CN209481509U - A kind of reaction unit in the source C1 and alkylation of toluene production styrene - Google Patents
A kind of reaction unit in the source C1 and alkylation of toluene production styrene Download PDFInfo
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- CN209481509U CN209481509U CN201920118009.0U CN201920118009U CN209481509U CN 209481509 U CN209481509 U CN 209481509U CN 201920118009 U CN201920118009 U CN 201920118009U CN 209481509 U CN209481509 U CN 209481509U
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 title claims abstract description 168
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 142
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims abstract description 141
- 238000005804 alkylation reaction Methods 0.000 title claims abstract description 43
- 230000029936 alkylation Effects 0.000 title claims abstract description 38
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 29
- 239000001257 hydrogen Substances 0.000 claims abstract description 61
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 61
- 239000003054 catalyst Substances 0.000 claims abstract description 53
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 51
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 111
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 52
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 45
- 238000000926 separation method Methods 0.000 claims description 30
- 239000000463 material Substances 0.000 claims description 24
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 239000012528 membrane Substances 0.000 claims description 9
- 229910052763 palladium Inorganic materials 0.000 claims description 9
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- 238000006206 glycosylation reaction Methods 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 abstract description 13
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 abstract description 9
- 230000008901 benefit Effects 0.000 abstract description 7
- 239000000047 product Substances 0.000 description 73
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 33
- 238000000034 method Methods 0.000 description 24
- 239000002994 raw material Substances 0.000 description 22
- 230000008569 process Effects 0.000 description 14
- 238000011143 downstream manufacturing Methods 0.000 description 13
- 239000006227 byproduct Substances 0.000 description 11
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 10
- 150000002431 hydrogen Chemical class 0.000 description 10
- 238000006555 catalytic reaction Methods 0.000 description 7
- 238000003860 storage Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 5
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000004148 unit process Methods 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229930040373 Paraformaldehyde Natural products 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 229920002866 paraformaldehyde Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical class [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002918 waste heat Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229960004217 benzyl alcohol Drugs 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 230000004087 circulation Effects 0.000 description 1
- 230000002153 concerted effect Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- JMNDBSWHIXOJLR-UHFFFAOYSA-N ethylbenzene;styrene Chemical compound CCC1=CC=CC=C1.C=CC1=CC=CC=C1 JMNDBSWHIXOJLR-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
Abstract
The utility model discloses the reaction units in the source C1 and alkylation of toluene production styrene, the reaction unit includes alkylated reaction unit and product separative unit, alkylated reaction unit includes the reaction vessel for being provided with the first catalyst bed, first top feed pipe, first bottom discharge pipe and at least 1 hydrogen output duct, at least 1 hydrogen output duct stretches to reaction vessel and is inserted into first catalyst bed, reaction vessel is connected with the source C1 and toluene source by the first top feed pipe and passes through the first bottom discharge pipe and is connected with the second top feed pipe of product separative unit.The utility model have many advantages, such as high-phenylethylene yield, Technical Economy preferably, system run all right, improve the source C1 and Benzyl Side-Chain alkylation prepare the Technical Economy of styrene technology and promotes possibility.
Description
Technical field
The utility model belongs to the field of catalytic reactions in technical field of chemical engineering, more particularly, is related to a kind of C1
The reaction unit in source and alkylation of toluene production styrene.
Background technique
In contemporary chemical industry, styrene is widely used in generating polyphenyl second as important organic synthesis raw material
Alkene, butadiene-styrene rubber, ion exchange resin, medicine and dyestuff etc., series chemical material yield are only second to world's high yield polymer
Yield, come the forefront of World Synthetic Resin amount.Traditional styrene Production is mostly used benzene and ethylene production ethylbenzene, then urges
Styrene product is made in fluidized dehydrogenation, and there are route length, reaction bed temperature high (600~660 DEG C), energy consumption are high and former for the technique
Expect the disadvantages of at high cost.
