CN105130736B - A kind of method for removing homogeneous VIII race metallic catalyst - Google Patents
A kind of method for removing homogeneous VIII race metallic catalyst Download PDFInfo
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- CN105130736B CN105130736B CN201510613009.4A CN201510613009A CN105130736B CN 105130736 B CN105130736 B CN 105130736B CN 201510613009 A CN201510613009 A CN 201510613009A CN 105130736 B CN105130736 B CN 105130736B
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Abstract
The present invention provides a kind of method for removing homogeneous VIII race metallic catalyst, there is provided the deactivators of three kind of VIII race's metal homogeneous catalyst, including oxidisability deactivators, alkaline deactivators and complexing deactivators, with the one or more in above-mentioned three kinds of deactivators reaction treatment is carried out with product mixture, then deactivators and product mixture are subjected to separating treatment, or carry out adsorption treatment with common adsorbents again after reaction treatment is carried out with deactivators, carrying out washing treatment is carried out with common eluant, eluent, finally separate reaching the purpose for effectively removing homogeneous VIII race metallic catalyst.It is low, simple and easy to do with cost, the characteristics of clearance is high, the common eluant, eluent or General Physics adsorbent of used solid-state reaction deactivators or liquid reactive deactivators and auxiliary are nontoxic and free of contamination material, and remained seldom in product, therefore be harmless to personnel, environment and to product.
Description
Technical field
The present invention relates to the minimizing technology of the catalyst of olefin metathesis reaction, and in particular to one kind removes homogeneous VIII race metal
The method of catalyst.
Background technology
Homogeneous VIII race metallic catalyst can be applied to alkylated reaction, the hydrogen that various VIII race metal homogeneous catalysts are catalyzed
Change reaction, it is oxidation reaction, cycloaddition reaction, itself olefin metathesis reactions, intersection olefin metathesis reactions, ring-opening polymerization, many
Alkene ring-closure reaction etc., with high catalytic efficiency, the features such as catalytic amount needed for reaction is few, but just because it is homogeneous catalyst,
Be still present in when reaction completes rear catalyst or catalyst relic in product mixed liquor, to the subsequent treatment of product, separation,
Refined and application can be adversely affected, the isomerization of such as carbon-carbon double bond, the isomerization of carbon-chain structure, backward reaction, side reaction,
Product or chemical breakdown, pyrolysis with product made from product etc..When requiring that product purity is high, nontoxic, low toxicity
Or in the case that stability is high, it is desirable to such catalyst is removed from generation species.
The research of this respect that there are some researchers to carry out.F.Edward Roberts et al. use organosulfur compound
To remove such catalyst (US 4,413,118Nov.1 1982), Robert H.Grubbs et al. use organic phosphine compound
To remove catalyst (US 6,376,690B1Apr.23,2002), both approaches are all the inorganic agents for making catalyst with adding
Complexing turns into the stronger material of polarity, is then removed by the method that polarity extracting agent is extracted, and such method removes catalysis
The effect of agent is fine, but used organosulfur compound and organic phosphine compound are all high price, high pollution, high toxicity
, it removes in catalyst process and adds extractant, is also highly difficult in the removal of sometimes these extractants introduced
, therefore from the aspect of cost, technique, environment and health, such method large-scale application has very big problem.
Leo A.Paquette et al. use lead tetraacetate (Organic Letters, 2 (9) (2000), 1259-1261)
Triphenylphosphine oxide or dimethyl sulfoxide (Organic are used to remove catalyst and its remnants, Yu MiAhn et al.
Letters, 3 (9) (2001), 1411-1412) remove catalyst and its remnants, but the former need to use under anaerobic environment
Lead tetraacetate is simultaneously filtered, and the latter needs further to remove the complexing of the catalyst and inorganic agent of depolarization by silica gel chromatographic column
Thing.The inorganic agent that both approaches are used is all toxic and complex process, removal cost are high.
