CN106831305A - A kind of method that long-chain olefin is prepared by medium chain alkene - Google Patents
A kind of method that long-chain olefin is prepared by medium chain alkene Download PDFInfo
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- C07—ORGANIC CHEMISTRY
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- C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
- C07C6/02—Metathesis reactions at an unsaturated carbon-to-carbon bond
- C07C6/04—Metathesis reactions at an unsaturated carbon-to-carbon bond at a carbon-to-carbon double bond
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Abstract
The present invention provides a kind of method that long-chain olefin is prepared by medium chain alkene, and methods described comprises the following steps：(1) the medium chain alkene with 7 to 12 carbon atoms is provided；(2) to adding homogeneous catalyst in the medium chain alkene, and make the medium chain alkene that metathesis reaction to occur under the conditions of olefin metathesis reactions；(3) produced in removal course of reaction with 2 to 6 small-numerator olefins of carbon atom, so as to the linear long-chain olefin of non-alpha for obtaining that there are 13 to 24 carbon atoms.The inventive method is to catalyst amount, feed postition, and the proportioning of raw material etc. is explored, have found most suitable reaction condition, the final long-chain olefin for obtaining higher degree, allow that long-chain olefin is realized being prepared from biomass material, solve the non-renewable problem of conventional raw material, expanded the range of application of long-chain olefin.
Description
The application is the invention name that Tianjin Co., Ltd of Si Ruiji high and new technologies research institute submitted on December 31st, 2015
Referred to as " a kind of method that long-chain olefin is prepared by medium chain bio-based alkene ", Application No. " 201511035169.1 " point
Case application.
Technical field
The present invention relates to organic synthesis field, and in particular to a kind of method that long-chain olefin is prepared by medium chain alkene.
Background technology
Long-chain olefin refers to the non-alpha-linear alpha-olefin of C13-C24, and long-chain olefin has many purposes, for example：Can as raw material
To produce surfactant, long chain silane, long chain mercaptans, long-chain amine, long-chain alcohol etc.；Itself can be directly as can be biological
The deep sea drilling oil of degraded is used.
There are several known methods to can be used to prepare long-chain olefin in current world wide, for example：Petroleum cracking method, alkene
Oligomerisation method (SHOP methods), Fischer-Tropsch methods and Olefin metathesis catalysis method.
Typical Olefin metathesis catalysis method is, with metal carbene compound as catalyst, to make that itself transposition occurs between alkene
It is most attraction at present the characteristics of selectivity of product is high with high income or cross metathesis reaction prepares long-chain olefin
The method for preparing long-chain olefin.Olefin metathesis catalyst can be divided into homogeneous catalysis method and heterogeneous catalysis method, used as raw material reaction
Alkene is generally from the mineral-based product of petroleum-based products or Coal Chemical Industry production.However, produced from petroleum base or Coal Chemical Industry
Mineral base medium chain olefin feedstock can reduce catalyst activity reduction inevitably containing N, P, S etc..
Fred Chun-Chien Twu et al. are disclosed in the A1 of patent US 2003/0224945 and are used heterogeneous catalysis
Agent (solid-state), is raw material using the alpha-olefin obtained by Fischer-Tropsch methods, and alkene long is prepared by olefin metathesis reactions
The method of hydrocarbon.Twu Fred et al. are disclosed using heterogeneous catalysis (solid-state) in the A1 of patent WO 03/101920, are utilized
The alpha-olefin obtained by SHOP methods is raw material, and the method that long-chain olefin is prepared by olefin metathesis reactions, using the method, is prepared
Can be used for the synthesis base base oil of deep sea drilling liquid.
The focus of current research is concentrated mainly on two principal themes：The research and development of new catalyst and look for more cheap, renewable
Raw material sources.
Homogeneous catalysts of olefin metathesis reactions is compared compared to heterogeneous catalysis, uses homogeneous catalysts of olefin metathesis reactions
Production long-chain olefin has the advantages that high catalytic efficiency, consumption are few, while also causing that reaction condition is gentle, three wastes are produced, raw
Product is easy to carry out.