The source C1 and toluene are reacted by side chain alkylation can be made styrene (coproduction ethylbenzene), be Recent study person's weight
The novel process of point concern, especially methanol and Benzyl Side-Chain alkylation process technology, the technology have raw material sources extensively and
Inexpensively, process flow is short, bed temperature is low, the low advantages such as low with product overall cost of process energy consumption, if catalyst skill can be broken through
Art bottleneck, Technical Economy are especially significant.In utility model patent CN103664485A, methanol, Benzyl Side-Chain are developed
Alkylation generates the process of styrene, ethylbenzene, solves the problems, such as that methanol comprehensive yield is low, but because catalysis reaction is acid
Alkali concerted catalysis reaction is the main active component of catalyst usually using X-type or Y type low silica-alumina ratio molecular sieve analog, such as practical
In new patent CN103539601A, the X-type or Y type low silica-alumina ratio molecular sieve that utility model person uses for catalyst precursor,
And it carries out alkali metal ion and has been modified so that so that catalyst is met higher middle highly basic active sites (influences catalyst catalytic performance
One of key factor), which substantially increases the conversion ratio of toluene and the total recovery of ethylbenzene, styrene, but the catalyst
Thermal stability, anti-carbon performance be still difficult to ensure, catalyst life is shorter, the hydrogen especially generated after methanol activation easily with
Active styrene reaction generates ethylbenzene, and primary target product styrene yield is caused to decline, therefore urgent by inhibiting benzene second
The yield of alkene hydrogenation reaction raising target product styrene.
Summary of the invention
The purpose of the utility model is to overcome the sources C1 in the prior art and Benzyl Side-Chain alkylation process technology to benzene second
Alkene yield is low, the problems such as Technical Economy difference, provides a kind of applied to the source C1 and the alkylated reaction unit of Benzyl Side-Chain.
The utility model provides the reaction unit in a kind of source C1 and alkylation of toluene production styrene, the reaction unit
Including alkylated reaction unit and product separative unit, the alkylated reaction unit includes being provided with the first catalyst bed
Reaction vessel, the first top feed pipe, the first bottom discharge pipe and at least 1 hydrogen output duct, at least 1 hydrogen are defeated
Conduit stretches to reaction vessel and is inserted into first catalyst bed out, and reaction vessel passes through the first top feed pipe and C1
Source and toluene source are connected and pass through the first bottom discharge pipe and be connected with the second top feed pipe of product separative unit.
According to the one embodiment in the source C1 described in the utility model and the reaction unit of alkylation of toluene production styrene, institute
Stating alkylated reaction unit further includes at least 1 side source radial direction C1 feed pipe, and at least 1 side source radial direction C1 feed pipe is from side
Portion protrudes into the reaction vessel and exports the top or centre for being located at first catalyst bed, wherein at least 1 side
The outlet of the portion source radial direction C1 feed pipe is located at the centre of first catalyst bed.
According to the one embodiment in the source C1 described in the utility model and the reaction unit of alkylation of toluene production styrene, institute
It states the side source radial direction C1 feed pipe to be also connected with the source C1, the tube wall aperture of the side source radial direction C1 feed pipe and the number of aperture in exit
More than the number of aperture of inlet.
According to the one embodiment in the source C1 described in the utility model and the reaction unit of alkylation of toluene production styrene, institute
Hydrogen output duct is stated to be made of composition metal palladium membrane material.
According to the one embodiment in the source C1 described in the utility model and the reaction unit of alkylation of toluene production styrene, institute
Stating product separative unit includes separation vessel, the second top feed pipe, ethylbenzene discharge nozzle, styrene discharge nozzle, the source unreacted C1
Feed back pipe, unreacted toluene feed back pipe and hydrogen feed back pipe, the separation vessel pass through unreacted toluene feed back pipe and the alkane
First top feed pipe of glycosylation reaction unit is connected, by the source unreacted C1 feed back pipe and the alkylated reaction unit extremely
The few 1 side source radial direction C1 feed pipe is connected and is connected by hydrogen feed back pipe with the outlet end of the hydrogen output duct.
