CN105585406B - A kind of method that long-chain olefin is prepared by medium chain bio-based alkene - Google Patents
A kind of method that long-chain olefin is prepared by medium chain bio-based alkene Download PDFInfo
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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 invention belongs to organic synthesis field, it is related to a kind of method that long-chain olefin is prepared by medium chain bio-based alkene, it using vegetable oil and small-numerator olefin is raw material by intersecting the medium chain bio-based alkene that olefin metathesis reactions obtain to particularly provide a kind of, the method that long-chain olefin is prepared through homogeneous catalyst catalytic reaction.Pass through technical scheme, to catalyst amount, feed postition, and proportioning of 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 to be prepared from biomass material, solve the non-renewable problem of conventional raw material, expanded the application of long-chain olefin.
Description
Technical field
The present invention relates to organic synthesis field, and in particular to a kind of to prepare long-chain olefin by medium chain bio-based alkene
Method.
Background technology
Long-chain olefin refers to C13-C24 non-alpha-linear alpha-olefin, and long-chain olefin has many purposes, such as:Can as raw material
To produce surfactant, long chain silane, long chain mercaptans, long-chain amine, long-chain alcohol etc.;Itself can directly as can biology
The deep sea drilling oil of degraded uses.
There are several known methods to can be used for preparing long-chain olefin in world wide at present, such as:Petroleum cracking method, alkene
Oligomerisation method (SHOP methods), Fischer-Tropsch methods and Olefin metathesis catalysis method.
Typical Olefin metathesis catalysis method is using metal carbene compound as catalyst, makes itself transposition occurs between alkene
Or the characteristics of cross metathesis is reacted to prepare long-chain olefin, has high income, and selectivity of product is high, it is current most attraction
The method for preparing long-chain olefin.Olefin metathesis catalyst can be divided into homogeneous catalysis method and heterogeneous catalysis method, as raw material reaction
Alkene is generally from the mineral-based product of petroleum-based products or coal chemical industry production.
Fred Chun-Chien Twu et et al. are disclosed in patent US 2003/0224945A1 to be urged using heterogeneous
Agent (solid-state), it is raw material using the alpha-olefin obtained by Fischer-Tropsch methods, long-chain is prepared by olefin metathesis reactions
The method of alkene.Twu Fred et al. are disclosed in patent WO 03/101920A1 using heterogeneous catalysis (solid-state), profit
It is raw material with the alpha-olefin obtained by SHOP methods, the method that long-chain olefin is prepared by olefin metathesis reactions, utilizes the method, system
The standby synthesis base base oil that can be used for 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, dosage are few, while also make it that reaction condition is gentle, three wastes produce, raw
Production is easy to carry out.
And medium chain bio-based alkene is obtained as the raw material for preparing long-chain olefin by the use of vegetable oil and small-numerator olefin,
Because vegetable oil is renewable resource, and wide material sources, compared to petroleum cracking raw material used in SHOP methods and
The raw material of the conventionally used coal chemical industry production of Fischer-Tropsch methods, sight that is more green, more meeting sustainable development
Read;In addition, vegetable oil and small-numerator olefin intersect that olefin metathesis reactions technique is simple, and three wastes produce, and reaction condition is gentle,
It is the method for ideal production medium chain alkene.
From different vegetable oil and/or small-numerator olefin, it is anti-that olefin metathesis with small-numerator olefin is intersected by vegetable oil
The bio-based alkene that should be obtained is also different, is additionally, since in vegetable oil in addition to containing saturation and single unsaturated 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 of generation
The composition of double unsaturated olefins so that the raw material that its olefin metathesis reactions obtains 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 one kind uses the homogeneous catalysts of olefin metathesis reactions of metal carbene class, makes medium chain
Bio-based alkene olefin metathesis reactions occur, so as to prepare the method for long-chain olefin, there is technique 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 obtain
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-
C6 small-numerator olefin, the alkene obtained by being acted on through catalysts of olefin metathesis reactions, 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, it is further preferred for 100:50~200;When C9 and C12 is as mixed material, the ratio of mixing is 100:1
~10000, preferably 100:20~500, it is further preferred for 100:50~200;C10 can be separately as raw material;C12
Can be separately as raw material.
Using preceding through lower column processing:Silica gel absorption 24 hours, high pure nitrogen Bubbling method remove most of dissolved oxygen, Ran Houjing
The further deoxygenation of CuCl oxygen scavengers 24 hours.
