CN105130736A - Method for removing homogeneous phase VIII metal catalyst - Google Patents
Method for removing homogeneous phase VIII metal catalyst Download PDFInfo
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- CN105130736A CN105130736A CN201510613009.4A CN201510613009A CN105130736A CN 105130736 A CN105130736 A CN 105130736A CN 201510613009 A CN201510613009 A CN 201510613009A CN 105130736 A CN105130736 A CN 105130736A
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Abstract
The invention provides a method for removing a homogeneous phase VIII metal catalyst, provides three deactivation agents comprising an oxidant deactivation agent, an alkali deactivation agent and a complexing deactivation agent of the homogeneous phase VIII metal catalyst. The method comprises the steps: performing reaction processing on one and more of the three deactivation agents and a product mixture, then separating the deactivation agents from the product mixture, or adsorbing with a common adsorbent after reaction of the deactivation agents and washing by a common eluent, and finally separating to achieve the aim of effectively removing the homogeneous phase VIII metal catalyst. The method has characteristics of low cost, simpliness and feasibility, and high removal rate, used solid reactive deactivation agents or liquid reactive deactivation agents and auxiliary common eluent or common physical adsorbent are nontoxic and non-pollution substances, and residue in the product is extremely less, and thus no harm is generated to people, environment and the product.
Description
Technical field
The present invention relates to the minimizing technology of the catalyzer of olefin metathesis reaction, be specifically related to a kind of method removing homogeneous phase VIII race metal catalyst.
Background technology
Homogeneous phase VIII race metal catalyst can be applicable to the alkylated reaction of various VIII metal homogeneous catalyst institute of race catalysis, hydrogenation, oxidizing reaction, cycloaddition reaction, self olefin metathesis reactions, intersection olefin metathesis reactions, ring-opening polymerization, polyenoid ring-closure reaction etc., there is catalytic efficiency high, the features such as the catalytic amount needed for reaction is few, but just because it is homogeneous catalyst, when reaction completes rear catalyst or catalyzer relic is still present in resultant mixed solution, to the subsequent disposal of product, be separated, refining and application can cause disadvantageous effect, as the isomerization of carbon-carbon double bond, the isomerization of carbon-chain structure, backward reaction, side reaction, resultant or the decomposition of goods obtained with resultant, pyrolysis etc.When requiring that product purity is high, nontoxic, low toxicity or stability high when, just require this type of catalyzer to remove from generation species.
The research of this respect that had some investigators to carry out.The people such as F.EdwardRoberts remove this type of catalyzer (US4 with organosulfur compound, 413, 118Nov.11982), the people such as RobertH.Grubbs use organic phosphine compound to remove catalyzer (US6, 376, 690B1Apr.23, 2002), these two kinds of methods are all make catalyzer become the stronger material of polarity with the treatment agent complexing added, then the method extracted by polarity extracting agent is removed, the effect that these class methods remove catalyzer still can, but the organosulfur compound used and organic phosphine compound are all high prices, high pollution, highly toxic, it is removed in catalyst process and adds extraction agent, at some time, the removal of the extraction agent that these are introduced also is very difficult, therefore from cost, technique, environment and healthy aspect are considered, this class methods large-scale application has very large problem.
The people such as LeoA.Paquette use lead tetraacetate (OrganicLetters, 2 (9) (2000), 1259-1261) remove catalyzer and remnants thereof, the people such as YuMiAhn use triphenylphosphine oxide or methyl-sulphoxide (OrganicLetters, 3 (9) (2001), 1411-1412) remove catalyzer and remnants thereof, but the former need use lead tetraacetate and filter under anaerobic environment, and the latter needs to come further except the catalyzer of depolarization and the complex compound for the treatment of agent through silica gel chromatographic column.The treatment agent that these two kinds of methods use is all toxic and complex process, removal cost are high.
The K.A. Byrd top grade people of Dow global technical company has applied for the patent (CN100590104CFeb17 removing catalyzer with adsorbent, 2010), they employ different gacs respectively, diatomite, silica gel, wilkinite, kaolin, ion exchange resin remove the metal homogeneous catalysts such as ruthenium, from the reacted mixture of the olefin metathesis of containing metal 30ppm, remove catalyzer, after absorption, metal content does not drop to 0.17ppm to 14ppm not etc.Effect is it is preferred that WestvacoNucal
tMthe gac of SN board.But, simple physisorphtion will to VIII race's metal catalyst of trace, low-pole, large volume reach remove require be very difficult, even the good WestvacoNucal of removal effect
tMthe gac of SN board, also needs to add a large amount of sorbent materials (being about 1/13rd of mixture weight), also needs to filter after absorption, and produces a large amount of sorbent material residue.