According to the one embodiment in the source C1 described in the utility model and the reaction unit of alkylation of toluene production styrene, institute
Stating reaction unit further includes ethylbenzene dehydrogenation reaction unit, and the product separative unit passes through the ethylbenzene discharge nozzle and the ethylbenzene
The third top feed pipe of dehydrogenation reaction unit is connected, and the ethylbenzene dehydrogenation reaction unit includes being provided with the second catalyst bed
Dehydrogenation container, third top feed pipe and products of dehydrogenation reactions discharge nozzle, the dehydrogenation container gone out by products of dehydrogenation reactions
Expects pipe is connected with the second top feed pipe of the product separative unit or with the first bottom discharge pipe of alkylated reaction unit.
Compared with prior art, the utility model overcomes that existing side chain alkylation technology styrene yield is low, reaction system
Unite stability, the problem that styrene yield is low and Technical Economy is poor, while can by the high added value Hydrogen Separation of by-product, mention
Pure and storage is transported to downstream process.The utility model provides the source C1 of high-phenylethylene yield and Benzyl Side-Chain is alkylated instead
Answer device and its process matched therewith, have many advantages, such as high-phenylethylene yield, Technical Economy preferably, system run all right, mention significantly
The high source C1 and Benzyl Side-Chain alkylation prepare the Technical Economy of styrene technology and promote possibility.
Detailed description of the invention
Fig. 1 shows the reaction according to the source C1 of the utility model exemplary embodiment and alkylation of toluene production styrene
Device and process flow diagram.
Fig. 2 shows the reaction units that styrene is produced according to the source C1 of the utility model comparative example 1 and alkylation of toluene
And process flow diagram.
Description of symbols:
1- alkylated reaction unit, 11- reaction vessel, 12- hydrogen output duct, the side the 13- source radial direction C1 feed pipe,
The first top feed of 14- pipe, the first bottom discharge of 15- pipe, the first catalyst bed of 16-；
2- product separative unit, 21- separation vessel, the second top feed of 22- pipe, 23- ethylbenzene discharge nozzle, 24- unreacted
The source C1 feed back pipe, 25- styrene discharge nozzle, 26- unreacted toluene feed back pipe, 27- hydrogen feed back pipe；
3- ethylbenzene dehydrogenation reaction unit, 31- dehydrogenation container, the second catalyst bed of 32-, 33- third top feed pipe,
34- products of dehydrogenation reactions discharge nozzle.
Specific embodiment
All features disclosed in this specification or disclosed all methods or in the process the step of, in addition to mutually exclusive
Feature and/or step other than, can combine in any way.
Any feature disclosed in this specification unless specifically stated can be equivalent or with similar purpose by other
Alternative features are replaced.That is, unless specifically stated, each feature is an example in a series of equivalent or similar characteristics
?.
Side chain alkylation reaction is because the source the C1 such as material benzenemethanol generates formaldehyde and hydrogen in reactor catalyst first, and formaldehyde is again
It reacts with the toluene after activation, mainly there is two kinds of products of styrene and ethylbenzene, wherein styrene is target product, but benzene second
Alkene is more active, easily reacts with byproduct hydrogen gas and generates ethylbenzene, so as to cause target product styrene yield significantly
It reduces.The utility model has carried out corresponding apparatus structure and process modification as starting point, improves alkylation benzene second
The Technical Economy of alkene technique and the popularization feasibility of the technology commercialization.
The reaction unit in the source C1 of the utility model and alkylation of toluene production styrene is specifically described below.This
The source C1 employed in utility model includes but is not limited to methanol, formaldehyde, dimethyl ether, paraformaldehyde, dimethoxym ethane and formalin.
Fig. 1 shows the reaction according to the source C1 of the utility model exemplary embodiment and alkylation of toluene production styrene
Device and process flow diagram.
As described in Figure 1, exemplary embodiment according to the present utility model, the source C1 and alkylation of toluene produce styrene
Reaction unit include alkylated reaction unit 1 and product separative unit 2, alkylated reaction unit 1 is mainly used for carrying out the source C1
With the key reaction of alkylation of toluene production styrene, product separative unit 2 is mainly used for realizing the separation of product.
Alkylated reaction unit 1 includes reaction vessel 11, the first top feed pipe for being provided with the first catalyst bed 16
14, the first bottom discharge pipe 15 and at least 1 hydrogen output duct 12, at least 1 hydrogen output duct 12, which stretch to reaction, to be held
Device 11 is simultaneously inserted into the first catalyst bed 16, and reaction vessel 11 is connected by the first top feed pipe 14 with the source C1 and toluene source
And it is connected by the first bottom discharge pipe 15 with the second top feed pipe 22 of product separative unit 2.
