CN104744202B - One method for entering to have more variable-pressure tubular reactor synthesis of vinyl norborene - Google Patents
One method for entering to have more variable-pressure tubular reactor synthesis of vinyl norborene Download PDFInfo
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- CN104744202B CN104744202B CN201510080886.XA CN201510080886A CN104744202B CN 104744202 B CN104744202 B CN 104744202B CN 201510080886 A CN201510080886 A CN 201510080886A CN 104744202 B CN104744202 B CN 104744202B
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- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims abstract description 19
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 19
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 title claims abstract description 16
- 229920002554 vinyl polymer Polymers 0.000 title claims abstract description 16
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 180
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims abstract description 150
- 238000006243 chemical reaction Methods 0.000 claims abstract description 118
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 27
- 238000007599 discharging Methods 0.000 claims abstract description 18
- INYHZQLKOKTDAI-UHFFFAOYSA-N 5-ethenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C=C)CC1C=C2 INYHZQLKOKTDAI-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- SDBVUYASTUMTFN-UHFFFAOYSA-N CC1=CC=CC=C1.C1=CC=CC1 Chemical compound CC1=CC=CC=C1.C1=CC=CC1 SDBVUYASTUMTFN-UHFFFAOYSA-N 0.000 claims description 38
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 26
- 230000003068 static effect Effects 0.000 claims description 14
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 5
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 4
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 claims description 3
- -1 cyclic aliphatic hydrocarbon Chemical class 0.000 claims description 3
- 230000007423 decrease Effects 0.000 claims description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 description 12
- 239000007789 gas Substances 0.000 description 11
- 238000004587 chromatography analysis Methods 0.000 description 10
- 238000002156 mixing Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 230000006872 improvement Effects 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000001993 dienes Chemical class 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- QPGJSDVSTAMPQZ-UHFFFAOYSA-N C1(=CC=CC=C1)C.C=CC=CC Chemical compound C1(=CC=CC=C1)C.C=CC=CC QPGJSDVSTAMPQZ-UHFFFAOYSA-N 0.000 description 3
- 238000005698 Diels-Alder reaction Methods 0.000 description 3
- 239000000539 dimer Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 description 2
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- UFERIGCCDYCZLN-UHFFFAOYSA-N 3a,4,7,7a-tetrahydro-1h-indene Chemical compound C1C=CCC2CC=CC21 UFERIGCCDYCZLN-UHFFFAOYSA-N 0.000 description 2
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 description 2
- 230000036772 blood pressure Effects 0.000 description 2
- 238000006471 dimerization reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000013638 trimer Substances 0.000 description 2
- QYYZXEPEVBXNNA-QGZVFWFLSA-N (1R)-2-acetyl-N-[4-(1,1,1,3,3,3-hexafluoro-2-hydroxypropan-2-yl)phenyl]-5-methylsulfonyl-1,3-dihydroisoindole-1-carboxamide Chemical compound C(C)(=O)N1[C@H](C2=CC=C(C=C2C1)S(=O)(=O)C)C(=O)NC1=CC=C(C=C1)C(C(F)(F)F)(C(F)(F)F)O QYYZXEPEVBXNNA-QGZVFWFLSA-N 0.000 description 1
- CQSIXFHVGKMLGQ-BWZBUEFSSA-N 1-[5-[(1r,2s,3r)-1,2,3,4-tetrahydroxybutyl]-1h-imidazol-2-yl]ethanone Chemical compound CC(=O)C1=NC=C([C@@H](O)[C@H](O)[C@H](O)CO)N1 CQSIXFHVGKMLGQ-BWZBUEFSSA-N 0.000 description 1
- 241000219495 Betulaceae Species 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of one method for entering to have more variable-pressure tubular reactor synthesis of vinyl norborene, the reaction channel of tubular reactor is provided with two or more discharging opening along the flow direction of material, and pressure declines step by step, comprises the following steps：Cyclopentadiene solution and 1,3 butadiene are reacted from the reaction channel that charging aperture once puts into tubular reactor jointly, so as to obtain vinyl norbornene；Reaction temperature in reaction channel is 120 DEG C 220 DEG C, pressure is 20 2MPa, and the time of staying is 24 120 minutes；The cyclopentadiene solution is made up of cyclopentadiene and dicyclopentadiene and inert organic solvents that may be present.The invention belongs to using entering the method that multichannel goes out variable-pressure tubular reactor safely and efficiently synthesis of vinyl norborene all the way.
