after hydrogenation, polymer, containing Al1400mg/Kg, containing Li230mg/Kg, glue temperature 70
DEG C, gelatin viscosity is 212.8cp, temperature be 70 DEG C or so, pressure be 0.1~0.5MPa under conditions of, 1%H2O2150mL makees
For oxidant and 0.4molCO2Add simultaneously, precipitation is separated off through centrifuge after reaction 50min.Pure glue through gel,
Dry, using Atomic Absorption Spectrometry examination wherein metal ion content, collect separation aqueous phase and residue.
Table 2CO2Influence of the feed postition to demetalization ion
As shown in Table 2, CO2Removing of the feed postition to metal ion in hydrogenation glue has no significant effect.
Embodiment 4
The addition for changing carbon dioxide is 0.01mol, and other conditions are same as Example 1.
Embodiment 5
The addition for changing carbon dioxide is 0.06mol, and other conditions are same as Example 1.
Embodiment 6
Change hydrogen peroxide concentration is 0.3wt%, and aqueous hydrogen peroxide solution addition is 150mL, other conditions and the phase of embodiment 1
Together.
Embodiment 7
Change hydrogen peroxide concentration is 0.3wt%, and aqueous hydrogen peroxide solution addition is 300mL, other conditions and the phase of embodiment 1
Together.
Embodiment 8
Change hydrogen peroxide concentration is 0.3wt%, and aqueous hydrogen peroxide solution addition is 100mL, other conditions and the phase of embodiment 1
Together.
Embodiment 9
Change hydrogen peroxide concentration is 1.0wt%, and aqueous hydrogen peroxide solution addition is 50mL, other conditions and the phase of embodiment 1
Together.
Embodiment 10
Change hydrogen peroxide concentration is 1.0wt%, and aqueous hydrogen peroxide solution addition is 150mL, other conditions and the phase of embodiment 1
Together.
Glue demetalization ion situation is hydrogenated with the different additions of table 3
Embodiment 11
It is 30 DEG C to change glue temperature, and other conditions are same as Example 1.
Embodiment 12
It is 90 DEG C to change glue temperature, and other conditions are same as Example 1.
Embodiment 13
The change reaction time is 10min, and other conditions are same as Example 7.
Embodiment 14
The change reaction time is 120min, and other conditions are same as Example 7.
Glue demetalization ion situation is hydrogenated with the different technology conditions of table 4
Embodiment 15
Basic glue is SIS before hydrogenation, and gelatin concentration is 15%（wt）, take it
Contain Ni870mg/Kg in glue 3000mL after hydrogenation, polymer, containing Al2100mg/Kg, containing Li345mg/Kg, glue temperature 70
DEG C, gelatin viscosity is 775.6cp, temperature be 70 DEG C or so, pressure be 0.1~0.5MPa under conditions of, 1.5%H2O2150mL
It is used as oxidant and CO2Add simultaneously, precipitation is separated off through centrifuge after reaction 40min.Pure glue is through gel, dry
It is dry, using Atomic Absorption Spectrometry examination wherein metal ion content.
The viscosity of table 5 is that 775.6cp is hydrogenated with glue demetalization ion situation
Claims (9)
1. the method for residual metal catalyst is removed in a kind of glue from hydrogenated polymers, it is characterised in that
1) in the glue formed by unsaturated polymer made from anionic polymerisation after catalytic hydrogenation reaction, oxygen is first added
Agent occurs to add carbon dioxide generation neutralization reaction after the completion of oxidation reaction, oxidation reaction；Or added in above-mentioned glue
Oxidation reaction occurs for oxidant, while adding carbon dioxide occurs neutralization reaction；Finally centrifuge out precipitation；
2) or in the glue that unsaturated polymer made from free radical or cationic polymerization is formed after catalytic hydrogenation reaction,
First add after organolithium, add addition carbon dioxide generation neutralization after the completion of oxidation reaction, oxidation reaction occur for oxidant anti-
Should；Or after in above-mentioned glue first adding organolithium, add oxidant and occur oxidation reaction, while adding carbon dioxide hair
Raw neutralization reaction；Finally centrifuge out precipitation；
The minimum amount of described carbon dioxide is 0.5 times of aluminium ion mole in glue, and research on maximum utilized quantity is to make the aqueous solution
PH value is neutrality.