The human hairs such as the KennethA.Burdett of Dow Chemical understand with the catalyzer in reaction system after nanometer film technology separation olefin metathesis and catalyst decomposes thing (US20080103346A1, May1,2008).This invention under certain conditions, can remove catalyzer and catalyst decomposes thing really preferably.But, even if we do not consider the factor such as the complicacy of its technique and the regeneration of nanometer film, its shortcoming is also apparent, namely the filtrate of membrane filtration molecular volume than catalyzer and resolvent little, this just means some bulky molecule, after the olefin metathesis reaction of such as triglyceride level, the catalyst residue that the mixture inside that it generates is contained just can not use this method to remove.
The people such as MartinaSandholzer remove this type of catalyzer (TetrahedronLetters51 (44) with preparing functional resin, 5827-5829,3Nov.2010), end is keyed on polymer carrier with the compound of carbon-carbon double bond, recycle its with carbon-carbon double bond and the complexing of olefin metathesis catalysts, make catalyzer together with macromolecule resin from reaction after generate mixture separation.Owing to preparing the complex process, with high costs of this type of functional resin, therefore this method at present cannot large-scale application.
In sum, a kind of method that can use on a large scale, that effectively can remove homogeneous phase VIII race metal catalyst is very necessary.
Summary of the invention
For overcoming shortcoming and defect of the prior art, the invention provides a kind of method removing homogeneous phase VIII race metal catalyst, be applicable to the alkylated reaction of various VIII metal homogeneous catalyst institute of race catalysis, hydrogenation, oxidizing reaction, cycloaddition reaction, self olefin metathesis reactions, intersection olefin metathesis reactions, ring-opening polymerization, polyenoid ring-closure reaction etc., the removal of VIII race's metal homogeneous catalyst in reaction system and/or catalyzer relic and/or VIII race's metal is remained in after being applicable to all VIII race's metal homogeneous catalyst catalyzed reactions, described method is with low cost, process is efficient, simple and easy to do.
The technical scheme that the present invention proposes is: a kind of method removing homogeneous phase VIII race metal catalyst, comprises steps A:
(1) at the temperature of 10 DEG C-200 DEG C, deactivators is added in product mixture and carries out reaction 15-300min, described deactivators is oxidisability deactivators, alkaline deactivators or complexing deactivators, and the mol ratio of described deactivators and homogeneous phase VIII race metal catalyst is 1-10000;
(2) deactivators, catalyzer and product mixture after step (1) process are carried out separating treatment.
Described oxidisability deactivators comprises inorganic peroxide, organo-peroxide, oxygen, ozone, air, and wherein, described inorganic peroxide comprises hydrogen peroxide (H
2o
2), sodium peroxide (Na
2o
2), calcium peroxide (CaO
2); Described organo-peroxide has following general formula: R
1-O-O-R
2,
Wherein, R
1and R
2be selected from H, C1-C20 alkyl, aryl, C1-C20 carbonyl, C1-C20 carbonate group, above-mentioned substituting group is not substituted or by following one or more replacements: C1-C10 alkyl, C1-C10 alkoxyl group, aryl and be selected from the functional group of hydroxyl, ketone, aldehyde, ester, carboxylic acid and halogen.
Metal in VIII race's metal homogeneous catalyst and/or part can oxidized property deactivators be oxidized, after oxidizing reaction occurs, oxidized metal complexing decline and/or the oxidized coordination ability that is rear and metal of its part decline, part and metal is caused to depart from, make original catalyst volume reduction and/or polarity become large, more easily wash away by adsorbent or by eluent.These class methods are applicable to target resultant should not the oxidized or further reaction system be oxidized of target product need.
Described alkaline deactivators comprises inorganic alkali compound, organo-alkali compound, and wherein, described inorganic alkali compound has following general formula: M
1oH, wherein M
1for basic metal such as K, Na, Cs; Described organo-alkali compound has following general formula: R
3oM
2, wherein: M
2for the basic metal such as metal K, Na, Li, R
3for alkyl, the aryl of C1-C5, or with alkyl, the aryl of substituted radical.
