CN104694150B - A kind of etherificate catalytic rectification method improving octane number and device - Google Patents
A kind of etherificate catalytic rectification method improving octane number and device Download PDFInfo
- Publication number
- CN104694150B CN104694150B CN201510130724.2A CN201510130724A CN104694150B CN 104694150 B CN104694150 B CN 104694150B CN 201510130724 A CN201510130724 A CN 201510130724A CN 104694150 B CN104694150 B CN 104694150B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- section
- tower
- reaction
- alcohol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 110
- 238000000034 method Methods 0.000 title claims abstract description 54
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 title claims abstract description 22
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 145
- 238000005194 fractionation Methods 0.000 claims abstract description 115
- 239000003054 catalyst Substances 0.000 claims abstract description 108
- 238000004821 distillation Methods 0.000 claims abstract description 80
- 238000006243 chemical reaction Methods 0.000 claims abstract description 78
- 239000007788 liquid Substances 0.000 claims abstract description 20
- 238000004508 fractional distillation Methods 0.000 claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 93
- 229930195733 hydrocarbon Natural products 0.000 claims description 85
- 150000002430 hydrocarbons Chemical class 0.000 claims description 85
- 239000004215 Carbon black (E152) Substances 0.000 claims description 70
- 239000000203 mixture Substances 0.000 claims description 53
- 238000006266 etherification reaction Methods 0.000 claims description 45
- 238000000926 separation method Methods 0.000 claims description 40
- 238000005204 segregation Methods 0.000 claims description 24
- 239000000945 filler Substances 0.000 claims description 19
- 238000009835 boiling Methods 0.000 claims description 14
- 238000006555 catalytic reaction Methods 0.000 claims description 11
- 229910000831 Steel Inorganic materials 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 239000010959 steel Substances 0.000 claims description 10
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 8
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000000470 constituent Substances 0.000 claims description 8
- 239000004571 lime Substances 0.000 claims description 8
- 238000011068 loading method Methods 0.000 claims description 8
- 208000012839 conversion disease Diseases 0.000 claims description 7
- 238000012856 packing Methods 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- 238000012546 transfer Methods 0.000 claims description 5
- 239000004744 fabric Substances 0.000 claims description 4
- 239000000835 fiber Substances 0.000 claims description 4
- 230000000149 penetrating effect Effects 0.000 claims description 4
- 239000011949 solid catalyst Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 230000008878 coupling Effects 0.000 abstract description 2
- 238000010168 coupling process Methods 0.000 abstract description 2
- 238000005859 coupling reaction Methods 0.000 abstract description 2
- 230000000630 rising effect Effects 0.000 abstract description 2
- 238000004904 shortening Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 108
- 239000000047 product Substances 0.000 description 38
- 150000001336 alkenes Chemical class 0.000 description 22
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 18
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 13
- 239000011347 resin Substances 0.000 description 12
- 229920005989 resin Polymers 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 10
- 238000011049 filling Methods 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- 238000000605 extraction Methods 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 5
- 238000005192 partition Methods 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- 238000007599 discharging Methods 0.000 description 4
- NUMQCACRALPSHD-UHFFFAOYSA-N tert-butyl ethyl ether Chemical compound CCOC(C)(C)C NUMQCACRALPSHD-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- -1 ether compound Chemical class 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- 238000005243 fluidization Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- 238000005406 washing Methods 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
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- 241000736911 Turritella communis Species 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000004231 fluid catalytic cracking Methods 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- HVZJRWJGKQPSFL-UHFFFAOYSA-N tert-Amyl methyl ether Chemical compound CCC(C)(C)OC HVZJRWJGKQPSFL-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention relates to a kind of etherificate catalytic rectification method improving octane number and device；Catalytic distillation tower body including a nested manifold type structure；Tower body includes rectifying section, multi-level unit catalysed fractionation section, intermediate fractionation section, shell structure catalysed fractionation section and stripping section from top to bottom successively.Tube side exothermic heat of reaction and chuck fractional distillation heat absorption is carried out thermal coupling by being configured to of shell structure catalysed fractionation section, and effectively suppresses the rising of reaction bed temperature, it is to avoid beds are overheated, at utmost reduce energy consumption；Catalyst structure is fixedly connected on below tower tray by multi-level unit catalysed fractionation segment structure, and cover all gas passage of this tower tray, product ether flows down step by step through downspout, but do not contact with catalyst, be conducive to shortening the product ether time of staying in the catalyst, product ether is avoided to contact again with catalyst, the caused back reaction of multiple-contact catalyst during solving the problems, such as product ether present in prior art under with liquid flow.