2nd, catalyst
Catalyst involved by this patent replaces catalysts for homogeneous metal olefin, relatively applicable for ruthenium metal ion
Catalyst, more applicable is first and second generation lattice granny rag catalyst or the novel N-heterocyclic carbenes ruthenium catalysis 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 dosage involved in the present invention for medium chain olefin feed weight 1000ppm extremely
10ppm, preferable amount 500ppm-20ppm, the dosage being more highly preferred to are 400ppm-30ppm.
First catalyst is added with a small amount of toluene or dichloromethane wiring solution-forming with facilitating, catalyst can disposably add
Enter, also graded adds.It is exactly to add different phase point of the catalyst in reaction several times to add by several times, is advantageous 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, preferably 30-70 DEG C, further preferred for 35-60 DEG C;
Reaction time is 1-72 hours, preferably 2-48 hours, further preferred for 3-24 hours.
4th, product
Because the combination of medium chain alkene is different, caused long-chain olefin can be different.Ignore anti-in olefin metathesis
It should can generate following height with the isomerization reaction occurred, during by the use of the combinations of different medium chain alkene as raw material simultaneously
Carbon olefin:
Involved small-numerator olefin (1)-small-numerator olefin (5) is C2-C6 small-numerator olefin in above reaction equation
Various combination, accessory substance (1)-accessory substance (5) is the caused carbon number due to isomerization and olefin metathesis reactions less than 13
The various combination of alkene.
The present invention also provides the method for removing above-mentioned small-numerator olefin:Due to during the course of the reaction, having ethene and/or third
The small-numerator olefin such as alkene and/or butylene and/or amylene and/or hexene produces, and need to disengage it from reaction system, makes reaction to predetermined
The Direction of Reaction moves, 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
Depart from reaction system rapidly together;B) method is depressurized: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, apply vacuum as big as possible, small-numerator olefin is departed from reaction system rapidly;
C) mixing method:Vacuum method and Bubbling method are used 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
It is prepared in matter raw material, solves the non-renewable problem of conventional raw material, expanded the application of long-chain olefin.
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, catalyst weight is reached finite concentration (ppm w/w) to reactant weight, method can also add catalyst twice, i.e.,
A part of catalyst is first added, when reaction proceeds to a certain degree, adds remaining catalyst.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.
Cooling medium temperature need to according to caused by raw material and reaction the difference of small-numerator olefin and adjust, the boiling point of raw material compared with
When low (such as C7, boiling point are 80-90 DEG C), to prevent significant loss, cooling medium will be lower, caused small-numerator olefin point
When son measures larger (such as hexene), for that can exclude reaction system, cooling medium temperature just need it is higher, according to reactant
The difference of system, it 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 raising tracheae valve and closing, 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 and raise tolerance and vacuum, enter inert gas
Amount and vacuum reach experiment necessary requirement.
In the oil bath of certain temperature, magnetic stirring apparatus is started, is reacted to the stipulated time.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 is added in device, top is sealed with degreasing cotton-wool and is compacted adsorbent.Sample 0.5g to be measured is taken to add
Enter into this syringe, sample is expelled in 20mL vial through syringe, add 3mL n-hexanes, after stirring, dissolving,
Draw solution 0.25mL, about 1.0mL is diluted to n-hexane in gas-chromatography sample bottle, 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 (30m × 0.25 μm of 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 1 different products of table
Embodiment 1, C7-C12 combination raw materials prepare higher olefins
Using the alkene of the C7-C12 bio-based medium chains of different ratio as raw material, reactant gross weight is 5g, and addition pushes away
Electronics base catalysts of olefin metathesis reactions 200ppm, caused small molecule alkene in course of reaction is removed with high pure nitrogen Bubbling method
Hydrocarbon, condensed fluid temperature is 20 DEG C in condenser pipe.Electromagnetic agitation is started, reacts 24h at 30 DEG C.Table 2 is gas chromatographic analysis
As a result.
2 different C7-C12 of table are with the influence for comparing conversion ratio
Test result shows that in addition to having olefin metathesis reactions generation, also there occurs the isomery that double bond migrates along carbochain
Change reaction so that product becomes complex.C7 ratio is higher in raw material, and C15 content is higher in product, C18's
Content is lower, and total conversion is higher.