The complex ability of the anionic group in alkalescence deactivators, it is made to replace original anion ligand, make metal together with the anionic group complexing in deactivators, together with sorbent material or eluent, be separated with resultant mixed solution, reach the object being separated this type of catalyzer, or part original in catalyzer is destroyed by alkaline deactivators, the complex ability of part is caused to decline, with metal separation, make original catalyst volume reduction and/or polarity become large, more easily wash away by adsorbent or by eluent.Both effect may be act in Individual existence or two existing simultaneously.These class methods be applicable to target resultant do not need with alkali reaction or target product further with the reaction system of alkali reaction.Can be used alone and also together can use with other materials (such as solvent).
Described complexing deactivators can be expressed as general formula:
wherein: R
4, R
5and R
6for one or more the replaced alkyl of C1-C4, the hydroxyalkyl of C1-C4 in the functional group of the alkyl of C1-C4, the hydroxyalkyl of C1-C4 or alkoxy, hydroxyl, ketone, aldehyde, ester, carboxylic acid and halogen.
The metal complexing metal that makes of VIII race is combined with complexing deactivators, with deactivators, is separated with resultant mixed solution.Select and be insoluble to product system and there is again the fluent meterial of strong complexing or solid matter as complexing deactivators, to be used alone or used in combination with special tensio-active agent, make its first and VIII race's metal complex, then the complex compound formed and deactivators are separated with resultant mixed solution together, to reach the object removing catalyzer.This method optionally can be combined with common adsorbents or eluent.
Preferably, when using oxygenant deactivators or alkaline deactivators, the treatment temp in step (1) is 50 DEG C-180 DEG C, and the treatment time is 30-150min; When using complexing agent deactivators, the treatment temp in step (1) is 10 DEG C-180 DEG C, and the treatment time is 30-150min.
Preferably, the mol ratio of described deactivators and homogeneous phase VIII race metal catalyst is 5-1000.
When using oxygenant deactivators or alkaline deactivators, when oxygenant deactivators or alkaline deactivators are insoluble to product mixture, the 0.1%-10% of described oxygenant deactivators or alkaline deactivators and the product mixture mass percent that need process; When using complexing agent deactivators, described complexing agent deactivators and the 1%-15% of product mixture mass percent that need process.
Further, after deactivators and VIII race's metal homogeneous catalyst react, for removing becoming the larger catalyzer of small volume, polarity and/or catalyzer relic and/or metal more up hill and dale, adsorption treatment can be carried out with common adsorbents again, comprising step B:
(1) under normal pressure or vacuum, under the adsorption temp of 10 DEG C-200 DEG C, carry out adsorption treatment 15-300min with sorbent material to remaining deactivators and the catalyzer that has been destroyed after process, wherein, the mass percent of sorbent material and resultant mixed solution is 0.5%-10%;
(2) with filtration and/or centrifugal method, sorbent material and product mixture are carried out separating treatment.
Preferably, in step B, the adsorption treatment time is 30 to 150min.
Physical absorbent bag expands gac, silica gel, molecular sieve, ion exchange resin, diatomite, wilkinite, kaolin.Mainly utilize their large specific surface area and their stronger adsorptive poweies of having.Wherein diatomite, atlapulgite and kaolinic physical absorbent require that its particle diameter has the percent of pass of more than 90% to 200 orders.Deactivators involved in the present invention is if solid-state, and itself also can be applied as sorbent material.
Further, after liquid deactivators and VIII race's metal homogeneous catalyst react, overwhelming majority catalyzer and/or catalyzer relic and/or metal are removed together with deactivators, for removing few remnants of catalyzer more up hill and dale, carrying out washing treatment can be carried out with common eluent again, comprise step C:
(3) under normal pressure or vacuum, under the adsorption temp of 10 DEG C-200 DEG C, carry out extraction treatment 1 to 240min with eluent to catalyzer remaining after process and deactivators, wherein, the volume percent of eluent and resultant mixed solution is 0.5%-50%;
(4) by the method for standing separation and/or centrifugation, eluent and product mixture are carried out separating treatment.
Preferably, the dissolution process time in step C is 30 to 150min.