2. the method as described in claim 1, it is characterised in that described addition carbon dioxide can be passed through carbon dioxide gas
Body, or the saturated aqueous solution of carbon dioxide is added, or two kinds are carried out simultaneously.
3. the method as described in claim 1, it is characterised in that the mole dosage of described oxidant is iron, cobalt, nickel in glue
In one or more and 1.0~7.0 times of total mole number of aluminium.
4. method as claimed in claim 3, it is characterised in that described oxidant is oxygen, hydrogen peroxide or alkyl peroxy
It is one or more of in thing.
5. method as claimed in claim 4, it is characterised in that described oxidant is hydrogen peroxide.
6. the method as described in claim 1, it is characterised in that the addition mole of organolithium:In glue iron ion, cobalt from
One or more of and aluminum ions integral molar quantities are 1 in son, nickel ion:0.5~5.
7. method as claimed in claim 6, it is characterised in that the organolithium includes n-BuLi, s-butyl lithium, phenyl
One or more in lithium, ethyl-lithium.
8. the method as described in any one of claim 1~7, it is characterised in that described oxidation reaction be temperature be 10~
150 DEG C, pressure be 0.01~1MPa under conditions of, react 0.1~10h.
9. method as claimed in claim 8, it is characterised in that described oxidation reaction is the pressure when temperature is 30~90 DEG C
Power be 0.1~0.5MPa under conditions of, react 0.1~2h.
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| CN105130736B (en) * | 2015-09-22 | 2017-09-26 | 天津斯瑞吉高新科技研究院有限公司 | A kind of method for removing homogeneous VIII race metallic catalyst |
| EP3676299B1 (en) * | 2017-08-29 | 2023-08-30 | ExxonMobil Chemical Patents Inc. | Carbon dioxide as a catalyst quench agent in solution polymerization, and products made therefrom |
| CN109734828A (en) * | 2018-12-25 | 2019-05-10 | 山东玉皇化工有限公司 | A method of removing unsaturated polymer residure after hydrogenation treatment metallic catalyst |
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| US3780138A (en) * | 1971-09-14 | 1973-12-18 | Shell Oil Co | Method for separating metal contaminant from organic polymers |
| US4595749A (en) * | 1984-11-23 | 1986-06-17 | Shell Oil Company | Direct removal of NI catalysts |
| CN1067898A (en) * | 1992-07-08 | 1993-01-13 | 北京燕山石油化工公司研究院 | The removal methods of residual metal catalyzer behind the hydrogenation of polymer |
| CN1233975A (en) * | 1996-08-29 | 1999-11-03 | 纳幕尔杜邦公司 | Catalyst recovery |
| CN101618886A (en) * | 2008-07-04 | 2010-01-06 | 中国石油化工股份有限公司 | Aluminum hydroxide and preparation method thereof |
| CN102875702A (en) * | 2011-07-13 | 2013-01-16 | 中国石油化工集团公司 | Method for removing metals from polymer |
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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 |
| US4595749A (en) * | 1984-11-23 | 1986-06-17 | Shell Oil Company | Direct removal of NI catalysts |
| CN1067898A (en) * | 1992-07-08 | 1993-01-13 | 北京燕山石油化工公司研究院 | The removal methods of residual metal catalyzer behind the hydrogenation of polymer |
| CN1233975A (en) * | 1996-08-29 | 1999-11-03 | 纳幕尔杜邦公司 | Catalyst recovery |
| CN101618886A (en) * | 2008-07-04 | 2010-01-06 | 中国石油化工股份有限公司 | Aluminum hydroxide and preparation method thereof |
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