Embodiment 2, C9-C10 combination raw materials prepare higher olefins
Using the alkene of the C9-C10 bio-based medium chains of different ratio as raw material, reactant gross weight is 5g, and addition pushes away
Electronics base catalysts of olefin metathesis reactions 200ppm, caused small-numerator olefin in course of reaction is removed to depressurize method, adjustment is true
Reciprocal of duty cycle is to 120mmHg;Condensed fluid temperature is 25 DEG C in condenser pipe.Electromagnetic agitation is started, reacts 19h at 50 DEG C.Table 3 is gas
Analysis of hplc result.
3 different C9-C10 of table are with the influence for comparing conversion ratio
As shown in Table 3, C9 is worked as:C10 ratio is 1:When 2, total conversion highest, work as C9:C10 ratio is 2:When 1,
C15 conversion ratio highest.
Embodiment 3, C9-C12 combination raw materials prepare higher olefins
Using the alkene of the C9-C12 bio-based medium chains of different ratio as raw material, reactant gross weight is 5g, and addition pushes away
Electronics base catalysts of olefin metathesis reactions toluene solution makes the 50ppm that catalyst concn is raw material weight, is removed instead with depressurizing method
Caused small-numerator olefin during answering, adjustment vacuum to 120mmHg;Condensed fluid temperature is 25 DEG C in condenser pipe.Start
Electromagnetic agitation, react 10h at 50 DEG C.Table 4 is gas chromatographic analysis result.
4 different C9-C12 of table are with the influence for comparing conversion ratio
Test result shows that, when C10 ratio is higher, total conversion is higher, and now C15 yields are relatively low and C18 yields
It is higher.
Embodiment 4, C9 are that raw material prepares higher olefins
5g bio-based C9 alkene is weighed, addition, which pushes away electronics base catalysts of olefin metathesis reactions toluene solution, makes catalyst concn
For the 100ppm 100ppm of raw material weight, caused small-numerator olefin in course of reaction is removed to depressurize method, adjustment vacuum is extremely
120mmHg;Condensed fluid temperature is 25 DEG C in condenser pipe.Electromagnetic agitation is started, reacts 7h at 50 DEG C.Table 5 is gas-chromatography
Analysis result.
The C9 of table 5 is that raw material prepares higher olefins
Embodiment 5, C12 are that raw material prepares higher olefins
Bio-based medium chain C12 alkene 5g are weighed, addition, which pushes away electronics base catalysts of olefin metathesis reactions toluene solution, to be made
Catalyst concn is the 100ppm 100ppm of raw material weight, removes caused small-numerator olefin in course of reaction to depressurize method, adjusts
Whole vacuum is to 120mmHg;Condensed fluid temperature is 25 DEG C in condenser pipe.Electromagnetic agitation is started, reacts 6h at 50 DEG C.Table 6
For gas chromatographic analysis result.
The C12 of table 6 is that raw material prepares higher olefins
Embodiment 6, C10 are that raw material prepares higher olefins under different catalysts concentration
5g bio-based C10 alkene is respectively weighed in two reaction bulbs, is separately added into and pushes away the catalysis of electronics base olefin metathesis reactions
Agent, catalyst concn is respectively reached 100ppm and 40ppm, caused small-numerator olefin in course of reaction removed to depressurize method,
Vacuum is adjusted to 120mmHg;Condensed fluid temperature is 25 DEG C in condenser pipe.Electromagnetic agitation is started, reacts 19h at 50 DEG C.
Table 7 is gas chromatographic analysis result.
The C10 of table 7 is that raw material prepares higher olefins
Analysis result shows, larger catalyst dosage, can improve total conversion, while also can make isomerization reaction more
Seriously, show as due to isomerization reaction and the raising of caused higher olefins content.
Embodiment 7, C9-C10 combination raw materials prepare the experiment of higher olefins multikilogram
As shown in Table 3, C9 is worked as:C10 ratio 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, and adding catalyst toluene solution makes catalyst
Concentration is the 25ppm of raw material weight, and coolant temperature is room temperature in condenser pipe, the small-numerator olefin caused by combined method removes,
Vacuum is adjusted to 120mmHg, bubbles volume is about 20 per minute.Start strong magnetic stirring apparatus, revolution 800rpm.At 50 DEG C
After lower reaction 6h, 25ppm catalyst is added again, continues 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 are that raw material prepares the experiment of higher olefins multikilogram
C12 alkene 1000g is weighed respectively in reactor, and adding catalyst toluene solution makes catalyst concn be raw material weight
The 50ppm of amount, coolant temperature is room temperature in condenser pipe, the small-numerator olefin caused by combined method removes, regulation vacuum to
120mmHg, bubbles volume are about 20 per minute.Start strong magnetic stirring apparatus, revolution 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 higher olefins are prepared 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 preferable using combination.