Description
The present invention relates to a kind of etherificate catalytic rectification method improving octane number and device, belong to petrochemical industry
Oil product process technology.
Background technology
The main blend component of Chinese commodity gasoline is catalytically cracked gasoline, accounts for more than the 80% of gasoline content.China
The composition characteristic of catalytically cracked gasoline is that olefin(e) centent is too high, and stability is poor, needs Olefin decrease to meet to content of olefin in gasoline
Restriction.On the other hand, light gasoline fraction contains abundant C5And C6Tertiary olefin, anti-with low-carbon alcohols using Tertiary olefin
Should generate and there is high-octane ether, the dual purpose that decreasing by gasoline olefin can be reached simultaneously and improve octane number.
Tertiary olefin is a kind of effective way improving octane number with the etherification reaction of alcohol, and this exothermic heat of reaction amount is big, and
And it is subject to Equilibrium limit, it is suitable for adopting catalytic reaction rectification method.Report about alkene and etherified catalytic distillation technology
As follows：
CN1348945 discloses a kind of ether product production method, and the lighter hydrocarbons containing tertiary olefin constituents are anti-with the etherificate of alcohol
First should carry out in independent (pre-) methyltertiarvbutyl ether reactor, enter again after reaching certain conversion ratio and in catalytic distillation tower, carry out depth
Degree etherification reaction and separation, product ether goes out device from catalytic distillation tower tower reactor, and unreacted lighter hydrocarbons and alcohol flow out from tower top, enter
Enter alcohol recovery tower.Alcohol reclaim that tower top stream goes out be alcohol and lighter hydrocarbons azeotropic mixture, and recycle, and tower reactor be unreacted gently
Hydrocarbon fraction, a portion light ends fractionation returns as the backflow of catalytic distillation tower, and another part is as product or further
The raw material extraction of processing.On the basis of above-mentioned technique, below catalytic distillation tower charging aperture, position produces one to CN1634832
Containing alcohol, ether, hydrocarbon side line mixed material, be recycled to pre-reactor entrance, to improve tower reactor ETBE product purity, reclaim simultaneously
Using unreacted fatty alcohol.US5491267 also discloses that similar side take-off circulating technology.
CN101245255, CN101245257, CN101245258 and CN101245259 disclose a kind of catalytic cracking and inhale
Receive the integrated etherification method of stabilisation systemss, load catalyst for etherification in Fcc Stabilizer, catalyst is selected from highly acid sun
One or more of ion exchange resin, molecular sieve catalyst and heteropolyacid catalyst.Hydro carbons raw material of etherification is mixed with fatty alcohol
Fcc Stabilizer is entered, in conversion zone and the catalyst for etherification haptoreaction of Fcc Stabilizer and carry out point after conjunction
Evaporate, separating obtained liquefied gas is obtained by the tower top of stabilizer, obtains stablizing containing ether compound in the bottom of towe of stabilizer
Gasoline.
US5188725 discloses a kind of fluid catalytic cracking process and etherification reaction combined method, and the main fluidisation that includes is urged
Change three parts of etherificate of cracking, the fractional distillation of crackate and C4 alkene and methanol, etherificate unit therein is by two fluidizations
Reactor and a catalytic distillation tower composition, the first fluidized bed adopts zeolite catalyst, and second fluidized bed is urged using sulfonate resin
Agent, catalytic distillation adopts method disclosed in US5000837.