The utility model is mainly led by being inserted at least 1 hydrogen output in the reaction vessel 11 to alkylated reaction unit
Pipe 12 separates from reaction member and exports by-product hydrogen, inhibits benzene to reduce the method for the concentration of hydrogen in reaction system
The hydrogenation reaction of ethylene, to realize the raising of styrene yield, structure improvement improves reaction efficiency, while reducing point
Scale and product separation costs from device, the final Technical Economy for improving alkylation preparation of styrene technique simultaneously improve the technology
Industrialization promotion feasibility.
Preferably, the hydrogen output duct 12 of the utility model is made of composition metal palladium membrane material, composition metal palladium
Membrane material has stronger through hydrogen capacity, can be used for the separation and production of hydrogen after membrane material is made, and then obtain high-purity
Hydrogen product.It is possible thereby to will in reaction vessel 11 generate hydrogen assemble it is defeated to hydrogen made of composition metal palladium membrane material
The tube wall of conduit 12 out, the permeable tube wall excessively of this hydrogen partial are delivered to hydrogen-holder or downstream work by hydrogen output duct 12
Sequence.
Preferred embodiment according to the present utility model, the alkylated reaction unit 1 of the utility model further include at least 1 side
The portion source radial direction C1 feed pipe 13, at least 1 side source radial direction C1 feed pipe 13 protrude into reaction vessel 11 and go out from side
Mouth is located at the top or centre of the first catalyst bed 16, wherein need to guarantee going out at least 1 side source radial direction C1 feed pipe 13
Mouth is located at the centre of the first catalyst bed 16.
Wherein, the source side radial direction C1 feed pipe 13 is also connected to feed the source C1, side diameter into reaction vessel 11 with the source C1
The number of aperture of tube wall aperture and exit to the source C1 feed pipe 13 is more than the number of aperture of inlet.
The source the C1 raw material fed by the side source radial direction C1 feed pipe 13 is that preheated (a little higher than reaction temperature) enters afterwards
In catalyst bed, because alkylated reaction is the endothermic reaction, bed temperature gradually decreases from the top to the bottom, excessively high top
Inlet temperature will lead to bed top material and crack and cause rapid catalyst deactivation, too low top in catalyst surface carbon distribution
Inlet temperature not can guarantee bottom catalyst bed and reach catalysis light-off temperature.And the utility model is by increasing at least 1
The side source radial direction C1 feed pipe 13, can by being passed through the source the C1 raw material slightly overheated to catalyst bed, and make its in reactor
Portion's material mixes rapidly, allows the axially and radially uniformity of temperature profile of catalyst bed, eliminates the ladder distribution in temperature field, more sharp
In the stable operation of reactor, also solves the problems, such as enlarge-effect for the design and processing of commercial plant in future.
Other than above structure improves, the alkylated reaction unit of the utility model can use more excellent in the prior art
Structure and catalyst, the utility model not to this carry out concrete restriction.
Product separative unit 2 in the utility model includes separation vessel 21, the second top feed pipe 22, ethylbenzene discharge nozzle
23, styrene discharge nozzle 25, the source unreacted C1 feed back pipe 24 and unreacted toluene feed back pipe 26, separation vessel 21 passes through unreacted
Toluene feed back pipe 26 is connected with the first top feed pipe 16 of alkylated reaction unit 1 to return isolated unreacted toluene
It returns and is alkylated production and improves toluene using conversion ratio, separation vessel 21 passes through the source unreacted C1 feed back pipe 24 and alkylation
At least 1 side source radial direction C1 feed pipe 13 of reaction member 1 be connected with by unreacted C1 source material also by side radial direction C1
Source feed pipe 13, which is added in separation vessel 21, participates in reaction.In addition, product separation system 2 is also equipped with hydrogen feed back pipe 27, point
From container 21 by the outlet end phase of hydrogen feed back pipe 27 and hydrogen output duct 12 also to store up the hydrogen separated
Deposit or enter downstream process.