And medium chain bio-based alkene as the raw material for preparing long-chain olefin is obtained by the use of vegetable oil and small-numerator olefin,
Because vegetable oil is renewable resource, and wide material sources, the petroleum cracking raw material used compared to SHOP methods and
The raw material of the conventionally used Coal Chemical Industry production of Fischer-Tropsch methods, more environmental protection, the sight for more meeting sustainable development
Read；Additionally, vegetable oil and small-numerator olefin intersect olefin metathesis reactions process is simple, three wastes are produced, reaction condition is gentle,
It is the method for ideal production medium chain alkene.
From different vegetable oil and/or small-numerator olefin, olefin metathesis are intersected by vegetable oil and small-numerator olefin anti-
The bio-based alkene that should be obtained is also different, is additionally, since in vegetable oil in addition to containing saturation and single unsaturation composition, also contains
There are the so-called how unsaturated compositions such as double unsaturated and three unsaturations, therefore can cause contain in the alkene of the medium chain for generating
The composition of double unsaturated olefins so that the raw material that its olefin metathesis reactions is obtained with SHOP methods or Fischer-Tropsch methods
Olefin metathesis reactions are compared, more particularity.
The content of the invention
The purpose of the present invention is that invention is a kind of uses the homogeneous catalysts of olefin metathesis reactions of metal carbene class, makes medium chain
Bio-based alkene occur olefin metathesis reactions, the method so as to prepare long-chain olefin, with process is simple, mild condition, institute
Obtain the features such as product purity is higher, raw material sources are extensive.
The technical scheme is that：
Using vegetable oil and small-numerator olefin by intersecting the life of the medium chain (C7-C12) that olefin metathesis reactions are obtained
Thing base alkene is raw material, and long-chain olefin is prepared through homogeneous catalyst catalytic reaction.
The program is illustrated respectively according to raw material, catalyst, reaction condition, product below.
1st, raw material：
The raw material for preparing long-chain olefin involved in the present invention is the bio-based alkene of medium chain, i.e. vegetable oil and C2-
The small-numerator olefin of C6, through the alkene obtained by catalysts of olefin metathesis reactions effect, in Chinese patent
CN201510799475.6 is documented.
Predominantly C7, C9, C10, C12, molecular formula are as follows：
When C7 and C12 is as mixed material, the ratio (equivalent proportion) of mixing is 1:1~100, preferably 1:3~20, enter
One step is preferably 1:5~10；When C9 and C10 is as mixed material, the ratio of mixing is 100:1~10000, preferably
100:20~500, further preferred is 100:50~200；When C9 and C12 is as mixed material, the ratio of mixing is 100:1
~10000, preferably 100:20~500, further preferred is 100:50~200；C10 can be separately as raw material；C12
Can be separately as raw material.
2nd, catalyst
Catalyst involved by this patent is homogeneous metal olefin displacement catalysts, and relatively applicable is ruthenium metal ion
Catalyst, more applicable is first and second generation lattice granny rag catalyst or the catalysis of the novel N-heterocyclic carbenes ruthenium containing electron donating group
Agent, the present invention mainly selects the homemade novel N-heterocyclic carbenes ruthenium catalyst containing electron donating group, in patent
Its preparation method is documented in CN201510178654.8.
Catalysts of olefin metathesis reactions consumption involved in the present invention for medium chain olefin feed weight 10ppm extremely
1000ppm, preferable amount is 20ppm-500ppm, and the consumption being more highly preferred to is 30ppm-400ppm.
First by catalyst with a small amount of toluene or dichloromethane wiring solution-forming to facilitate addition, catalyst can disposably add
Enter, also graded is added.It is exactly to divide catalyst in the different phase of reaction to add several times to add by several times, is conducive to conversion ratio
Improve.Preferably, catalyst is divided into two parts of equivalent, respectively at start reaction when and the reaction time carry out 1/3 when addition.
3rd, olefin metathesis reactions
Reaction temperature is 20-80 DEG C, and preferably 30-70 DEG C, further preferred is 35-60 DEG C；
Reaction time is 1-72 hours, and preferably 2-48 hours, further preferred was 3-24 hours.
4th, product
Because the combination of medium chain alkene is different, the long-chain olefin of generation can be different.Ignore anti-in olefin metathesis
During with the combination of different medium chain alkene as raw material, should can generate following height with the isomerization reaction for occurring simultaneously
Carbon olefin：
● C7-C12 is combined：
● C9-C10 is combined
● C9-C12 is combined
● C12 reacts
● C10 reacts
Involved small-numerator olefin (1)-small-numerator olefin (5) is the small-numerator olefin of C2-C6 in above reaction equation
Various combination, accessory substance (1)-accessory substance (5) is the carbon number that is produced due to isomerization and olefin metathesis reactions less than 13
The various combination of alkene.