The K.A. Byrd top grade people of Dow global technical company have applied for the patent (CN with adsorbent Adsorption catalyst
100590104C Feb 17,2010), they used respectively different activated carbons, diatomite, silica gel, bentonite, kaolin,
Ion exchange resin removes the metal homogeneous catalyst such as ruthenium, from the reacted mixture of the olefin metathesis of the 30ppm containing metal
Catalyst is removed, tenor drops to 0.17ppm to 14ppm after absorption.Effect most preferably Westvaco NucalTM
The activated carbon of SN boards.But, simple physisorphtion will reach to micro, low pole, VIII race's metallic catalyst of large volume
Require it is highly difficult to removing, even the preferable Westvaco Nucal of removal effectTMThe activated carbon of SN boards, it is also desirable to
Substantial amounts of adsorbent (about 1st/13rd of mixture weight) is added, filtering is also needed to after absorption, and produce a large amount of absorption
Agent residue.
Kenneth A.Burdett of Dow Chemical et al. have been invented with anti-after nanometer membrane technology separation olefin metathesis
Answer the catalyst and catalyst analyte (US 20080103346A1, May 1,2008) in system.This invention is in some conditions
Under, catalyst and catalyst analyte can be preferably removed really.But, even if we do not consider its technique complexity and
The factors such as the regeneration of nanometer film, its shortcoming is also it will be apparent that i.e. the molecular volume of the filtrate of membrane filtration is than catalyst
And its analyte is small, this means that after the olefin metathesis reaction of such as triglycerides, it is generated to some bulky molecules
Mixture inside the catalyst residue that contains the method cannot be used to remove.
Martina Sandholzer et al. remove such catalyst (Tetrahedron with functional resin is prepared
Letters 51 (44), 5827-5829,3Nov.2010), compound of the end with carbon-carbon double bond is keyed to macromolecule and carried
On body, recycle the carbon-carbon double bond that it is carried to be complexed with olefin metathesis catalysts, make catalyst together with macromolecule resin
The mixture separation generated after reaction.Due to preparing the complex process, with high costs of such functional resin, therefore this side
Method at present can not large-scale application.
In summary, it is a kind of can large-scale use, effectively to remove the method for homogeneous VIII race metallic catalyst be very
It is necessary.
The content of the invention
To overcome shortcoming and defect of the prior art, the invention provides a kind of removal homogeneous VIII race metallic catalyst
Method, it is adaptable to alkylated reaction that various VIII race metal homogeneous catalysts are catalyzed, hydrogenation, oxidation reaction, cycloaddition
Reaction, itself olefin metathesis reactions, intersection olefin metathesis reactions, ring-opening polymerization, polyenoid ring-closure reaction etc., it is adaptable to all
The VIII race's metal homogeneous catalyst and/or catalyst remained in after VIII race's metal homogeneous catalyst catalytic reaction in reaction system is residual
The removal of piece and/or VIII race's metal, methods described is with low cost, processing is efficient, simple and easy to do.
Technical scheme proposed by the present invention is：A kind of method for removing homogeneous VIII race metallic catalyst, including step A：
(1) at a temperature of 10 DEG C -200 DEG C, deactivators is added into product mixture and carry out reaction 15-
300min, the deactivators are oxidisability deactivators, alkaline deactivators or complexing deactivators, the deactivators and homogeneous VIII race
The mol ratio of metallic catalyst is 1-10000；
(2) deactivators, catalyst and product mixture after step (1) processing are subjected to separating treatment.
The oxidisability deactivators include inorganic peroxide, organic peroxide, oxygen, ozone, air, wherein, institute
Stating inorganic peroxide includes hydrogen peroxide (H2O2), sodium peroxide (Na2O2), calper calcium peroxide (CaO2)；The organic peroxy
Thing has below formula：R1-O-O-R2,
Wherein, R1And R2Selected from H, C1-C20 alkyl, aryl, C1-C20 carbonyls, C1-C20 carbonate groups, above-mentioned substituent
It is unsubstituted or by following one or more substitutions：C1-C10 alkyl, C1-C10 alkoxies, aryl and selected from hydroxyl, ketone,
Aldehyde, ester, the functional group of carboxylic acid and halogen.