The product separative unit used in the utility model can be identical as the device structures such as separator in the prior art,
Only the utility model improves Technical Economy by further being recycled isolated material.
Preferred embodiment according to the present utility model, the reaction unit of the utility model further include ethylbenzene dehydrogenation reaction unit
3, product separative unit 2 is connected by ethylbenzene discharge nozzle 23 with the third top feed pipe 33 of ethylbenzene dehydrogenation reaction unit 3, ethylbenzene
Dehydrogenation reaction unit 3 is anti-including the dehydrogenation container 32, third top feed pipe 33 and dehydrogenation for being provided with the second catalyst bed 32
Answer product discharge pipe 34, dehydrogenation container 31 by the second top of products of dehydrogenation reactions discharge nozzle 34 and product separative unit 2 into
Expects pipe 22 is connected or is connected with the first bottom discharge pipe 15 of alkylated reaction unit 1.
The utility model after product separative unit 2 by adding ethylbenzene dehydrogenation reaction unit 3, the ethylbenzene after enabling separation
Enough further occurrence dehydrogenation reactions and the more styrene target products of by-product, while because of the bed temperature of Ethylbenzene Dehydrogenation Reactor
It is higher, the waste heat of its products of dehydrogenation reactions can be made full use of to preheat side chain alkylation reaction raw materials, reach the comprehensive benefit of raw material
With；Also, the product separative unit 2 that products of dehydrogenation reactions can enter side chain alkylation reaction simultaneously carries out multi-cycle separation processing,
Improve the utilization rate of separation system and the overall technology economy of this technique.
The ethylbenzene dehydrogenation reaction unit used in the utility model can use in the prior art preferably structure and catalysis
Agent, the utility model do not carry out concrete restriction to this.
Optimum embodiment according to the present utility model, when reaction, reaction vessel of the methylbenzene raw material from alkylated reaction unit 1
11 tops are contacted into reaction vessel 11 and with the first catalyst bed 16, and C1 raw material is required according to reaction from reaction vessel respectively
11 top and side wall enter in reaction vessel 11 and contact with the first catalyst bed 16；At reaction conditions, toluene and C1
Raw material generates styrene, hydrogen and ethylbenzene in the first catalyst bed reaction, and it is defeated that hydrogen through composition metal palladium film enters hydrogen
Hydrogen-holder or downstream process are collected into after conduit 12 out, styrene and ethylbenzene enter product through the first bottom discharge pipe and divides
It is separated from unit 2, the circulations such as toluene and methanol after separation are again introduced into alkylated reaction unit process, benzene after separation
Ethylene is then used as product to be directly entered styrene product storage tank or downstream process, and ethylbenzene then enters ethylbenzene dehydrogenation reaction unit by-product
More styrene products.
The source C1 and alkylation of toluene production are carried out using the reaction unit in the above-mentioned source C1 and alkylation of toluene production styrene
When styrene, specifically, reaction is added from the first top feed pipe 14 of alkylated reaction unit 1 in toluene and the part source C1 and is held
Styrene, hydrogen and ethylbenzene are generated in device 11 and with 16 haptoreaction of the first catalyst bed, hydrogen is defeated by least 1 hydrogen
Enter hydrogen-holder or downstream process after conduit 12 exports out, institute's styrene and ethylbenzene enter product through the first bottom discharge pipe 15
Separative unit 2 is separated, and separating obtained styrene is directly entered styrene product storage tank or downstream process as product,
In, the source C1 is methanol, formaldehyde, dimethyl ether, paraformaldehyde, dimethoxym ethane or formalin.
Further, when alkylated reaction unit 1 further includes at least 1 side source radial direction C1 feed pipe 13, simultaneously will
The part source C1 is added in reaction vessel 11 from least 1 side source radial direction C1 feed pipe 13 and participates in reaction, by product separative unit
The 2 isolated sources unreacted C1 are also added in reaction vessel 11 from least 1 side source radial direction C1 feed pipe 13 and participate in reaction,
The isolated unreacted toluene of product separative unit 2 is added instead from the first top feed pipe 14 of alkylated reaction unit 1
It answers and participates in reaction in container 11.Improve material utilization and develop skill economy while, catalyst bed can be allowed axial
It is uniform with radial temperature profile, eliminate the ladder distribution in temperature field and the stable operation of more conducively reactor.