The method that the present invention also provides the above-mentioned small-numerator olefin of removal：Due to during the course of the reaction, having ethene and/or third
Alkene and/or the small-numerator olefin such as butylene and/or amylene and/or hexene are produced, and need to disengage it from reaction system, make reaction to predetermined
The Direction of Reaction is moved, and improves conversion ratio.The method for removing small-numerator olefin has：A) Bubbling method：It is higher than small molecule in reaction temperature
In the case of boiling olefins, inert gas (such as nitrogen, argon gas) is passed through in reaction solution, makes small-numerator olefin with inert gas
It is rapid together to depart from reaction system；B) depressurize method：Reaction system is decompressed to certain vacuum degree, according to raw material and reaction temperature
Difference, in the case where raw material does not lose, applies vacuum as big as possible, small-numerator olefin is departed from reaction system rapidly；
C) mixing method：Will vacuum method and Bubbling method use simultaneously, small-numerator olefin is departed from reaction system rapidly.
By technical scheme, to catalyst amount, proportioning of feed postition, and raw material etc. is explored,
Most suitable reaction condition is have found, the final long-chain olefin for obtaining higher degree so that long-chain olefin can be realized from biology
Prepared in matter raw material, solve the non-renewable problem of conventional raw material, expanded the range of application of long-chain olefin.
Specific embodiment
Operating method：In glove box, by the reactant of constant weight, (single alkene or several alkene press certain weight ratio
Mixed olefins) be added to and be placed with the reaction bulb of electromagnetic agitation, add a certain amount of catalyst toluene with micro syringe
Solution, makes catalyst weight that finite concentration (ppm w/w) is reached to reactant weight, it is also possible to which method adds catalyst twice, i.e.,
A part of catalyst is first added, when reaction proceeds to a certain degree, remaining catalyst is added.Tracheae and condenser pipe will be raised
Air extraction connector is respectively installed on two grounds of reaction bulb, then air extraction connector is connected into condenser pipe upper end, is closed and is raised tracheae
After the valve of air extraction connector, reaction bulb is taken out from glove box.
The difference of the small-numerator olefin that cooling medium temperature need to be produced according to raw material and reaction and adjust, the boiling point of raw material compared with
When low (such as C7, boiling point is 80-90 DEG C), to prevent significant loss, cooling medium will be lower, the small-numerator olefin point of generation
Son measure larger (such as hexene) when, be that can exclude reaction system, cooling medium temperature be accomplished by it is higher, according to reactant
The difference of system, can be adjusted in the range of 15-30 DEG C.
When reaction needs Bubbling method to remove small-numerator olefin, high pure nitrogen input pipe is linked to feeding tracheae, by oil vacuole
Meter is connected to air extraction connector, first opens High Purity Nitrogen valve, then opening air extraction connector valve, regulation High Purity Nitrogen air inflow (according to
The size of reaction-ure mixture, 100-1 bubble about per second in oil vacuole meter).When reaction needs to be removed under reduced pressure small-numerator olefin,
In the state of tracheae valve closing is raised, vavuum pump, regulation vacuum to required vacuum are started.When reaction needs mixing method to remove
During small-numerator olefin, open and raise tracheae valve, start vavuum pump, while adjust raising tolerance and vacuum, enter inert gas
Amount and vacuum reach experiment necessary requirement.
In the oil bath of uniform temperature, magnetic stirring apparatus, reaction to stipulated time are started.Sampling carries out gas-chromatography point
Analysis.
The preparation of gas-chromatography sample：Degreasing cotton-wool is added in 1 milliliter of syringe, syringe outlet is sealed, to injection
The adsorbent of 1 cm height, top degreasing cotton-wool is added to seal and be compacted adsorbent in device.Sample 0.5g to be measured is taken to add
Enter in this syringe, sample is expelled in the vial of 20mL through syringe, add 3mL n-hexanes, after stirring, dissolving,
Draw solution 0.25mL, about 1.0mL is diluted in gas-chromatography sample bottle with n-hexane, carries out gas Chromatographic Determination.It contains
Amount reads the peak area percent of gas-chromatography.