Metal and/or part in VIII race's metal homogeneous catalyst can the oxidations of being oxidized property deactivators, oxidation reaction hair
After life, oxidized metal complexing decline and/or its part decline after being oxidized with the coordination ability of metal, cause part and
Metal departs from, and makes that original catalyst volume reduces and/or polarity becomes big, it is easier to is adsorbed by adsorbent or is eluted agent and wash
Go.Such method is applied to the reaction system that target product should not be oxidized or target product need to be aoxidized further.
The alkaline deactivators include inorganic alkali compound, organo-alkali compound, wherein, the inorganic alkali compound has
Below formula：M1OH, wherein M1For alkali metal such as K, Na, Cs；The organo-alkali compound has below formula:R3OM2, wherein：
M2For the alkali metal such as metal K, Na, Li, R3For C1-C5 alkyl, aryl, or the alkyl with substituted radical, aryl.
The complexing power of anionic group in alkaline deactivators, makes it replace original anion ligand, makes metal
Together with the anionic group complexing in deactivators, together with adsorbent or eluant, eluent, separate, reach with product mixed liquor
The purpose of such catalyst is separated, or part original in catalyst is destroyed by alkaline deactivators, causes the complexing energy of part
Power declines, and is separated with metal, makes that original catalyst volume reduces and/or polarity becomes big, it is easier to be adsorbed by adsorbent or by
Eluant, eluent is washed away.Both effect is probably effect presence simultaneously in individualism or two.Such method is generated suitable for target
The reaction system that thing does not react with alkali or target product further need to react with alkali.Can be used alone can also be with other things
Matter (such as solvent) is used together.
The complexing deactivators are represented by below formula：Wherein：R4、R5And R6For C1-C4
Alkyl, C1-C4 hydroxyalkyl or by one in the functional group of alkoxy, hydroxyl, ketone, aldehyde, ester, carboxylic acid and halogen or many
Individual replaced C1-C4 alkyl, C1-C4 hydroxyalkyl.
VIII race is metal complexing to make metal be combined with complexing deactivators, with deactivators, with product mixed liquor point
From.From insoluble in product system, liquid or solid matter with strong complexing, as complexing deactivators, individually make again
It is used in mixed way with or with special surfactant, makes it first and VIII race's metal complex, the complex compound then formed and deactivators
Separated together with product mixed liquor, to reach the purpose for removing catalyst.The method optionally can with common adsorbents or
Eluant, eluent is used in combination.
When preferably, using oxidant deactivators or alkaline deactivators, the treatment temperature in step (1) is 50 DEG C -180
DEG C, processing time is 30-150min；During using complexing agent deactivators, the treatment temperature in step (1) is 10 DEG C -180 DEG C, place
The reason time is 30-150min.
It is preferred that, the mol ratio of the deactivators and homogeneous VIII race metallic catalyst is 5-1000.
When using oxidant deactivators or alkaline deactivators, when oxidant deactivators or alkaline deactivators are insoluble in generation
During thing mixture, the oxidant deactivators or alkaline deactivators and the product mixture mass percent that need to handle
0.1%-10%；During using complexing agent deactivators, the complexing agent deactivators and the product mixture quality percentage that need to be handled
The 1%-15% of ratio.
Further, after deactivators and VIII race's metal homogeneous catalyst react, for will become small volume,
The larger catalyst of polarity and/or catalyst relic and/or metal are more thoroughly removed, and can be carried out again with common adsorbents
Adsorption treatment, including step B：
(1) under normal pressure or vacuum, under 10 DEG C -200 DEG C of adsorption temp, with adsorbent to remaining deactivation after processing
Agent and the catalyst being destroyed carry out adsorption treatment 15-300min, wherein, the quality percentage of adsorbent and product mixed liquor
Than for 0.5%-10%；
(2) adsorbent and product mixture are subjected to separating treatment with the method for filtering and/or centrifugation.