Inorganic eluent comprises water, and organic elution agent comprises the polyols such as glycerol, tetramethylolmethane, trolamine,
When using liquid catalyst deactivators, if deactivators is completely insoluble with resultant mixed solution or extremely difficulty mixes, so the effect of deactivators will play not exclusively, now add dispersion agent can strengthen the specific surface area of deactivators, strengthen the reaction probabilities of deactivators and catalyzer and/or catalyzer relic, thus improve the removal effect of deactivators, as described in following steps:
Described step (1) is: at the temperature of 10 DEG C-200 DEG C, deactivators and dispersion agent is added in product mixture and carries out reaction 15 to 300min, and described deactivators comprises oxidisability deactivators, alkaline deactivators, complexing deactivators; Described dispersion agent can be expressed as general formula:
wherein: R
7, R
8, R
9for the hydroxyalkyl of hydroxyl, C1-C4, the acyl group of C10-C20 independently of one another, and R
7, R
8, R
9in the middle of have one and only have one to be the acyl group of C10-C20, R
10, R
11, R
12for the hydroxyalkyl of hydroxyl, C1-C4, the acyl group of C10-C20 independently of one another, and R
10, R
11, R
12in the middle of have one and only have one to be the acyl group of C10-C20.
Further, dispersant dosage is the mass percent of deactivators is 5%-100%, and preferably, dispersant dosage is the mass percent of deactivators is 10%-50%.
The liquid deactivators had and resultant mixed solution are immiscible, if use eluent, so eluent and resultant mixed solution are also immiscible.Now just can use the method for high efficient mixed, accelerate the speed of eluent and catalyst reaction, or improve the washing effect of eluent.High efficient mixed or can use dispersion agent less.
High efficient mixed herein refers to the stirring means that design is special, can make the deactivators insoluble with resultant mixed solution or eluent in resultant mixed solution, be dispersed into the drop being greater than 300 nanometers and being less than 150 microns by this method, thus increase the probability of deactivators and catalyst reaction or accelerate the dissolution rate of eluent and remaining catalyst debris and deactivators; Meanwhile, after stirring stops, scattered deactivators or eluent reassemble than being easier to again, are convenient to be separated.
Method involved in the present invention can be used alone, and also can two or more use together.The selection of method is depending on production technique, to factors such as the requirements of product or goods.
Due to after use VIII race metal homogeneous catalyst catalyzed reaction, reduce its resultant extremely important in the isomerization rate of the carbon-carbon double bond of separation, purifying, forming process and operational phase, can the isomerization rate that effectively reduce carbon-carbon double bond be the important indicator of method validity.In the present invention, the validity of determination methods is mainly carried out with the isomerization rate that can reduce 9-decylenic acid glyceryl ester.
Accompanying drawing explanation
Fig. 1 is the forward and backward gas chromatogram of 9-decenoate isomerization.
Embodiment
Embodiment 1 one kinds removes the method for homogeneous phase VIII race metal catalyst, comprises the following steps:
(1), at ambient pressure, at the temperature of 30 DEG C, 2g sodium methylate is added in 100g sample I fully to stir and carries out reaction 120min;
(2) be cooled to room temperature, after leaving standstill 1h, filter to isolate supernatant liquid.
Get filtrate and do isomerization experiments, after tested, 9-decylenic acid isomerization rate is 3.48%.
Embodiment 2 one kinds removes the method for homogeneous phase VIII race metal catalyst, comprises the following steps:
(1), at ambient pressure, at the temperature of 80 DEG C, 3 grams of solid glycerine sodium are added in 100g sample I fully to stir and carry out reaction 120min;
(2) be cooled to room temperature, after leaving standstill 1h, filter to isolate supernatant liquid.
Get filtrate and do isomerization experiments, after tested, 9-decylenic acid isomerization rate is 5.23%.
Embodiment 3 one kinds removes the method for homogeneous phase VIII race metal catalyst, comprises the following steps:
(1), at ambient pressure, at the temperature of 80 DEG C, 2 grams are ground to 200 object calcium peroxides and are added in 100g sample I fully to stir and carry out reaction 180min;
(2) be cooled to room temperature, after leaving standstill 1h, filter to isolate supernatant liquid.
Get filtrate and do isomerization experiments, after tested, 9-decylenic acid isomerization rate is 4.22%.
Embodiment 4 one kinds removes the method for homogeneous phase VIII race metal catalyst, comprises the following steps:
(1), at ambient pressure, at the temperature of 60 DEG C, the 9-decenoyl diethanolamine solution of the triethylamine of 5 gram 78% is added in 100g sample I fully to stir and carries out reaction 120min;
(2) carry out centrifugation (1900rpm, 10min) immediately after having stirred, isolate supernatant liquid.