Tester：Agilent 7890A gas chromatographs are furnished with automatic sampler.Gas-chromatography test parameter is：Chromatogram
Post：The HP-5 (0.25 μm of 30m × 250 μ m) of Agilent, injector temperature：250 DEG C, sample size：1 μ L, split ratio：50:1,
Fid detector：280 DEG C, carrier gas：N2, post case：100 DEG C of holdings 1min, 10 DEG C/min rise to 250 DEG C, keep 15min.Barrier film is true
Empty pump (GM-0.5B, Tian Jinjin rise experimental facilities Co., Ltd).
The retention time of the different products of table 1
Embodiment 1, C7-C12 combination raw materials prepare higher olefins
As raw material, reactant gross weight is 5g to alkene with the C7-C12 bio-based medium chains of different ratio, and addition is pushed away
Electronics base catalysts of olefin metathesis reactions 200ppm, with the small molecule alkene produced in high pure nitrogen Bubbling method removal course of reaction
Hydrocarbon, condensed fluid temperature is 20 DEG C in condenser pipe.Electromagnetic agitation is started, 24h is reacted at 30 DEG C.Table 2 is gas chromatographic analysis
As a result.
The difference of table 2 C7-C12 is with the influence for comparing conversion ratio
Test result shows, in addition to having olefin metathesis reactions and occurring, also there occurs the isomery that double bond is migrated along carbochain
Change reaction so that product becomes complex.The ratio of C7 is higher in raw material, and the content of C15 is higher in product, C18's
Content is lower, and total conversion is higher.
Embodiment 2, C9-C10 combination raw materials prepare higher olefins
As raw material, reactant gross weight is 5g to alkene with the C9-C10 bio-based medium chains of different ratio, and addition is pushed away
Electronics base catalysts of olefin metathesis reactions 200ppm, with the small-numerator olefin produced in the method removal course of reaction that depressurizes, adjustment is true
Reciprocal of duty cycle is to 120mmHg；Condensed fluid temperature is 25 DEG C in condenser pipe.Electromagnetic agitation is started, 19h is reacted at 50 DEG C.Table 3 is gas
Analysis of hplc result.
The difference of table 3 C9-C10 is with the influence for comparing conversion ratio
As shown in Table 3, C9 is worked as:The ratio of C10 is 1:When 2, total conversion highest works as C9:The ratio of C10 is 2:When 1,
The conversion ratio highest of C15.
Embodiment 3, C9-C12 combination raw materials prepare higher olefins
As raw material, reactant gross weight is 5g to alkene with the C9-C12 bio-based medium chains of different ratio, and addition is pushed away
Electronics base catalysts of olefin metathesis reactions toluene solution makes the 50ppm that catalyst concn is raw material weight, and to depressurize, method removal is anti-
The small-numerator olefin produced during answering, adjustment vacuum to 120mmHg；Condensed fluid temperature is 25 DEG C in condenser pipe.Start
Electromagnetic agitation, 10h is reacted at 50 DEG C.Table 4 is gas chromatographic analysis result.
The difference of table 4 C9-C12 is with the influence for comparing conversion ratio
Test result shows that, when the ratio of C10 is higher, total conversion is higher, and now C15 yields are relatively low and C18 yields
It is higher.
Embodiment 4, C9 prepares higher olefins for raw material
5g bio-based C9 alkene is weighed, addition pushes away electronics base catalysts of olefin metathesis reactions toluene solution makes catalyst concn
It is the 100ppm 100ppm of raw material weight, with the small-numerator olefin produced in the method removal course of reaction that depressurizes, adjustment vacuum is extremely
120mmHg；Condensed fluid temperature is 25 DEG C in condenser pipe.Electromagnetic agitation is started, 7h is reacted at 50 DEG C.Table 5 is gas-chromatography
Analysis result.
The C9 of table 5 prepares higher olefins for raw material
Embodiment 5, C12 prepares higher olefins for raw material
Bio-based medium chain C12 alkene 5g are weighed, addition pushes away electronics base catalysts of olefin metathesis reactions toluene solution to be made
Catalyst concn is the 100ppm of raw material weight, with the small-numerator olefin produced in the method removal course of reaction that depressurizes, adjusts vacuum
Spend to 120mmHg；Condensed fluid temperature is 25 DEG C in condenser pipe.Electromagnetic agitation is started, 6h is reacted at 50 DEG C.Table 6 is gas phase
Chromatography result.