It is preferred that, the adsorption treatment time is 30 to 150min in step B.
Physical absorbent bag expands activated carbon, silica gel, molecular sieve, ion exchange resin, diatomite, bentonite, kaolin.It is main
If utilizing their big specific surface area and stronger adsorption capacity that they have.Wherein diatomite, atlapulgite and
Kaolinic physical absorbent requires that its particle diameter has more than 90% percent of pass to 200 mesh.Deactivators involved in the present invention are such as
Fruit is solid-state, and itself can also be applied as adsorbent.
Further, after liquid deactivators and VIII race's metal homogeneous catalyst react, most catalyst and/
It is the few remnants for more thoroughly removing catalyst or catalyst relic and/or metal have been removed together with deactivators,
Reusable common eluant, eluent carries out carrying out washing treatment, including step C：
(3) under normal pressure or vacuum, under 10 DEG C -200 DEG C of adsorption temp, with eluant, eluent to catalysis remaining after processing
Agent and deactivators carry out extraction processing 1 to 240min, wherein, the percent by volume of eluant, eluent and product mixed liquor is 0.5%-
50%；
(4) eluant, eluent and product mixture are subjected to separating treatment with standing separation and/or the method for centrifugation.
It is preferred that, the dissolution process time in step C is 30 to 150min.
Inorganic eluant, eluent includes water, and organic elution agent includes the polyhydroxy chemical combination such as glycerine, pentaerythrite, triethanolamine
Thing,
When using liquid catalyst deactivators, if deactivators and product mixed liquor it is fairly insoluble or it is extremely difficult mix,
So the effect of deactivators will play not exclusively, and the specific surface area of deactivators can be increased, increase and go by now adding dispersant
Agent living and catalyst and/or the reaction probabilities of catalyst relic, so that the removal effect of deactivators is improved, such as following steps institute
State：
The step (1) is：At a temperature of 10 DEG C -200 DEG C, deactivators and dispersant are added to product mixture
Middle to carry out reaction 15 to 300min, the deactivators include oxidisability deactivators, alkaline deactivators, complexing deactivators；It is described
Dispersant is represented by below formula： Wherein：R7、R8、R9For independently of one another
Hydroxyl, C1-C4 hydroxy alkyl, C10-C20 acyl group, and R7、R8、R9Central have one and only one of which is C10-C20
Acyl group, R10、R11、R12For hydroxyl independently of one another, C1-C4 hydroxy alkyl, C10-C20 acyl group, and R10、R11、R12When
In have one and only one of which be C10-C20 acyl group.
Further, dispersant dosage is that the mass percent of deactivators is 5%-100%, it is preferred that dispersant dosage
It is 10%-50% for the mass percent of deactivators.
Some liquid deactivators and product mixed liquor are immiscible, if using eluant, eluent, then eluant, eluent with
Product mixed liquor is also immiscible.The method efficiently mixed just can be now used, accelerates eluant, eluent and catalyst is anti-
The speed answered, or improve the clean result of eluant, eluent.Efficiently mixing can without or use dispersant less.
Efficient mixing herein refers to design special stirring means, can made by the method insoluble with product mixed liquor
Deactivators or eluant, eluent be dispersed into product mixed liquor and be less than 150 microns of drop more than 300 nanometers, so as to increase
Agent living and the probability or quickening eluant, eluent and the rate of dissolution of remaining catalyst debris and deactivators of catalyst reaction；Meanwhile,
After stopping is stirred, scattered deactivators or eluant, eluent are easier to reassemble again, are easy to separation.
Method involved in the present invention can be used alone, can also two or more be used together.The choosing of method
Select depending on the factors such as production technology, requirement to product or product.