Description
Technical field
The invention belongs to organic compound synthesis technical field, it is related to that a kind of to go out variable-pressure tubular type anti-by entering multichannel all the way
The method for answering device synthesis of vinyl norborene；Under high-temperature and high-pressure conditions, realized by 1,3-butadiene using tubular reactor
Vinyl norbornene is prepared through Diels-Alder additive reaction with cyclopentadiene.
Background technology
Vinyl norbornene (VNB) is a kind of Organic Ingredientss, it is convenient to synthesizes ethylidene by isomerization reaction and drops ice
Piece alkene (ENB).At present, ethylidene norbornene is mainly used in the Third monomer of synthesis of ternary EP rubbers (EPDM).
Under high-temperature and high-pressure conditions, 1,3-butadiene (BD) and cyclopentadiene (CPD) carry out Diels-Alder and are synthesized
Vinyl norbornene.Reaction equation is as follows：
The reaction of 1,3-butadiene and cyclopentadiene is strong exothermal reaction, H ° of Δ298=-22kcal/mol.Reaction is in high temperature
React under high pressure, therefore there is potential safety hazard under traditional synthesis.
Further, since cyclopentadiene and 1,3-butadiene are all conjugated diolefins, and divinyl macromer and parent are double each other across
Alkene body.Therefore, have other dimers, trimer, polymer by-product to produce.
Dimer byproducts be produce in building-up process it is most.Wherein, VCH (VCH) and cyclo-octadiene
(COD) generated by 1,3- butadiene dimerization.Tetrahydroindene (THI) then directly generated by cyclopentadiene (CPD) and butadiene (BD) or
Vinyl norbornene (VNB) be heated isomery generation.Dicyclopentadiene (DCPD) is generated by cyclopentadiene (CPD) dimerization.
In system, all kinds of dimers (VCH, VNB, THI, DCPD) still have activated double bonds, can be as dienophile higher
At a temperature of Jing Diels-Alder react to form trimer by-products again with divinyl macromer (BD, CPD).Additionally, 1,3-butadiene exists
Also easily autohemagglutination under high temperature.
With the alpha-Naphthol of 50-3000ppm as polymerization inhibitor, toluene or normal hexane are Chinese patent CN1580015 (2005)
Solvent, (dicyclopentadiene content in cyclopentadiene is less than 5- to reaction mass cyclopentadiene liquid quality fraction 70-80%
8wt%), molar ratio 1,3-butadiene：Cyclopentadiene=1/1-2/1, temperature 130-160 DEG C, pressure 1-8MPa, in autoclave
Once feeding intake in batch reactor is carried out, and the response time is 0.25-4h；And think as far as possible expire liquid status under operation will be to this
Reaction is favourable, so also propose that using singly entering singly to go out TFR, the time of staying is 0.25-1h, other conditions and kettle
Formula reactor is the same.The selectivity of the vinyl norbornene of two kinds of reactors is only 25.91-36.28%, and side reaction is on the high side,
Poly species by-product is not yet referred to particularly.
SUMITOMO CHEMICAL chemical company (Sumitomo Chemical, 1990 (2):Production technology 4-11) is with lazy first
Property aromatic hydrocarbons be solvent, add the liquid phase that polymerization inhibitor carries out dicyclopentadiene to decompose, and rectification obtains highly purified cyclopentadiene.1,
3- butadiene and high-purity cyclopentadiene are with 1.2:1 mol ratio is squeezed into
Reaction, 140 DEG C of temperature, pressure 4MPa, the time of staying are 35min.There is no gas phase portion in this reactor, in order to suppress polymer
Generate, United States Patent (USP) US4777309 (1988) is also added into the N of a small amount of (2500ppm), N- diethyl hydroxyls in reaction system
Amine or 4- oxygen -2,2,6,6- tetramethyl piperidine -1- oxygen-derived free radicals are used as polymerization inhibitor.Reactor keeps successive reaction under full liquid status
After 1000 hours, in reactor, inwall does not totally see the polymer of precipitation, and in reactant liquor, polymer concentration only has 0.04wt%,
Chromatography result butadiene conversion is 21-22%, and the selectivity of product ethylene base norborene is 67.8%.
The content of the invention
The technical problem to be solved in the present invention is to provide one kind under high-temperature and high-pressure conditions, goes out by using multichannel is entered all the way
The method of variable-pressure tubular reactor safely and efficiently synthesis of vinyl norborene.