Get filtrate isomerization experiments, after tested, 9-decylenic acid isomerization rate is 2.58%.
Embodiment 5 one kinds removes the method for homogeneous phase VIII race metal catalyst, comprises the following steps:
(1), at ambient pressure, at the temperature of 60 DEG C, the 9-decenoyl diethanolamine solution of the triethylamine of 5 gram 78% is added in 100g sample I fully to stir and carries out reaction 120min;
(2) carry out centrifugation (1900rpm, 10min) immediately after having stirred, isolate supernatant liquid;
(3) in the supernatant liquor in step (1), add 10 grams of glycerine, stir 5 hours;
(4) stir rear leaving standstill, isolate supernatant liquid.
Do isomerization experiments with supernatant liquor, after tested, 9-decylenic acid isomerization rate is 0.30%.
Embodiment 6 one kinds removes the method for homogeneous phase VIII race metal catalyst, comprises the following steps:
(1), at ambient pressure, at the temperature of 60 DEG C, the 9-decenoyl diethanolamine solution of the triethylamine of 12 gram 90% is added in 100g sample I fully to stir and carries out reaction 120min,
(2) carry out centrifugation (1900rpm, 10min) after having stirred, isolate supernatant liquid;
(3) in the supernatant liquor in step (2), add 4 grams of trolamines, fully stir 60 minutes;
(4) leave standstill, isolate supernatant liquid.
Do isomerization experiments with supernatant liquor, after tested, 9-decylenic acid isomerization rate is 0.26%.
Embodiment 7 one kinds removes the method for homogeneous phase VIII race metal catalyst, comprises the following steps:
(1), at ambient pressure, at the temperature of 60 DEG C, the 9-decenoyl diethanolamine solution of the triethylamine of 5 gram 78% is added in 100g sample I fully to stir and carries out reaction 120min,
(2) carry out centrifugation (1900rpm, 10min) immediately after having stirred, isolate supernatant liquid;
(3) in the supernatant liquor in step (2), 8g water is added, moderate-speed mixer 60 minutes;
(4) again carry out centrifugation (1900rpm, 10min), isolate supernatant liquid.
Isomerization experiments is done with supernatant liquor.After tested, 9-decylenic acid isomerization rate is 1.58%.
Embodiment 8 one kinds removes the method for homogeneous phase VIII race metal catalyst, comprises the following steps:
(1), at ambient pressure, at the temperature of 80 DEG C, be that the oleic monoesters solution of the triethylamine of 60 DEG C 85% is added in 100g sample I fully to stir and carries out reaction 20min by 5 grams of temperature;
(2) carry out centrifugation (1900rpm, 10min) immediately, isolate supernatant liquid;
(3) in the supernatant liquor in step (1), add 10 grams of glycerine, fully stir 190 minutes;
(4) stratification, isolates supernatant liquid.
Isomerization experiments is done with supernatant liquid.After tested, 9-decylenic acid isomerization rate is 0.35%.
Embodiment 9 one kinds removes the method for homogeneous phase VIII race metal catalyst, comprises the following steps:
(1), at ambient pressure, at the temperature of 60 DEG C, be that the oleic monoesters solution of the triethylamine of 60 DEG C 85% is added in 100g sample I fully to stir and carries out reaction 120min by 5 grams of temperature;
(2) carry out centrifugation (1900rpm, 10min) immediately after having stirred, isolate supernatant liquid;
(3) in the supernatant liquor in step (1), add 3 grams of atlapulgites, 40mmHg, 120 DEG C fully stir 90 minutes;
(4) with the cloth funnel suction filtration having Celite pad.
Do isomerization experiments with filtrate, after tested, 9-decylenic acid isomerization rate is 0.18%.
Embodiment 10 1 kinds removes the method for homogeneous phase VIII race metal catalyst, comprises the following steps:
(1), at normal pressure, under normal temperature, the aqueous isopropanol of the triethylamine of 5 gram 50% (v/v) is added to moderate-speed mixer in 100g sample I and carries out reaction 240min;
(2) the sample water washing 2 times of each 20ML, isolates supernatant liquid.
Isomerization experiments is done with clear liquid.After tested, 9-decylenic acid isomerization rate is 0.15%.