Add due to after using VIII race's metal homogeneous catalyst catalytic reaction, reducing its product in separation, purifying, shaping
The isomerization rate of the carbon-carbon double bond of work and service stage is extremely important, and can effectively reduce the isomerization rate of carbon-carbon double bond be side
The important indicator of method validity.In the present invention, mainly judged so that the isomerization rate of 9- decene acid glycerides can be reduced
The validity of method.
Brief description of the drawings
Fig. 1 is the forward and backward gas chromatogram of 9- decenoate isomerization.
Embodiment
A kind of method for removing homogeneous VIII race metallic catalyst of embodiment 1, comprises the following steps：
(1) at ambient pressure, at a temperature of 30 DEG C, 2g sodium methoxides is added into 100g samples I and are sufficiently stirred for being reacted
120min；
(2) room temperature is cooled to, supernatant liquor is filtered to isolate after standing 1h.
Filtrate is taken to do isomerization experiments, after tested, 9- decylenic acids isomerization rate is 3.48%.
A kind of method for removing homogeneous VIII race metallic catalyst of embodiment 2, comprises the following steps：
(1) at ambient pressure, at a temperature of 80 DEG C, 3 grams of solid glycerine sodium is added into 100g samples I and are sufficiently stirred for carrying out
React 120min；
(2) room temperature is cooled to, supernatant liquor is filtered to isolate after standing 1h.
Filtrate is taken to do isomerization experiments, after tested, 9- decylenic acids isomerization rate is 5.23%.
A kind of method for removing homogeneous VIII race metallic catalyst of embodiment 3, comprises the following steps：
(1) at ambient pressure, at a temperature of 80 DEG C, it is ground to the calper calcium peroxide of 200 mesh by 2 grams and adds into 100g samples I
It is sufficiently stirred for carrying out reaction 180min；
(2) room temperature is cooled to, stands after 1h, filters to isolate supernatant liquor.
Filtrate is taken to do isomerization experiments, after tested, 9- decylenic acids isomerization rate is 4.22%.
A kind of method for removing homogeneous VIII race metallic catalyst of embodiment 4, comprises the following steps：
(1) at ambient pressure, at a temperature of 60 DEG C, the 9- decenoyls diethanolamine solution of 5 gram 78% of triethylamine is added
It is sufficiently stirred for carrying out reaction 120min into 100g samples I；
(2) (1900rpm, 10min) is immediately centrifuged after the completion of stirring, supernatant liquor is isolated.
Filtrate isomerization experiments are taken, after tested, 9- decylenic acids isomerization rate is 2.58%.
A kind of method for removing homogeneous VIII race metallic catalyst of embodiment 5, comprises the following steps：
(1) at ambient pressure, at a temperature of 60 DEG C, the 9- decenoyls diethanolamine solution of 5 gram 78% of triethylamine is added
It is sufficiently stirred for carrying out reaction 120min into 100g samples I；
(2) (1900rpm, 10min) is immediately centrifuged after the completion of stirring, supernatant liquor is isolated；
(3) 10 grams of glycerine are added in the supernatant into step (1), are stirred 5 hours；
(4) stood after the completion of stirring, isolate supernatant liquor.
With supernatant and isomerization experiments are done, after tested, 9- decylenic acids isomerization rate is 0.30%.
A kind of method for removing homogeneous VIII race metallic catalyst of embodiment 6, comprises the following steps：
(1) at ambient pressure, at a temperature of 60 DEG C, the 9- decenoyls diethanolamine solution of 12 gram 90% of triethylamine is added
It is sufficiently stirred for carrying out reaction 120min into 100g samples I,
(2) (1900rpm, 10min) is centrifuged after the completion of stirring, supernatant liquor is isolated；
(3) 4 grams of triethanolamines are added in the supernatant into step (2), are sufficiently stirred for 60 minutes；
(4) stand, isolate supernatant liquor.
With supernatant and isomerization experiments are done, after tested, 9- decylenic acids isomerization rate is 0.26%.