In order to solve above-mentioned technical problem, the present invention provides a kind of one and enters to have more variable-pressure tubular reactor synthesis of vinyl
The method of norborene：The reaction channel of tubular reactor is provided with two or more discharging opening along the flow direction of material, pressure by
Level declines, and comprises the following steps：
Cyclopentadiene solution and 1,3- butadiene are once put into into jointly the reaction channel of tubular reactor from charging aperture
Inside reacted, so as to obtain vinyl norbornene；Reaction temperature in reaction channel is 120 DEG C -220 DEG C, pressure is 20-
2MPa, the time of staying are 24-120 minutes；
The cyclopentadiene solution is made up of cyclopentadiene and dicyclopentadiene and inert organic solvents that may be present；
In cyclopentadiene solution, the total concentration (that is, 2 concentration sums) of cyclopentadiene and dicyclopentadiene is 10-100wt%；Ring
Pentadiene is 0.43-19 with dicyclopentadiene mass ratio:1；
1,3-butadiene (is calculated on the basis of pressing cyclopentadiene, dicyclopentadiene is equivalent to two with the cyclopentadiene solution
The cyclopentadiene of molecule) mol ratio be 0.1-2:1.
As the improvement of the method for the synthesis of vinyl norborene of the present invention：The inert organic solvents are straight chain fatty
At least one of hydrocarbon, cyclic aliphatic hydrocarbon, aromatic hydrocarbons (that is, be any one or appoint several mixture).
As the further improvements in methods of the synthesis of vinyl norborene of the present invention：At the tubular reactor charging
Be provided with static mixer, (counterbalance valve is used to adjust reaction pressure counterbalance valve to be designed with after the tubular reactor each discharging opening
Power) so that reaction system (arbitrarily can be adjusted by counterbalance valve along the pressure decline of the discharging opening of the flow direction arrangement of material
Section).
As the further improvements in methods of the synthesis of vinyl norborene of the present invention：
5 discharging openings are set altogether；The 1,3- butadiene is 0.2-1 with the mol ratio of the cyclopentadiene:1 (preferably
0.2-0.8:1), reaction temperature is 140 DEG C -180 DEG C；
First paragraph reaction pressure is 10-20MPa, second segment reaction pressure is 8-15MPa, and the 3rd section of reaction pressure is 6-
10MPa, the 4th section of reaction pressure are 4-7MPa, and the 5th section of reaction pressure is 0-4Mpa.
Remarks explanation：It is " first paragraph " from charging aperture to first discharging opening, remaining is by that analogy.
As the further improvements in methods of the synthesis of vinyl norborene of the present invention：Straight chain aliphatic hydrocarbons are octane, ring
Shape aliphatic hydrocarbon is hexamethylene, and aromatic hydrocarbons is toluene.
As the further improvements in methods of the synthesis of vinyl norborene of the present invention：
From the cyclopentadiene toluene solution that mass fraction is 60wt%, cyclopentadiene with dicyclopentadiene mass ratio is
19:1；
5 discharging openings are set altogether；The 1,3- butadiene is 0.2 with the mol ratio of the cyclopentadiene:1, reaction temperature
For 140 DEG C；
It is 12MPa that first paragraph reaction pressure is 15MPa, second segment reaction pressure, and the 3rd section of reaction pressure is 9MPa, the 4th
Section reaction pressure is 6MPa, and the 5th section of reaction pressure is 0MPa；5th discharging opening zero discharge.
First～the 5th discharge hole for discharge amount percentage is followed successively by 40% (time of staying 24min), 30% (during stop
Between 48min), 20% (time of staying 72min), 10% (time of staying 96min), 0% (time of staying 120min).
In the present invention：The effect of the static mixer arranged at charging aperture is by two kinds of materials quick mix homogeneously.Often
Counterbalance valve is designed with after individual discharging opening, it is possible to achieve multistage blood pressure lowering regulates and controls.
In the present invention, when there is toluene (for a kind of inert organic solvents) in cyclopentadiene solution, just it is named as ring
Pentadiene toluene solution.Remaining is by that analogy.