Embodiment 11 1 kinds removes the method for homogeneous phase VIII race metal catalyst, comprises the following steps:
(1), at 100mmHg, the temperature of 120 DEG C, the trolamine that 5 grams of diatomite do carrier is added in 100g sample I fully to stir and carries out reaction 120min;
(2) carry out centrifugation (1900rpm, 10min) after cooling, isolate supernatant liquid.
Isomerization experiments is done with supernatant liquor.After tested, 9-decylenic acid isomerization rate is 1.57%.
Embodiment 12 1 kinds removes the method for homogeneous phase VIII race metal catalyst, comprises the following steps:
(1) at normal pressure, at the temperature of 120 DEG C, in 100g sample I, be blown into the air of 50 DEG C, fully stir and carry out reaction 120min;
(2) add 5% (w/w) atlapulgite, 40mmHg, 120 DEG C fully stir 90 minutes;
(3) with the cloth funnel suction filtration having Celite pad.
Filtrate does isomerization experiments, and after tested, 9-decylenic acid isomerization rate is 7.83%.
Embodiment 13 1 kinds removes the method for homogeneous phase VIII race metal catalyst, comprises the following steps:
(1) at normal pressure, at the temperature of 120 DEG C, in 100g sample I, be blown into the air of 50 DEG C, fully stir and carry out reaction 180min;
(2) add 5% (w/w) atlapulgite, 40mmHg, 120 DEG C fully stir 90 minutes;
(3) with the cloth funnel suction filtration having Celite pad.
Filtrate does isomerization experiments, and after tested, 9-decylenic acid isomerization rate is 5.06%.
Embodiment 14 1 kinds removes the method for homogeneous phase VIII race metal catalyst, comprises the following steps:
(1) at normal pressure, the temperature of 80 DEG C, add 5 grams of 3%KOH/ glycerine solutions and be added in 100g sample I, high-speed mixing 30min;
(2) be cooled to room temperature, standing 1h isolates supernatant liquor.
Get supernatant liquid and do isomerization experiments.After tested, 9-decylenic acid isomerization rate 0.22%.
Embodiment 15 1 kinds removes the method for homogeneous phase VIII race metal catalyst, comprises the following steps:
(1), at normal pressure, at the temperature of 60 DEG C, 5g trolamine is added to 100g sample I, high efficient mixed 30min;
(2) carry out centrifugation (1900rpm, 10min), isolate supernatant liquid.
Do isomerization experiments with supernatant liquor, through GC test analysis, after tested, 9-decylenic acid isomerization rate is 3.62%.
Embodiment 16 1 kinds removes the method for homogeneous phase VIII race metal catalyst, comprises the following steps:
(1), at normal pressure, at the temperature of 80 DEG C, 5g trolamine is added to 100g sample I, high efficient mixed 15min;
(2) carry out centrifugation (1900rpm, 10min), isolate supernatant liquid.
Do isomerization experiments with supernatant liquor, through GC test analysis, after tested, 9-decylenic acid isomerization rate is 1.81%.
Embodiment 17 1 kinds removes the method for homogeneous phase VIII race metal catalyst, comprises the following steps:
(1), at normal pressure, at the temperature of 100 DEG C, 5g trolamine is added to 100g sample I, high efficient mixed 10min;
(2) carry out centrifugation (1900rpm, 10min), isolate supernatant liquid.
Do isomerization experiments with supernatant liquor, through GC test analysis, after tested, 9-decylenic acid isomerization rate is 1.92%.
Embodiment 18 1 kinds removes the method for homogeneous phase VIII race metal catalyst, comprises the following steps:
(1) at normal pressure, the temperature of 80 DEG C, add 5 grams of trolamines and be added in 100g sample I, high-speed mixing 120min;
(2), after reaction terminates, leave standstill 15min at 80 DEG C, isolate supernatant liquid;
(3) add 3g trolamine in the supernatant liquid in step (1), under room temperature, fully stir 30min;
(4) left at room temperature 15min, isolates supernatant liquid and does isomerization experiments.
After tested, 9-decylenic acid isomerization rate is 0.23%.