Further, when reaction unit further includes ethylbenzene dehydrogenation reaction unit 3, dehydrogenation is added in separating obtained ethylbenzene
Dehydrogenation by-product is carried out in container 31 and obtains products of dehydrogenation reactions, and gained products of dehydrogenation reactions is back to 2 weight of product separative unit
New separation and recovery, while the waste heat preheating of gained products of dehydrogenation reactions being utilized to enter the raw material of alkylated reaction unit 1, be conducive to
Improve the utilization rate of separative unit and the overall technology economy of this technique.
The utility model is described in further detail with comparative example combined with specific embodiments below.
Embodiment 1:
Reaction unit structure as shown in Figure 1, the reaction unit mainly by alkylated reaction unit 1,2 and of product separative unit
3 three parts of ethylbenzene dehydrogenation reaction unit composition.
Wherein, alkylated reaction unit 1 mainly includes reaction vessel, 3 composition metal palladium-membrane hydrogen output ducts, 3
Side radial direction C1 material feeding tube, the first top feed pipe (being sent into methylbenzene raw material and part C1 raw material) and distributor and first
Catalyst bed, the first bottom discharge pipe (output styrene and ethylbenzene).First top feed pipe respectively with the extraneous source C1 and first
Benzene pipeline is connected, while being also connected with the unreacted toluene feed back pipe of product separative unit, the first bottom discharge pipe and product point
The second top feed pipe from unit is connected.3 side radial direction C1 are provided on the reaction vessel side wall of alkylated reaction unit
Side entry feed pipeline protrudes into the inside of the first catalyst bed, at the same with the source the unreacted C1 feed back pipe from product separative unit
It is connected；The hydrogen output duct of composition metal palladium film protrude into the inside of catalyst bed and with hydrogen-holder or downstream process phase
Even, while the hydrogen output duct of composition metal palladium film is connected with the hydrogen feed back pipe of product separative unit.
Second top feed pipe of product separative unit is connected with the first bottom discharge pipe of alkylated reaction unit, simultaneously
Also it is connected with the products of dehydrogenation reactions discharge nozzle of ethylbenzene dehydrogenation reaction unit.Product separative unit is using existing mature separation skill
Art respectively separates hydrogen, the unreacted source C1, unreacted toluene, styrene, ethylbenzene, wherein hydrogen and composition metal palladium
The hydrogen output duct of film enters hydrogen-holder or downstream process together after being connected, the unreacted source C1 and the fresh source C1 raw material are mixed
Merge fast with the material in reaction vessel into the first catalyst bed inside by side radial direction C1 side entry feed pipe after preheating
Speed is uniformly mixed, and unreacted toluene passes through alkylated reaction unit process container after mixing and preheat with fresh methylbenzene raw material
The first top feed pipe enter the first catalyst bed react, third top of the by-product ethylbenzene through ethylbenzene dehydrogenation reaction unit
Portion's feed pipe enter the second catalyst bed of ethylbenzene dehydrogenation occur dehydrogenation reaction, gained styrene product be directly entered storage tank or under
Swim process.
The third top feed pipe of ethylbenzene dehydrogenation reaction unit is connected with the ethylbenzene discharge nozzle of product separative unit, and ethylbenzene is de-
The products of dehydrogenation reactions discharge nozzle of hydrogen reaction member is connected with the first bottom discharge pipe of alkylated reaction unit or divides with product
The second top feed pipe from unit is connected.