One embodiment of the present of invention is described in detail above, but the content is only the preferable implementation of the present invention
Example, it is impossible to be considered as the practical range for limiting the present invention.All equivalent changes made according to the present patent application scope and improvement
Deng, all should still belong to the present invention patent covering scope within.
Claims (10)
- A kind of 1. method that long-chain olefin is prepared by medium chain bio-based alkene, it is characterised in that:Utilize vegetable oil and small point Sub- alkene is raw material by intersecting the medium chain bio-based alkene that olefin metathesis reactions obtain, through homogeneous catalyst catalytic reaction To prepare long-chain olefin;Wherein, the small-numerator olefin has the small-numerator olefin of 2 to 6 carbon atoms;The long-chain olefin is Non-alpha-linear alpha-olefin with 13 to 24 carbon atoms;The medium chain alkene is the Medium chain with 7 to 12 carbon atoms Growth base alkene, and selected from following any group:(1) equivalent proportion is 1:1~100 C7 alkene and the mixture of C12 alkene;(2) equivalent proportion is 100:1~10000 C9 alkene and the mixture of C10 alkene;(3) equivalent proportion is 100:1~10000 C9 alkene and the mixture of C12 alkene;(4) C9 alkene;Wherein, the molecular formula difference of the C7 alkene, C9 alkene, C10 alkene and C12 alkene is as follows:a、C7b、C9c、C10d、C12
- 2. a kind of method for preparing long-chain olefin by medium chain bio-based alkene according to claim 1, its feature exist In:Before using the medium chain bio-based olefine reaction, through lower column processing:Silica gel absorption 24 hours, high pure nitrogen bubbling Method removes most of dissolved oxygen, then through the further deoxygenation of CuCl oxygen scavengers 24 hours.
- 3. a kind of method for preparing long-chain olefin by medium chain bio-based alkene according to claim 1, its feature exist In:From the novel N-heterocyclic carbenes ruthenium catalyst containing electron donating group, catalyst amount is medium chain olefin feed weight 1000ppm to 10ppm, catalyst can disposably be added or added by several times.
- 4. a kind of method for preparing long-chain olefin by medium chain bio-based alkene according to claim 3, its feature exist In:The catalyst amount is the 500ppm-20ppm of medium chain olefin feed weight, and catalyst is divided into two parts of equivalent, respectively at When starting the homogeneous catalyst catalytic reaction and reaction time of the homogeneous catalyst catalytic reaction carries out addition when 1/3.
- 5. a kind of method for preparing long-chain olefin by medium chain bio-based alkene according to claim 1, its feature exist In:The reaction temperature of the homogeneous catalyst catalytic reaction is 20-80 DEG C.
- 6. a kind of method for preparing long-chain olefin by medium chain bio-based alkene according to claim 5, its feature exist In:The reaction temperature of the homogeneous catalyst catalytic reaction is 35-60 DEG C.
- 7. a kind of method for preparing long-chain olefin by medium chain bio-based alkene according to claim 1, its feature exist In:The reaction time of the homogeneous catalyst catalytic reaction is 1-72 hours.
- 8. a kind of method for preparing long-chain olefin by medium chain bio-based alkene according to claim 7, its feature exist In:The reaction time of the homogeneous catalyst catalytic reaction is 3-24 hours.
- 9. a kind of method that long-chain olefin is prepared by medium chain bio-based alkene according to claim any one of 1-8, It is characterized in that:The method for also including removing small-numerator olefin after the homogeneous catalyst catalytic reaction terminates, may be selected as follows Any one: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 rapidly reaction system with inert gas;B) method is depressurized:Reaction system is decompressed to certain vacuum degree, according to raw material and the difference of reaction temperature, not lost in raw material In the case of, apply vacuum as big as possible, small-numerator olefin is departed from reaction system rapidly;C) mixing method:The vacuum method and the Bubbling method are used simultaneously, small-numerator olefin is departed from reaction system rapidly.
- 10. a kind of method for preparing long-chain olefin by medium chain bio-based alkene according to claim 9, its feature exist In:The inert gas is nitrogen or argon gas.
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