Embodiment 19 1 kinds removes the method for homogeneous phase VIII race metal catalyst, comprises the following steps:
(1) at normal pressure, the temperature of 80 DEG C, add 5 grams of trolamines and be added in 100g sample I, high-speed mixing 15min;
(2), after reaction terminates, carry out centrifugation (1900rpm, 10min), isolate supernatant liquid;
(3) add 3g glycerine in the supernatant liquid in step (2), under room temperature, fully stir 30min;
(4) carry out centrifugation (1900rpm, 10min), isolate supernatant liquid.
Isomerization experiments is done with supernatant liquor.After tested, 9-decylenic acid isomerization rate is 0.12%.
In the embodiment above, it is the olefin metathesis reactions for the vegetables oil of Grubbs ruthenium catalyst catalysis and alpha-olefin, wherein, sample I is the product mixture using the vegetables oil of Grubbs ruthenium catalyst catalysis and the olefin metathesis reactions of alpha-olefin, and in mixture, ruthenium concentration is 15ppm.
Isomerization experiments: take and remove the resultant mixed solution 2g after catalyzer in 20mL bottle through deactivators, put into magnetic stir bar, induction stirring 2h in 180 DEG C of oil baths, under argon shield.Gas-chromatography sample is made as follows after being cooled to room temperature.
The methanol solution of sodium methylate 2mL of the resultant mixed solution 0.5g and 0.5% after above-mentioned isomerization experiments is joined in 20mL bottle, screws bottle cap, the lower 60 DEG C of heating esterification reaction of organic acid 1h of induction stirring.Be cooled to room temperature, add 3mL normal hexane, stir extraction.After leaving standstill 30min, draw upper solution 0.25mL, in chromatography of gases sample bottle, be diluted to 1.0mL with normal hexane, carry out gas-chromatography test.
Fig. 1 is the comparison of gas chromatogram before and after the isomerization of 9-decenoate, as shown in Figure 1, in retention time, the isomerized 9-decenoate do not had completely is that 8.36min place has one unimodal, after isomerization occurs, four peaks can be there are at 8.21min, 8.32min, 8.44min, 8.63min, wherein retention time is that the peak of 8.32min is 9-decenoate, and other three peaks are the new peaks produced because of isomerization.The new peak area sum occurred after isomerization and the percentage ratio of the ratio of the total area at above-mentioned four peaks, be isomerization rate.
Without the sample I of any catalyzer deactivators process, after isomerization test, its isomerization rate is 70.52%.
Claims (15)
1. remove a method for homogeneous phase VIII race metal catalyst, it is characterized in that: comprise experimental procedure A:
(1) at normal pressure, the temperature of 10 DEG C-200 DEG C, deactivators is added in product mixture and carries out reaction 15-300min, described deactivators is oxidisability deactivators, alkaline deactivators or complexing deactivators, and the mol ratio of described deactivators and homogeneous phase VIII race metal catalyst is 1-10000;
(2) deactivators, catalyzer and product mixture after step (1) process are carried out separating treatment.
2. a kind of method removing homogeneous phase VIII race metal catalyst according to claim 1, it is characterized in that: the described oxidisability deactivators in step (1) comprises inorganic peroxide, organo-peroxide, oxygen, ozone, air, wherein, described inorganic peroxide comprises hydrogen peroxide (H
2o
2), sodium peroxide (Na
2o
2), calcium peroxide (CaO
2); Described organo-peroxide has following general formula: R1-O-O-R2,
Wherein, R1 and R2 is selected from H, C1-C20 alkyl, aryl, C1-C20 carbonyl, C1-C20 carbonate group.
3. a kind of method removing homogeneous phase VIII race metal catalyst according to claim 1, it is characterized in that: the described alkaline deactivators in step (1) comprises inorganic alkali compound, organo-alkali compound, wherein, described inorganic alkali compound has following general formula: M
1oH, wherein M
1for basic metal; Described organo-alkali compound has following general formula: R
3oM
2, wherein, M
2for basic metal, R
3for alkyl, the aryl of C1-C5.
4. a kind of method removing homogeneous phase VIII race metal catalyst according to claim 1, is characterized in that: the described complexing deactivators in step (1) can be expressed as
wherein: R
4, R
5and R
6for the alkyl of C1-C4, the hydroxyalkyl of C1-C4.
5. a kind of method removing homogeneous phase VIII race metal catalyst according to claim 1, it is characterized in that: preferably, when using oxygenant deactivators or alkaline deactivators, the treatment temp in step (1) is 50 DEG C-180 DEG C, and the treatment time is 30-150min; When using complexing agent deactivators, the treatment temp in step (1) is 10 DEG C-180 DEG C, and the treatment time is 30-150min.