The multichannel of entering all the way for realizing said method of the present invention goes out variable-pressure tubular reactor, with prior art phase
Than having the advantages that：
(1) tubular reactor is applied to 1,3- butadiene and cyclopentadiene under High Temperature High Pressure and passes through Diels- by the present invention
Alder reactions prepare the production process of vinyl norbornene, as this tubular reactor has to enter multichannel all the way and go out, Er Qieke
The characteristics of realizing each section of independent transformation blood pressure lowering, is cracked into the volume increase reaction of cyclopentadiene in order to dicyclopentadiene, favorably
In carrying out the cyclopentadiene of higher concentration is remained in reaction channel with reaction, vinyl norbornene production process is made
Safety and combined coefficient are greatly improved；
(2) present invention can not use polymerization inhibitor, alleviate the detached difficulty of subsequent products；
(3) present invention adopts high concentration cyclopentadiene for raw material, further improves reaction rate and its selectivity；
(4) tubular reactor of the invention is provided with static mixer at charging, can realize the quick mix homogeneously of material, passes
Matter efficiency high, can reduce because of the bad caused side reaction of mass transfer, improve the selectivity of reaction, compared with conventional tank reactor,
Without the need for the dynamic equipment such as agitator, not only contribute to reduce energy consumption, reduce production cost, and be conducive to the sealing of reactor, carry
The safety of high production；
(5) tubular reactor heat transfer efficiency of the invention is high, can be moved rapidly into or removal system heat, make reaction exist
Carry out close under conditions of isothermal, it is to avoid the generation of reaction focus, so as to effectively suppress side reaction；
(6) tubular reactor heat-resistant pressure-resistant grade of the invention is high, is particularly suitable for vinyl norbornene and synthesizes this behaviour
Make harsh, the inflammable and explosive reaction of condition；
(7) the vinyl norbornene yield and purity obtained by tubular reactor of the present invention is above conventional reactor, and 1,3
The selectivity of butadiene (generates the amount and the 1,3 butadiene total amounts for consuming of 1,3 butadiene consumed by vinyl norbornene
Ratio, similarly hereinafter) may be up to 78.6wt%, the conversion ratio of 1,3-butadiene (react the 1 of consumption, 3 butadiene amounts and add 1,
It is the ratio of 3 butadiene total amounts, similarly hereinafter) 54.7wt%, it is adaptable to the production process of fourth vinyl norbornene.
Description of the drawings
Below in conjunction with the accompanying drawings the specific embodiment of the present invention is described in further detail.
Fig. 1 is that the present invention enters the schematic diagram that multichannel goes out variable-pressure tubular reactor all the way.
Specific embodiment
The many lateral line discharging tubular reactor structures adopted in following examples are as shown in figure 1, a diameter of Dn20mm, is divided into
5 sections, import section start installs static mixer, promotes gas-liquid mixed.It is each intersegmental with 180 ° of elbows connections, to reduce occupation of land face
Product.Reactor inlet is cyclopentadiene solution and two line of 1,3-butadiene merges common charging all the way, raw materials used for ring penta 2
Alkene solution and 1,3- butadiene liquid.In addition, streamwise, every one section arrange a material discharging opening, each discharging opening
After be fitted with counterbalance valve.
With reference to specific embodiment, the present invention will be further described, but embodiments of the present invention not limited to this.
Embodiment 1：
(that is, the cyclopentadiene toluene solution is by ring penta 2 to prepare the cyclopentadiene toluene solution that mass fraction is 60wt%
Alkene and dicyclopentadiene and toluene composition；In the cyclopentadiene toluene solution, cyclopentadiene and dicyclopentadiene it is total dense
Spend for 60wt%), wherein cyclopentadiene and dicyclopentadiene mass ratio are 19:1.
Under normal temperature condition, 1,3-butadiene and cyclopentadiene toluene solution are delivered in pipe reaction device, 1,3- fourth
Diene mass flow is 7.9g/min, and cyclopentadiene toluene solution mass flow is 80.0g/min, i.e. 1,3-butadiene and ring
The mol ratio of pentadiene is 0.2.Two strands of material Jing static mixers of 1,3- butadiene and cyclopentadiene toluene solution mix laggard
Entering conversion zone, reacting in tubular reactor, reaction temperature is 140 DEG C, the pressure of each conversion zone is controlled by counterbalance valve,
A section reaction pressure each from front to back is followed successively by 15MPa, 12MPa, 9MPa, 6MPa, 0MPa, from front to back each discharge hole for discharge amount institute
Account for percentage ratio be followed successively by 40% (time of staying 24min), 30% (time of staying 48min), 20% (time of staying 72min),
10% (time of staying 96min), 0% (time of staying 120min), every segment length of wherein tubular reactor can be according to stop
Time and caliber calculating (this is routine techniquess), similarly hereinafter.Jing gas chromatographic analysiss, 1,3-butadiene in corresponding outlet material
Selectivity be respectively 85.6wt%, 79.6wt%, 72.1wt%, 60.1wt%, 0wt%, corresponding 1,3-butadiene turn
Rate is respectively 38.5wt%, 56.6wt%, 71.2wt%, 80.8wt%, 0wt%.So, 1,3-butadiene overall selectivity is
78.6wt%, total conversion are 54.7wt%.