The C12 of table 6 prepares higher olefins for raw material
Embodiment 6, C10 prepares higher olefins for raw material under different catalysts concentration
5g bio-based C10 alkene is respectively weighed in two reaction bulbs, is separately added into and is pushed away the catalysis of electronics base olefin metathesis reactions
Agent, makes catalyst concn respectively reach 100ppm and 40ppm, with the small-numerator olefin produced in the method removal course of reaction that depressurizes,
Adjust vacuum to 120mmHg；Condensed fluid temperature is 25 DEG C in condenser pipe.Electromagnetic agitation is started, 19h is reacted at 50 DEG C.
Table 7 is gas chromatographic analysis result.
The C10 of table 7 prepares higher olefins for raw material
Analysis result shows that larger catalyst consumption can improve total conversion, while isomerization reaction also can be made more
Seriously, the higher olefins content for showing as being produced due to isomerization reaction is improved.
Embodiment 7, C9-C10 combination raw materials prepare the experiment of higher olefins multikilogram
As shown in Table 3, C9 is worked as:The ratio of C10 is 1:When 2, total conversion highest, so put with the combination raw materials of this ratio
Amount prepares higher olefins.
C9 alkene 310g and C10 alkene 690g is weighed respectively in reactor, adds catalyst toluene solution to make catalyst
Concentration is the 25ppm of raw material weight, and coolant temperature is room temperature in condenser pipe, and the small-numerator olefin for producing is removed with combined method,
To 120mmHg, bubbles volume is about 20 per minute to regulation vacuum.Strong magnetic stirring apparatus is started, revolution is 800rpm.At 50 DEG C
After lower reaction 6h, 25ppm catalyst is added again, continue to react 14h.Gas chromatographic analysis result is as shown in table 8.
The multikilogram C9-C10 combination raw materials of table 8 prepare higher olefins
Embodiment 8, C12 prepares the experiment of higher olefins multikilogram for raw material
C12 alkene 1000g is weighed respectively in reactor, adds catalyst toluene solution to make catalyst concn be raw material weight
The 50ppm of amount, in condenser pipe coolant temperature be room temperature, with combined method remove produce small-numerator olefin, regulation vacuum to
120mmHg, bubbles volume is about 20 per minute.Strong magnetic stirring apparatus is started, revolution is 800rpm.24h is reacted at 50 DEG C.
The multikilogram C12 raw materials of table 9 prepare higher olefins
Compared by embodiment it can be found that prepare higher olefins using combination alkene, than doing original with a kind of independent alkene
During material, conversion ratio is higher.
Above-described embodiment has carried out detailed analysis to the product of the bio-based olefine reaction of the medium chain of various combination,
Draw and preferably used combination.
One embodiment of the present of invention has been described in detail above, but the content is only preferable implementation of the invention
Example, it is impossible to be considered as limiting practical range of the invention.All impartial changes made according to the present patent application scope and improvement
Deng all should still belong within patent covering scope of the invention.
Claims (10)
1. a kind of method that long-chain olefin is prepared by medium chain alkene, it is characterised in that methods described comprises the following steps：
(1) medium chain alkene is provided, wherein the medium chain alkene is with 7 to 12 alkene of carbon atom；
(2) to adding homogeneous catalyst in the medium chain alkene, and the medium chain alkene is made in olefin metathesis reactions
Under the conditions of there is metathesis reaction；With
(3) small-numerator olefin produced in removal course of reaction, so as to obtain long-chain olefin, wherein the small-numerator olefin is tool
There are 2 to 6 small-numerator olefins of carbon atom, the long-chain olefin is with 13 to 24 non-alpha-linear alpha-olefins of carbon atom.