A kind of method for removing homogeneous VIII race metallic catalyst of embodiment 7, comprises the following steps：
(1) at ambient pressure, at a temperature of 60 DEG C, the 9- decenoyls diethanolamine solution of 5 gram 78% of triethylamine is added
It is sufficiently stirred for carrying out reaction 120min into 100g samples I,
(2) (1900rpm, 10min) is immediately centrifuged after the completion of stirring, supernatant liquor is isolated；
(3) 8g water, moderate-speed mixer 60 minutes are added in the supernatant into step (2)；
(4) (1900rpm, 10min) is centrifuged again, supernatant liquor is isolated.
Isomerization experiments are done with supernatant.After tested, 9- decylenic acids isomerization rate is 1.58%.
A kind of method for removing homogeneous VIII race metallic catalyst of embodiment 8, comprises the following steps：
(1) at ambient pressure, at a temperature of 80 DEG C, by oleic monoesters of 5 grams of temperature for 60 DEG C of 85% triethylamine
Solution, which is added into 100g samples I, to be sufficiently stirred for carrying out reaction 20min；
(2) (1900rpm, 10min) is immediately centrifuged, supernatant liquor is isolated；
(3) 10 grams of glycerine are added in the supernatant into step (1), are sufficiently stirred for 190 minutes；
(4) stratification, isolates supernatant liquor.
Isomerization experiments are done with supernatant liquor.After tested, 9- decylenic acids isomerization rate is 0.35%.
A kind of method for removing homogeneous VIII race metallic catalyst of embodiment 9, comprises the following steps：
(1) at ambient pressure, at a temperature of 60 DEG C, by oleic monoesters of 5 grams of temperature for 60 DEG C of 85% triethylamine
Solution, which is added into 100g samples I, to be sufficiently stirred for carrying out reaction 120min；
(2) (1900rpm, 10min) is immediately centrifuged after the completion of stirring, supernatant liquor is isolated；
(3) in the supernatant into step (1) add 3 grams of atlapulgites, 40mmHg, 120 DEG C be sufficiently stirred for 90 minutes；
(4) with the cloth funnel suction filtration for having Celite pad.
Isomerization experiments are made of filtrate, after tested, 9- decylenic acids isomerization rate is 0.18%.
A kind of method for removing homogeneous VIII race metallic catalyst of embodiment 10, comprises the following steps：
(1) under normal pressure, normal temperature, the aqueous isopropanol of the triethylamine of 5 gram 50% (v/v) is added into 100g samples I
Moderate-speed mixer carries out reaction 240min；
(2) sample each 20ML water washing 2 times, isolates supernatant liquor.
Isomerization experiments are done with clear liquid.After tested, 9- decylenic acids isomerization rate is 0.15%.
A kind of method for removing homogeneous VIII race metallic catalyst of embodiment 11, comprises the following steps：
(1) 100mmHg, at a temperature of 120 DEG C, the triethanolamine that 5 grams of diatomite are done into carrier is added into 100g samples I
It is sufficiently stirred for carrying out reaction 120min；
(2) (1900rpm, 10min) is centrifuged after cooling down, supernatant liquor is isolated.
Isomerization experiments are done with supernatant.After tested, 9- decylenic acids isomerization rate is 1.57%.
A kind of method for removing homogeneous VIII race metallic catalyst of embodiment 12, comprises the following steps：
(1) in normal pressure, at a temperature of 120 DEG C, 50 DEG C of air is blown into 100g samples I, is sufficiently stirred for being reacted
120min；
(2) (w/w) atlapulgite of Jia 5%, 40mmHg, 120 DEG C be sufficiently stirred for 90 minutes；
(3) with the cloth funnel suction filtration for having Celite pad.
Filtrate does isomerization experiments, after tested, and 9- decylenic acids isomerization rate is 7.83%.
A kind of method for removing homogeneous VIII race metallic catalyst of embodiment 13, comprises the following steps：
(1) in normal pressure, at a temperature of 120 DEG C, 50 DEG C of air is blown into 100g samples I, is sufficiently stirred for being reacted
180min；
(2) (w/w) atlapulgite of Jia 5%, 40mmHg, 120 DEG C be sufficiently stirred for 90 minutes；
(3) with the cloth funnel suction filtration for having Celite pad.