Embodiment 2：
Cyclopentadiene toluene solution of the mass fraction for 60wt% is prepared, wherein cyclopentadiene with the ratio of dicyclopentadiene is
19:1.Under normal temperature condition, 1,3-butadiene and cyclopentadiene toluene solution are delivered in pipe reaction device, 1,3-butadiene
Mass flow is 14.3g/min, and cyclopentadiene toluene solution mass flow is 73.0g/min, i.e. 1,3-butadiene and ring penta 2
The mol ratio of alkene is 0.4.Two strands of materials of 1,3- butadiene and cyclopentadiene toluene solution enter anti-Jing after static mixer mixes
Section is answered, is reacted in tubular reactor, reaction temperature is 180 DEG C, the pressure of each conversion zone is controlled by counterbalance valve, in the past
Backward each section reaction pressure is followed successively by 20MPa, 15MPa, 10MPa, 6MPa, 2MPa, from front to back shared by each discharge hole for discharge amount
Percentage ratio be followed successively by 30% (time of staying 24min), 25% (time of staying 48min), 20% (time of staying 72min), 15%
(time of staying 96min), 10% (time of staying 120min).Jing gas chromatographic analysiss, 1,3- fourths two in corresponding outlet material
The selectivity of alkene is respectively 65.1wt%, 60.1wt%, 50.1wt%, 36.2wt%, 33.7wt%, corresponding 1,3-butadiene
Conversion ratio be respectively 36.2wt%, 54.2wt%, 69.5wt%, 78.4wt%, 82.4wt%.So, 1,3-butadiene is total
Selectivity is 53.4wt%, and total conversion is 58.3wt%.
Embodiment 3：
Cyclopentadiene solution (that is, only cyclopentadiene and dicyclopentadiene be made up of) of the mass fraction for 100wt% is prepared,
Wherein cyclopentadiene and the ratio of dicyclopentadiene are 4:1.Under normal temperature condition, 1,3-butadiene and cyclopentadiene solution are delivered to
In pipe reaction device, 1,3-butadiene mass flow is 6.7g/min, and cyclopentadiene toluene solution mass flow is 82.0g/
Min, i.e. 1,3-butadiene is 0.1 with the mol ratio of cyclopentadiene.Two gangs of material Jing are quiet for 1,3- butadiene and cyclopentadiene solution
Conversion zone is entered after the mixing of state blender, is reacted in tubular reactor, reaction temperature is 220 DEG C, by counterbalance valve control
The pressure of each conversion zone is made, a section reaction pressure each from front to back is followed successively by 20MPa, 15MPa, 10MPa, 7MPa, 4MPa, from going to
Afterwards each discharge hole for discharge amount percentage be followed successively by 20% (time of staying 24min), 20% (time of staying 48min), 20%
(time of staying 72min), 20% (time of staying 96min), 20% (time of staying 120min).Jing gas chromatographic analysiss, accordingly
Outlet material in 1,3- butadiene selectivity be respectively 76.1wt%, 71.4wt%, 64.7wt%, 49.5wt%,
40.6wt%, the conversion ratio of corresponding 1,3-butadiene be respectively 49.5wt%, 61.6wt%, 70.4wt%, 78.4wt%,
86.4wt%.So, 1,3-butadiene overall selectivity is 60.5wt%, and total conversion is 69.3wt%.