2. method according to claim 1, it is characterised in that the medium chain alkene is selected from by C7 alkene, C9 alkene
At least one of group of hydrocarbon, C10 alkene and C12 alkene composition or various, the C7 alkene, C9 alkene, C10 alkene and C12 alkene
The molecular formula difference of hydrocarbon is as follows：
A, C7 alkene：
B, C9 alkene：
C, C10 alkene：
D, C12 alkene：
3. method according to claim 2, it is characterised in that the medium chain alkene is selected from following any group：
(1) equivalent proportion is 1:1~100, preferably 1:3~20 C7 alkene and the mixture of C12 alkene；
(2) equivalent proportion is 100:1~10000, preferably 100:20~500 C9 alkene and the mixture of C10 alkene；
(3) equivalent proportion is 100:1~10000, preferably 100:20~500 C9 alkene and the mixture of C12 alkene；
(4) C9 alkene；
(5) C10 alkene；
(6) C12 alkene.
4. method according to claim 3, it is characterised in that the medium chain alkene is selected from following any group：
(1) equivalent proportion is 1:5~10 C7 alkene and the mixture of C12 alkene；
(2) equivalent proportion is 100:50~200 C9 alkene and the mixture of C10 alkene；
(3) equivalent proportion is 100:50~200 C9 alkene and the mixture of C12 alkene.
5. method according to claim 1, it is characterised in that the medium chain alkene be using vegetable oil with have 2
To 6 small-numerator olefins of carbon atom by intersecting the medium chain bio-based alkene that olefin metathesis reactions are obtained.
6. method according to claim 1, it is characterised in that：
The homogeneous catalyst is that homogeneous metal olefin replaces catalysts；
Catalyst amount is the 10ppm to 1000ppm of medium chain olefin feed weight；
The feed postition of catalyst is added or addition by several times for disposable.
7. method according to claim 6, it is characterised in that：
The homogeneous catalyst is that first generation Ge Labu catalyst, second generation Ge Labu catalyst or the N- containing electron donating group are miscellaneous
Ring Cabbeen ruthenium catalyst；
Catalyst amount is the 20ppm to 500ppm of medium chain olefin feed weight；
The feed postition of catalyst to add by several times, wherein catalyst is divided into two parts of equivalent, it is when reaction is started and anti-
Addition when 1/3 is carried out between seasonable.
8. method according to claim 1, it is characterised in that：
Reaction temperature is 20-80 DEG C, more preferably preferably 30-70 DEG C, 35-60 DEG C；And/or
Reaction time is 1-72 hours, preferably 2-48 hours, more preferably 3-24 hours.
9. the method according to any one of claim 1-8, it is characterised in that any one in adopting with the following method is made a return journey
Except small-numerator olefin：
A) Bubbling method：In the case where reaction temperature is higher than small-numerator olefin boiling point, inert gas is passed through in reaction solution, made small
Molecular olefine departs from reaction system with inert gas；
B) depressurize method：In the case where raw material does not lose, apply vacuum as big as possible, small-numerator olefin is departed from reactant
System；
C) mixing method：The Bubbling method and the decompression method are carried out simultaneously, small-numerator olefin is departed from reaction system.
10. method according to claim 1, it is characterised in that：
The medium chain alkene is that equivalent proportion is 1:1 to 1:5 C7 alkene and the mixture of C12 alkene, the homogeneous catalysis
Agent is to push away electronics base catalysts of olefin metathesis reactions, in terms of the total amount of the medium chain alkene, the use of the homogeneous catalyst
It is 200ppm to measure, and reaction temperature is 30 DEG C, and the reaction time is 24 hours, and by being produced in nitrogen bubbling law removal course of reaction
Raw small-numerator olefin；Or
The medium chain alkene is that equivalent proportion is 1:5 to 5:1 C9 alkene and the mixture of C10 alkene, the homogeneous catalysis
Agent is to push away electronics base catalysts of olefin metathesis reactions, in terms of the total amount of the medium chain alkene, the use of the homogeneous catalyst
It is 200ppm to measure, and reaction temperature is 50 DEG C, and the reaction time is 19 hours, and is gone by decompression method with the vacuum of 120mmHg
Except the small-numerator olefin of generation in course of reaction；Or
The medium chain alkene is that equivalent proportion is 1:2 to 2:1 C9 alkene and the mixture of C12 alkene, the homogeneous catalysis
Agent is to push away electronics base catalysts of olefin metathesis reactions, in terms of the total amount of the medium chain alkene, the use of the homogeneous catalyst