Filtrate does isomerization experiments, after tested, and 9- decylenic acids isomerization rate is 5.06%.
A kind of method for removing homogeneous VIII race metallic catalyst of embodiment 14, comprises the following steps：
(1) at a temperature of normal pressure, 80 DEG C, 5 grams of 3%KOH/ glycerites is added and are added into 100g samples I, it is mixed at a high speed
Close 30min；
(2) room temperature is cooled to, 1h is stood and isolates supernatant.
Supernatant liquor is taken to do isomerization experiments.After tested, 9- decylenic acids isomerization rate 0.22%.
A kind of method for removing homogeneous VIII race metallic catalyst of embodiment 15, comprises the following steps：
(1) in normal pressure, at a temperature of 60 DEG C, 5g triethanolamines is added to 100g samples I, 30min is efficiently mixed；
(2) (1900rpm, 10min) is centrifuged, supernatant liquor is isolated.
Isomerization experiments are done with supernatant, through GC test analysis, after tested, 9- decylenic acids isomerization rate is 3.62%.
A kind of method for removing homogeneous VIII race metallic catalyst of embodiment 16, comprises the following steps：
(1) in normal pressure, at a temperature of 80 DEG C, 5g triethanolamines is added to 100g samples I, 15min is efficiently mixed；
(2) (1900rpm, 10min) is centrifuged, supernatant liquor is isolated.
Isomerization experiments are done with supernatant, through GC test analysis, after tested, 9- decylenic acids isomerization rate is 1.81%.
A kind of method for removing homogeneous VIII race metallic catalyst of embodiment 17, comprises the following steps：
(1) in normal pressure, at a temperature of 100 DEG C, 5g triethanolamines is added to 100g samples I, 10min is efficiently mixed；
(2) (1900rpm, 10min) is centrifuged, supernatant liquor is isolated.
Isomerization experiments are done with supernatant, through GC test analysis, after tested, 9- decylenic acids isomerization rate is 1.92%.
A kind of method for removing homogeneous VIII race metallic catalyst of embodiment 18, comprises the following steps：
(1) at a temperature of normal pressure, 80 DEG C, 5 grams of triethanolamines is added and are added into 100g samples I, mixed at high speed
120min；
(2) after reaction terminates, 15min is stood at 80 DEG C, supernatant liquor is isolated；
(3) 3g triethanolamines are added in the supernatant liquor in step (1), 30min is sufficiently stirred at room temperature；
(4) 15min is stood at room temperature, is isolated supernatant liquor and is done isomerization experiments.
After tested, 9- decylenic acids isomerization rate is 0.23%.
A kind of method for removing homogeneous VIII race metallic catalyst of embodiment 19, comprises the following steps：
(1) at a temperature of normal pressure, 80 DEG C, 5 grams of triethanolamines is added and are added into 100g samples I, mixed at high speed
15min；
(2) after reaction terminates, (1900rpm, 10min) is centrifuged, supernatant liquor is isolated；
(3) 3g glycerine is added in the supernatant liquor in step (2), 30min is sufficiently stirred at room temperature；
(4) (1900rpm, 10min) is centrifuged, supernatant liquor is isolated
Isomerization experiments are done with supernatant.After tested, 9- decylenic acids isomerization rate is 0.12%.
In the embodiment above, be using Grubbs ruthenium catalysts be catalyzed vegetable oil and alpha-olefin olefin metathesis reactions as
Example, wherein, sample I is that the product of the olefin metathesis reactions for the vegetable oil and alpha-olefin being catalyzed using Grubbs ruthenium catalysts is mixed
Ruthenium concentration is 15ppm in compound, mixture.
Isomerization experiments：The product mixed liquor 2g after deactivators remove catalyst is weighed in 20mL bottles, is put
Enter magnetic stir bar, the electromagnetic agitation 2h in 180 DEG C of oil baths, under argon gas protection.It is cooled to after room temperature and gas is made as follows
Phase chromatographic sample.