Embodiment 4：
(that is, the cyclopentadiene toluene solution is by ring penta 2 to prepare the cyclopentadiene toluene solution that mass fraction is 30wt%
Alkene and dicyclopentadiene and toluene composition；In the cyclopentadiene toluene solution, cyclopentadiene and dicyclopentadiene it is total dense
Spend for 30wt%), wherein cyclopentadiene and the ratio of dicyclopentadiene are 1.5:1.Under normal temperature condition, 1,3-butadiene and ring penta
Diene toluene solution is delivered in pipe reaction device, and 1,3-butadiene mass flow is 14.0g/min, and cyclopentadiene toluene is molten
Liquid mass flow is 71.0g/min, i.e. 1,3-butadiene is 0.8 with the mol ratio of cyclopentadiene.1,3- butadiene and ring penta 2
Two strands of materials of alkene toluene solution enter conversion zone Jing after static mixer mixing, react in tubular reactor, reaction temperature
Spend for 140 DEG C, the pressure of each conversion zone controlled by counterbalance valve, a section reaction pressure each from front to back be followed successively by 15MPa, 12MPa,
9MPa, 6MPa, 4MPa, from front to back each discharge hole for discharge amount percentage be followed successively by 10% (time of staying 24min), 15%
(time of staying 48min), 20% (time of staying 72min), 25% (time of staying 96min), 30% (time of staying 120min).
Jing gas chromatographic analysiss, in corresponding outlet material the selectivity of 1,3-butadiene be respectively 63.8wt%, 57.6wt%,
52.6wt%, 46.8wt%, 44.7wt%, the conversion ratio of corresponding 1,3-butadiene be respectively 17.9wt%, 31.4wt%,
41.5wt%, 50.2wt%, 56.2wt%.So, 1,3-butadiene overall selectivity is 50.7wt%, and total conversion is
44.2wt%.
Embodiment 5：
Cyclopentadiene toluene solution of the mass fraction for 30wt% is prepared, wherein cyclopentadiene with the ratio of dicyclopentadiene is
0.67:1.Under normal temperature condition, 1,3-butadiene and cyclopentadiene toluene solution are delivered in pipe reaction device, 1,3- fourth two
Alkene mass flow is 16.5g/min, and cyclopentadiene toluene solution mass flow is 67.0g/min, i.e. 1,3-butadiene and ring penta
The mol ratio of diene is 2.0.Two strands of materials of 1,3- butadiene and cyclopentadiene toluene solution are entered Jing after static mixer mixes
Conversion zone, reacts in tubular reactor, and reaction temperature is 140 DEG C, controls the pressure of each conversion zone by counterbalance valve, from
After going to, each section of reaction pressure is followed successively by 10MPa, 8MPa, 6MPa, 4MPa, 4MPa, from front to back shared by each discharge hole for discharge amount
Percentage ratio be followed successively by 0%, 10% (time of staying 48min), 20% (time of staying 72min), 30% (time of staying 96min),
40% (time of staying 120min).Jing gas chromatographic analysiss, in corresponding outlet material, the selectivity of 1,3-butadiene is respectively
0wt%, 56.7wt%, 50.7wt%, 45.5wt%, 35.3wt%, the conversion ratio of corresponding 1,3-butadiene are respectively
0wt%, 43.5wt%, 52.4wt%, 59.9wt%, 65.3wt%.So, 1,3-butadiene overall selectivity is 43.5wt%,
Total conversion is 58.9wt%.
Embodiment 6：
(that is, the cyclopentadiene toluene solution is by ring penta 2 to prepare the cyclopentadiene toluene solution that mass fraction is 10wt%
Alkene and dicyclopentadiene and toluene composition；In the cyclopentadiene toluene solution, cyclopentadiene and dicyclopentadiene it is total dense
Spend for 10wt%), wherein cyclopentadiene and the ratio of dicyclopentadiene are 0.43:1.Under normal temperature condition, 1,3-butadiene and ring
Pentadiene toluene solution is delivered in pipe reaction device, 1,3-butadiene mass flow be 12.8g/min, cyclopentadiene toluene
Solution quality flow is 78.0g/min, i.e. 1,3-butadiene is 2.0 with the mol ratio of cyclopentadiene.1,3- butadiene and ring penta
Two strands of materials of diene toluene solution enter conversion zone Jing after static mixer mixing, react in tubular reactor, react
Temperature be 120 DEG C, the pressure of each conversion zone is controlled by counterbalance valve, a section reaction pressure each from front to back be followed successively by 15MPa,
12MPa, 9MPa, 6MPa, 0MPa, from front to back each discharge hole for discharge amount percentage be followed successively by for the 40% (time of staying
24min), 30% (time of staying 48min), 20% (time of staying 72min), 10% (time of staying 96min), 0%.Jing gas phases
Chromatography, in corresponding outlet material the selectivity of 1,3-butadiene be respectively 46.6wt%, 40.5wt%, 32.2wt%,
26.9wt%, 0wt%, the conversion ratio of corresponding 1,3-butadiene be respectively 26.7wt%, 32.8wt%, 41.2wt%,
50.4wt%, 0wt%.So, 1,3-butadiene overall selectivity is 43.9wt%, and total conversion is 33.8wt%.