6. a kind of method removing homogeneous phase VIII race metal catalyst according to claim 1, is characterized in that: preferred, the mol ratio of described deactivators and homogeneous phase VIII race metal catalyst is 5-1000.
7. a kind of method removing homogeneous phase VIII race metal catalyst according to claim 1, it is characterized in that: when using oxygenant deactivators or alkaline deactivators, when oxygenant deactivators or alkaline deactivators are insoluble to product mixture, the 0.1%-10% of the product mixture mass percent of described oxygenant deactivators or alkaline deactivators and required process; When using complexing agent deactivators, when complexing agent deactivators is insoluble to product mixture, the 1%-15% of the product mixture mass percent of described complexing agent deactivators and required process.
8. a kind of method removing homogeneous phase VIII race metal catalyst according to claim 1, is characterized in that: carry out high efficient mixed after deactivators can being added product mixture in step (1).
9. a kind of method removing homogeneous phase VIII race metal catalyst according to claim 1, is characterized in that: also comprise step B:
(1) under normal pressure or vacuum, under the adsorption temp of 10 DEG C-200 DEG C, carry out adsorption treatment 15-300min with sorbent material to remaining deactivators and the catalyzer that has been destroyed after process, wherein, the mass percent of sorbent material and resultant mixed solution is 0.5%-10%;
(2) with filtration or centrifugal method, sorbent material and product mixture are carried out separating treatment.
10. a kind of method removing homogeneous phase VIII race metal catalyst according to claim 9, is characterized in that: preferred, in step B, the adsorption treatment time is 30 to 150min.
11., according to the arbitrary a kind of described method removing homogeneous phase VIII race metal catalyst of claim 1 or 9, is characterized in that: also comprise step C:
(1) under normal pressure or vacuum, under the adsorption temp of 10 DEG C-200 DEG C, carry out extraction treatment 1 to 240min with eluent to catalyzer remaining after process and deactivators, wherein, the volume percent of eluent and resultant mixed solution is 0.5%-50%;
(2) by the method for standing separation or centrifugation, eluent and product mixture are carried out separating treatment.
12. a kind of methods removing homogeneous phase VIII race metal catalyst according to claim 11, is characterized in that: preferred, the dissolution process time in step C is 30 to 150min.
13. a kind of methods removing homogeneous phase VIII race metal catalyst according to claim 1, it is characterized in that: in described step (1), deactivators and dispersion agent are added in product mixture and react, described dispersion agent can be expressed as general formula:
wherein, R
7, R
8, R
9for being selected from hydroxyl, the hydroxyalkyl of C1-C4, the acyl group of C10-C20, and R
7, R
8, R
9in the middle of have one and only have one to be the acyl group of C10-C20, R
10, R
11, R
12for being selected from hydroxyl, the hydroxyalkyl of C1-C4, the acyl group of C10-C20, and R
10, R
11, R
12in the middle of have one and only have one to be the acyl group of C10-C20.
14. a kind of methods removing homogeneous phase VIII race metal catalyst according to claim 13, is characterized in that: the mass percent of dispersion agent and deactivators is 5%-100%.
15. a kind of methods removing homogeneous phase VIII race metal catalyst according to claim 14, is characterized in that: preferred, the mass percent of dispersion agent and deactivators is 10%-50%.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1067898A (en) * | 1992-07-08 | 1993-01-13 | 北京燕山石油化工公司研究院 | Method for removing residual metal catalyst after polymer hydrogenation |
| CN102875702A (en) * | 2011-07-13 | 2013-01-16 | 中国石油化工集团公司 | Method for removing metals from polymer |
| CN104072645A (en) * | 2013-03-28 | 2014-10-01 | 中国石油化工股份有限公司 | Method for removing residual metal catalysts from hydrogenation polymer glue solution |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1067898A (en) * | 1992-07-08 | 1993-01-13 | 北京燕山石油化工公司研究院 | Method for removing residual metal catalyst after polymer hydrogenation |
| CN102875702A (en) * | 2011-07-13 | 2013-01-16 | 中国石油化工集团公司 | Method for removing metals from polymer |
| CN104072645A (en) * | 2013-03-28 | 2014-10-01 | 中国石油化工股份有限公司 | Method for removing residual metal catalysts from hydrogenation polymer glue solution |
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