It is reacted using the above-mentioned source C1 and Benzyl Side-Chain alkylated reaction device, process flow is as follows:
Alkylated reaction unit and ethylbenzene dehydrogenation reaction unit are packed full with side chain alkylation catalyst and second respectively in advance
Benzene dehydrogenation and corresponding filler, and with compressed nitrogen by reaction unit equipment and blowing pipeline it is clean, purge step
Repeat, and is qualification with oxygen content < 0.2% (wt%) in system, heating or the condensing plant (figure in activation system
In it is not shown), reaction will be entered from the top of alkylated reaction unit after toluene and preheated to > 425 DEG C of the part source C1 raw material
Catalysis reaction occurs for the first catalyst bed of container, generates the products such as hydrogen, ethylbenzene and styrene.Meanwhile in reaction vessel
Side wall have the 3 sides source C1 material feed pipe by the part source C1 raw material be sent into the first catalyst bed inside or above, with
Material in reaction vessel is uniformly mixed rapidly, and hydrogen is led through the composition metal palladium-membrane hydrogen output inside insertion catalyst bed
Pipe infiltration enters hydrogen-holder or downstream process after collecting, and reacts the ethylbenzene of generation, styrene, the unreacted source C1 and not anti-
The products such as the toluene answered enter subsequent product separative unit, this part object through the first bottom discharge pipe of alkylated reaction unit
Material takes sample result (reaction condition are as follows: benzene and methanol molar ratio 5:1, combined feed are empty as shown in table 1 after gas chromatographic analysis
Fast 2h-1, normal pressure, bed temperature control be 440 DEG C)；
Product separative unit is using existing mature isolation technics, respectively by hydrogen, the unreacted source C1, unreacted first
Benzene, styrene, ethylbenzene separation, wherein after the hydrogen after separation is mixed with the hydrogen material of composition metal palladium-membrane hydrogen output duct
Enter hydrogen-holder or downstream hydrogen manufacturing procedure together, after the source C1 after separation is mixed with the fresh source C1 raw material and after preheating
Entered inside catalyst bed by side radial direction C1 side entry feed pipe and be uniformly mixed rapidly with material in reaction vessel, after separation
Toluene mix and preheat with fresh methylbenzene raw material after by the first top feed pipe of alkylated reaction unit process container
It reacts into the first catalyst bed, the ethylbenzene after separation enters through the third top feed pipe of ethylbenzene dehydrogenation reaction unit
The more styrene of dehydrogenation reaction by-product occur for the second catalyst bed, and styrene product is directly entered styrene after separation
Storage tank or downstream styrene manufacturing procedure.
Unreacted ethylbenzene is after ethylbenzene dehydrogenation reaction unit dehydrogenation from products of dehydrogenation reactions discharge nozzle and alkylated reaction
The product material of unit output enters product separative unit after mixing rapidly together and carries out product separation, and each product divides after separation
Not Jin Ru corresponding storage tank or downstream process, each material recycles by this method.
Comparative example 1:
This comparative example use reaction unit and process flow as shown in Fig. 2, the reaction unit by alkylated reaction unit 1
It is formed with 2 two parts of product separative unit.
Wherein, alkylated reaction unit 1 mainly includes reaction vessel, top feed pipe (feeding methylbenzene raw material and part C1
Raw material) and distributor and catalyst bed, bottom discharge pipe (output styrene and ethylbenzene).Top feed pipe respectively with extraneous C1
Source is connected with toluene pipeline, while being also connected with the unreacted toluene feed back pipe of product separative unit, bottom discharge pipe and product
The top feed pipe of separative unit is connected, and wherein bottom discharge pipe takes after sample that the results are shown in Table 1 after gas chromatographic analysis
(reaction condition are as follows: benzene and methanol molar ratio 5:1, combined feed air speed 2h-1, normal pressure, bed temperature control be 440 DEG C).
The top feed pipe of product separative unit is connected with the bottom discharge pipe of alkylated reaction unit, product separative unit
Using existing mature isolation technics, hydrogen, the unreacted source C1, unreacted toluene, styrene, ethylbenzene are separated respectively,
Middle hydrogen enters hydrogen-holder or downstream process, and the unreacted source C1 passes through alkylation after mixing and preheat with the fresh source C1 raw material
The top feed pipe of reactor enters inside catalyst bed to be uniformly mixed rapidly with the material in reaction vessel, unreacted first
Benzene by the top feed pipe of alkylated reaction unit process container enters catalysis after mixing and preheat with fresh methylbenzene raw material
Agent bed reacts, and gained styrene product is directly entered storage tank or downstream process.