It is 50ppm to measure, and reaction temperature is 50 DEG C, and the reaction time is 10 hours, and is removed by the method that depressurizes with the vacuum of 120mmHg
The small-numerator olefin produced in course of reaction；Or
The medium chain alkene is C9 alkene, and the homogeneous catalyst is to push away electronics base catalysts of olefin metathesis reactions, with institute
State the total amount meter of medium chain alkene, the consumption of the homogeneous catalyst is 100ppm, and reaction temperature is 50 DEG C, the reaction time is
7 hours, and the small-numerator olefin produced in course of reaction is removed by the method that depressurizes with the vacuum of 120mmHg；Or
The medium chain alkene is C12 alkene, and the homogeneous catalyst is to push away electronics base catalysts of olefin metathesis reactions, with institute
State the total amount meter of medium chain alkene, the consumption of the homogeneous catalyst is 100ppm, and reaction temperature is 50 DEG C, the reaction time is
6 hours, and the small-numerator olefin produced in course of reaction is removed by the method that depressurizes with the vacuum of 120mmHg；Or
The medium chain alkene is C10 alkene, and the homogeneous catalyst is to push away electronics base catalysts of olefin metathesis reactions, with institute
The total amount meter of medium chain alkene is stated, the consumption of the homogeneous catalyst is 100ppm or 40ppm, and reaction temperature is 50 DEG C, instead
It is 19 hours between seasonable, and the small-numerator olefin produced in course of reaction is removed by the method that depressurizes with the vacuum of 120mmHg；
Or
The medium chain alkene is that equivalent proportion is 1:2 C9 alkene and the mixture of C10 alkene, the homogeneous catalyst are to push away
Electronics base catalysts of olefin metathesis reactions；First add and the described of 25ppm is calculated as with the total amount of the medium chain alkene homogeneously urges
Agent, reacts 6 hours at 50 DEG C；The homogeneous catalyst that 25ppm is calculated as with the total amount of the medium chain alkene is added,
Continue to react 14 hours；It is small using what is produced in the combined method removal course of reaction that nitrogen bubble and 120mmHg vacuums depressurize
Molecular olefine；Or
The medium chain alkene C12 alkene, the homogeneous catalyst is to push away electronics base catalysts of olefin metathesis reactions；With described
The total amount meter of medium chain alkene, the consumption of the homogeneous catalyst is 50ppm, and reaction temperature is 50 DEG C, and the reaction time is 24
Hour；The combined method depressurized using nitrogen bubble and 120mmHg vacuums removes the small-numerator olefin produced in course of reaction.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201611247886.5A CN106831305B (en) | 2015-12-31 | 2015-12-31 | A kind of method that long-chain olefin is prepared by medium chain alkene |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201511035169.1A CN105585406B (en) | 2015-12-31 | 2015-12-31 | A kind of method that long-chain olefin is prepared by medium chain bio-based alkene |
| CN201611247886.5A CN106831305B (en) | 2015-12-31 | 2015-12-31 | A kind of method that long-chain olefin is prepared by medium chain alkene |
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| US4078013A (en) * | 1976-11-22 | 1978-03-07 | Emery Industries, Inc. | Olefin metathesis catalysts and process utilizing same |
| CN102227394A (en) * | 2008-11-26 | 2011-10-26 | 埃莱文斯可更新科学公司 | Methods of producing jet fuel from natural oil feedstocks through metathesis reactions |
| CN102317250A (en) * | 2008-12-23 | 2012-01-11 | 埃克森美孚研究工程公司 | From reproducible raw material production synthetic hydrocarbon fluid, softening agent and synthetic lubricant base oil material |
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| CN104356165A (en) * | 2014-11-03 | 2015-02-18 | 天津斯瑞吉高新科技研究院有限公司 | Novel N-heterocyclic carbene ruthenium catalyst containing electron donating group and preparation method thereof |
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| US4078013A (en) * | 1976-11-22 | 1978-03-07 | Emery Industries, Inc. | Olefin metathesis catalysts and process utilizing same |
| CN102227394A (en) * | 2008-11-26 | 2011-10-26 | 埃莱文斯可更新科学公司 | Methods of producing jet fuel from natural oil feedstocks through metathesis reactions |
| CN102317250A (en) * | 2008-12-23 | 2012-01-11 | 埃克森美孚研究工程公司 | From reproducible raw material production synthetic hydrocarbon fluid, softening agent and synthetic lubricant base oil material |
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