The methanol solution of sodium methylate 2mL of product mixed liquor 0.5g and 0.5% after above-mentioned isomerization experiments is added to
In 20mL bottles, bottle cap, the lower 60 DEG C of heating esterification reaction of organic acid 1h of electromagnetic agitation are screwed.Room temperature is cooled to, 3mL n-hexanes are added,
Stirring extraction.Stand after 30min, draw upper solution 0.25mL, be diluted in chromatography of gases sample bottle with n-hexane
1.0mL, carries out gas-chromatography test.
Fig. 1 be 9- decenoate isomerization before and after gas chromatogram comparison, as shown in figure 1, completely without isomery
The 9- decenoates of change are to have one unimodal at 8.36min in retention time, after isomerization occurs, can 8.21min,
There are four peaks in 8.32min, 8.44min, 8.63min, and wherein retention time is 9- decenoates for 8.32min peak,
And other three peaks are the new peaks produced because of isomerization.The new peak area sum occurred after isomerization and aforementioned four peak
The percentage of the ratio between the gross area, as isomerization rate.
Sample I without the processing of any catalyst deactivators, after isomerization test, its isomerization rate is 70.52%.
Claims (7)
1. a kind of method for removing homogeneous Grubbs ruthenium catalysts, it is characterised in that：Including experimental procedure A：
(1) at a temperature of normal pressure, 10 DEG C -200 DEG C, deactivators is added into product mixture and carry out reaction 15-
300min, the deactivators are complexing deactivators, and the mol ratio of the deactivators and homogeneous Grubbs ruthenium catalysts is 1-
10000；Wherein described product mixture is the olefin metathesis reactions of the vegetable oil that Grubbs ruthenium catalysts are catalyzed and alpha-olefin
Product mixture；
(2) deactivators, catalyst and product mixture after step (1) processing are subjected to separating treatment；
The complexing deactivators in step (1) areWherein：R4、R5And R6For C1-C4 alkyl,
C1-C4 hydroxyalkyl.
2. a kind of method for removing homogeneous Grubbs ruthenium catalysts according to claim 1, it is characterised in that：Step (1)
In treatment temperature be 10 DEG C -180 DEG C, processing time is 30-150min.
3. a kind of method for removing homogeneous Grubbs ruthenium catalysts according to claim 1, it is characterised in that：The deactivation
The mol ratio of agent and homogeneous Grubbs ruthenium catalysts is 5-1000.
4. a kind of method for removing homogeneous Grubbs ruthenium catalysts according to claim 1, it is characterised in that：Also include step
Rapid B：
(1) under normal pressure or vacuum, under 10 DEG C -200 DEG C of adsorption temp, with adsorbent to remaining deactivators after processing and
The catalyst being destroyed carries out adsorption treatment 15-300min, wherein, the mass percent of adsorbent and product mixed liquor is
0.5%-10%；
(2) adsorbent and product mixture are subjected to separating treatment with the method for filtering or centrifugation.
5. a kind of method for removing homogeneous Grubbs ruthenium catalysts according to claim 4, it is characterised in that：In step B
The adsorption treatment time is 30 to 150min.
6. a kind of method of the homogeneous Grubbs ruthenium catalysts of removal according to claim 1 or 4, it is characterised in that：Also wrap
Include step C：
(1) under normal pressure or vacuum, under 10 DEG C -200 DEG C of extraction temperature, with eluant, eluent to catalyst remaining after processing and
Deactivators carry out extraction processing 1 to 240min, wherein, the percent by volume of eluant, eluent and product mixed liquor is 0.5%-
50%；
(2) eluant, eluent and product mixture are subjected to separating treatment with standing separation or the method for centrifugation.
7. a kind of method for removing homogeneous Grubbs ruthenium catalysts according to claim 6, it is characterised in that：In step C
The extraction processing time be 30 to 150min.
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