Response data after the alkylation reactor bottoms material analysis of 1 embodiment and comparative example of table
| Sample | Methanol conversion | Selectivity of styrene | Ethylbenzene selectivity |
| Comparative example 1 | 45% | 12.5% | 35.2% |
| Embodiment 1 | 72% | 69.6% | 22.5% |
The methanol conversion and selectivity of styrene that the utility model obtains as seen from Table 1 are obviously higher than traditional alkyl
It is that micronizing technology obtains as a result, therefore the utility model has apparent technical advantage, and higher warp will be created for enterprise
Ji benefit.
To sum up, the utility model overcomes that existing side chain alkylation technology styrene yield is low, reaction system stability, benzene
Yield of ethene is low and the poor problem of Technical Economy, at the same can by the high added value Hydrogen Separation of by-product, purification and store or
It is transported to downstream process, it is whole to have many advantages, such as that high-phenylethylene yield, Technical Economy be preferable, system run all right, it mentions significantly
The high source C1 and Benzyl Side-Chain alkylation prepare the Technical Economy of styrene technology and promote possibility.
The utility model is not limited to specific embodiment above-mentioned.The utility model expands to any in this specification
The new feature of middle disclosure or any new combination, and disclose any new method or process the step of or any new group
It closes.
Claims (6)
1. the reaction unit in a kind of source C1 and alkylation of toluene production styrene, which is characterized in that the reaction unit includes alkane
Glycosylation reaction unit and product separative unit, the alkylated reaction unit include the reaction appearance for being provided with the first catalyst bed
Device, the first top feed pipe, the first bottom discharge pipe and at least 1 hydrogen output duct, at least 1 hydrogen output duct
It stretches to reaction vessel and is inserted into first catalyst bed, reaction vessel passes through the first top feed pipe and the source C1 and first
Benzene source is connected and passes through the first bottom discharge pipe and is connected with the second top feed pipe of product separative unit.
2. the reaction unit in the source C1 and alkylation of toluene production styrene according to claim 1, which is characterized in that the alkane
Glycosylation reaction unit further includes at least 1 side source radial direction C1 feed pipe, and at least 1 side source radial direction C1 feed pipe is from side
Portion protrudes into the reaction vessel and exports the top or centre for being located at first catalyst bed, wherein at least 1 side
The outlet of the portion source radial direction C1 feed pipe is located at the centre of first catalyst bed.
3. the reaction unit in the source C1 and alkylation of toluene production styrene according to claim 2, which is characterized in that the side
The portion source radial direction C1 feed pipe is also connected with the source C1, the tube wall aperture of the side source the radial direction C1 feed pipe and number of aperture in exit is more than
The number of aperture of inlet.
4. the reaction unit in the source C1 and alkylation of toluene production styrene according to claim 1, which is characterized in that the hydrogen
Gas output duct is made of composition metal palladium membrane material.
5. the reaction unit in the source C1 and alkylation of toluene production styrene according to claim 2, which is characterized in that the production
Product separative unit includes separation vessel, the second top feed pipe, ethylbenzene discharge nozzle, styrene discharge nozzle, the source unreacted C1 feed back
Pipe, unreacted toluene feed back pipe and hydrogen feed back pipe, the separation vessel pass through unreacted toluene feed back pipe and the alkylation
First top feed pipe of reaction member is connected, by least the 1 of the source unreacted C1 feed back pipe and the alkylated reaction unit
Root side radial direction C1 source feed pipe is connected and is connected by hydrogen feed back pipe with the outlet end of the hydrogen output duct.
6. the reaction unit in the source C1 and alkylation of toluene production styrene according to claim 5, which is characterized in that described anti-
Answering device further includes ethylbenzene dehydrogenation reaction unit, and the product separative unit passes through the ethylbenzene discharge nozzle and the ethylbenzene dehydrogenation
The third top feed pipe of reaction member is connected, and the ethylbenzene dehydrogenation reaction unit includes being provided with taking off for the second catalyst bed
Hydrogen tank, third top feed pipe and products of dehydrogenation reactions discharge nozzle, the dehydrogenation container pass through products of dehydrogenation reactions discharge nozzle
It is connected with the second top feed pipe of the product separative unit or with the first bottom discharge pipe of alkylated reaction unit.
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