Comparative example 1,
Contrast with embodiment 1, prepare mass fraction for 60wt% cyclopentadiene toluene solution, wherein cyclopentadiene with it is double
The ratio of cyclopentadiene is 19:1.Under normal temperature condition, 1,3-butadiene and cyclopentadiene toluene solution are delivered to pipe reaction dress
In putting, using singly entering singly to go out, 1,3-butadiene mass flow is 4.0g/min to tubular reactor, cyclopentadiene toluene solution quality
Flow is 42.10g/min, i.e. 1,3-butadiene is 0.2 with the mol ratio of cyclopentadiene.1,3- butadiene and cyclopentadiene first
Two strands of materials of benzole soln enter conversion zone Jing after static mixer mixing, react in tubular reactor, and reaction temperature is
140 DEG C, reaction pressure 15Mpa；The time of staying is 120 minutes；Jing gas chromatographic analysiss, 1,3- fourths two in corresponding outlet material
Alkene overall selectivity is 51.5wt%, and total conversion is 54.6wt%.
Comparative example 2,
Contrast with embodiment 1, prepare mass fraction for 60wt% cyclopentadiene toluene solution, wherein cyclopentadiene with it is double
The ratio of cyclopentadiene is 19:1.Under normal temperature condition, 1,3-butadiene and cyclopentadiene toluene solution are delivered to pipe reaction dress
In putting, using singly entering singly to go out, 1,3-butadiene mass flow is 4.0g/min to tubular reactor, cyclopentadiene toluene solution quality
Flow is 42.10g/min, i.e. 1,3-butadiene is 0.2 with the mol ratio of cyclopentadiene.1,3- butadiene and cyclopentadiene first
Two strands of materials of benzole soln enter conversion zone Jing after static mixer mixing, react in tubular reactor, and reaction temperature is
140 DEG C, the pressure of each conversion zone, reaction pressure 6Mpa are controlled by counterbalance valve.The time of staying is 120 minutes；Jing gas chromatograies
Analysis, in corresponding outlet material, 1,3-butadiene overall selectivity is 63.8wt%, and total conversion is 35.3wt%.
Comparative example 3,
Compared with Example 4, prepare mass fraction for 30wt% cyclopentadiene toluene solution, wherein cyclopentadiene with it is double
The ratio of cyclopentadiene is 1.5:1.Under normal temperature condition, 1,3-butadiene and cyclopentadiene toluene solution are delivered to pipe reaction dress
In putting, using singly entering singly to go out, 1,3-butadiene mass flow is 14.0g/min to tubular reactor, cyclopentadiene toluene solution matter
Amount flow is 71.0g/min, i.e. 1,3-butadiene is 0.8 with the mol ratio of cyclopentadiene.1,3- butadiene and cyclopentadiene first
Two strands of materials of benzole soln enter conversion zone Jing after static mixer mixing, react in tubular reactor, and reaction temperature is
140 DEG C, reaction pressure 6Mpa.The time of staying is 120 minutes；Jing gas chromatographic analysiss, 1,3- fourths two in corresponding outlet material
Alkene overall selectivity is 42.3wt%, and total conversion is 40.2wt%.
Comparative example 4,
Contrast with embodiment 5, prepare mass fraction for 30wt% cyclopentadiene toluene solution, wherein cyclopentadiene with it is double
The ratio of cyclopentadiene is 0.67:1.Under normal temperature condition, 1,3-butadiene and cyclopentadiene toluene solution are delivered to pipe reaction
In device, 1,3-butadiene mass flow is 16.5g/min, and cyclopentadiene toluene solution mass flow is 67.0g/min, i.e.
1,3- butadiene is 2.0 with the mol ratio of cyclopentadiene toluene solution.1,3- butadiene is static with two gangs of material Jing of cyclopentadiene
Conversion zone is entered after blender mixing, is reacted in tubular reactor, reaction temperature is 140 DEG C, and reaction pressure is 6Mpa.
The time of staying is 120 minutes；Jing gas chromatographic analysiss, 1,3-butadiene overall selectivity are 34.6wt%, and total conversion is
58.2wt%.
Finally, in addition it is also necessary to it is noted that listed above is only several specific embodiments of the invention.Obviously, this
It is bright to be not limited to above example, there can also be many deformations.One of ordinary skill in the art can be from present disclosure
The all deformations directly derived or associate, are considered as protection scope of the present invention.
Claims (4)
1. a method for entering to have more variable-pressure tubular reactor synthesis of vinyl norborene, is characterized in that：Tubular reactor
Reaction channel is provided with 5 discharging openings along the flow direction of material, and pressure declines step by step, comprises the following steps：
Cyclopentadiene solution and 1,3- butadiene are entered from the reaction channel that charging aperture once puts into tubular reactor jointly
Row reaction, the time of staying is 24-120 minutes, so as to obtain vinyl norbornene；；
The cyclopentadiene solution is made up of cyclopentadiene and dicyclopentadiene and inert organic solvents that may be present；In ring
In pentadiene solution, the total concentration of cyclopentadiene and dicyclopentadiene is 10-100wt%；Cyclopentadiene and dicyclopentadiene matter
The ratio of amount is 0.43-19:1；
1,3- butadiene is 0.1-2 with the mol ratio of the cyclopentadiene solution:1；
It is provided with static mixer at the tubular reactor charging, after the tubular reactor each discharging opening, is designed with back pressure
Valve, so that pressure decline of the reaction system along the discharging opening of the flow direction arrangement of material；
5 discharging openings are set altogether；The 1,3- butadiene is 0.2-1 with the mol ratio of the cyclopentadiene:1, reaction temperature is
140℃-180℃；
First paragraph reaction pressure is 10-20MPa, second segment reaction pressure is 8-15MPa, and the 3rd section of reaction pressure is 6-10MPa,
4th section of reaction pressure is 4-7MPa, and the 5th section of reaction pressure is 0-4MPa.
2. the method for synthesis of vinyl norborene according to claim 1, is characterized in that：The inert organic solvents are
At least one of straight chain aliphatic hydrocarbons, cyclic aliphatic hydrocarbon, aromatic hydrocarbons.
3. the method for synthesis of vinyl norborene according to claim 2, is characterized in that：The straight chain aliphatic hydrocarbons are pungent
Alkane, cyclic aliphatic hydrocarbon are hexamethylene, and aromatic hydrocarbons is toluene.
4. the method for synthesis of vinyl norborene according to claim 3, is characterized in that：
From the cyclopentadiene toluene solution that mass fraction is 60wt%, cyclopentadiene is 19 with dicyclopentadiene mass ratio:
1；
5 discharging openings are set altogether；The 1,3- butadiene is 0.2 with the mol ratio of the cyclopentadiene:1, reaction temperature is 140
℃；
First paragraph reaction pressure is 15MPa, second segment reaction pressure is 12MPa, and the 3rd section of reaction pressure is 9MPa, and the 4th section anti-
Pressure is answered to be 6MPa, the 5th section of reaction pressure is 0Mpa；
5th discharging opening zero discharge.
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| US4777309A (en) * | 1986-01-18 | 1988-10-11 | Sumitomo Chemical Company, Limited | Continuous process for producing 5-vinyl-2-norbornene |
| CN1580015A (en) * | 2004-05-20 | 2005-02-16 | 吉林市大宇化工有限公司 | Method for synthesizing 5-vinyl-2-norbornaene |
| CN102123973A (en) * | 2008-08-19 | 2011-07-13 | 法思特有限责任公司 | Process for producing ethylidene norbornene |
| CN104058912A (en) * | 2014-07-01 | 2014-09-24 | 上海华畅环保设备发展有限公司 | Method and device for utilizing catalyst in ethylidene norbornene isosynthesis technology |
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| US4777309A (en) * | 1986-01-18 | 1988-10-11 | Sumitomo Chemical Company, Limited | Continuous process for producing 5-vinyl-2-norbornene |
| CN1580015A (en) * | 2004-05-20 | 2005-02-16 | 吉林市大宇化工有限公司 | Method for synthesizing 5-vinyl-2-norbornaene |
| CN102123973A (en) * | 2008-08-19 | 2011-07-13 | 法思特有限责任公司 | Process for producing ethylidene norbornene |
| CN104058912A (en) * | 2014-07-01 | 2014-09-24 | 上海华畅环保设备发展有限公司 | Method and device for utilizing catalyst in ethylidene norbornene isosynthesis technology |
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