In technology disclosed in US5679872, draw side line from catalytic distillation tower charging aperture position below, send into dividing of alcohol
Reclaim unreacted alcohol from tower.By adjusting side line flow velocity, obtain highly purified ether from the bottom of towe of catalytic distillation tower, this technical staff
Skill complex operation, equipment investment and high energy consumption.Disclosed in US5607557, technology is, by the side line thing producing from catalytic distillation tower
Material introduces a membrane separator, separates ethanol and recycles, and remaining hydrocarbon is returned catalytic distillation tower.
Flow process disclosed in US5248836 is made up of a fixed bed pre-reactor and a catalytic distillation tower, by reacting
The material that device flows out feeds below catalytic distillation tower conversion zone, supplements ethanol, liquid is arranged at conversion zone bottom above reaction zone
Reception device, the liquid of collection from side take-off and is delivered to tubular reactor, tower reactor produces ETBE, overhead extraction is unreacted
C4With the azeotropic mixture of ethanol, wash recovery alcohol with water.US6107526 discloses a kind of methyltertiarvbutyl ether reactor and etherificate catalytic distillation combination
The technique producing ETBE, raw material first passes through two-stage methyltertiarvbutyl ether reactor after pretreatment, enters back into catalytic distillation tower, and tower reactor produces
ETBE, the mixture of overhead extraction alcohol and hydrocarbon, need washing and the unreacted ethanol of Distillation recovery.
US5243102 discloses a kind of two-stage catalytic distillation flow process, is substantially carried out C in first order catalytic distillation tower5Alkene
The etherificate of hydrocarbon, the material of overhead extraction is divided into two strands, and therein one is passed through a methyltertiarvbutyl ether reactor, allow unreacted alkene with
Alcohol reacts further, then loops to the stripping section of catalytic distillation tower, and tower bottoms is concomitantly introduced into the second catalysis with the methanol supplementing
Distillation column, is substantially carried out the etherificate of C6 alkene in after-fractionating tower, it is methanol and C that tower top flows out material6The mixture of hydrocarbon.
Method disclosed in US5015782 is with C4And C4Above isomeric olefine is raw material, the fixed bed reaction of two series connection
Device and a catalytic distillation tower, load mesoporous molecular sieve in reactor, load sulfonate resin in tower.Raw material through washing, one section
Etherificate, two-stage nitration etherificate, finally obtain MTBE in catalytic distillation tower reactor.
Also disclose catalytic distillation tower in multiple patents to combine with boiling point reactors, or catalytic distillation tower and fixed bed
The flow process of pre-reactor combination, that is, the alkene in raw material and methanol be introduced into a reactor, occur liquid phase anti-in the reactor
Should, the effluent of reactor is fed in catalytic distillation tower, and unreacted alkene continues to react with alcohol, the methanol of excess and not anti-
The hydrocarbon answered is discharged as overhead distillate, and the mixture of ether or ether and heavy hydrocarbon is discharged as bottom product, and described patent is
US4336407、US5243102、US5352848、US5015783、US5399787、US5003124and US 4,950,803.
Boiling point reactors disclosed in US20060030741 are by the addition of methanol with the feature of catalytic distillation tower combination technique
Amount controls in the scope less than stoichiometric proportion, so that alcohol is reacted completely, catalytic distillation tower top occurs without azeotropic mixture, tower top effluent
Matter contains unreactive hydrocarbons.This method needs strictly to control the feed molar ratio of methanol by the concentration monitoring methanol in reaction zone, otherwise
Arise that in low-conversion or the low etherification product of tower, methanol content is exceeded, in addition, the alkene of excess easily occurs polyreaction.
US6930206, US 20040210090 and WO 2003104168 discloses one kind and is used for synthesizing tertiary amyl-methyl ether
(TAME) partition wall type catalytic distillation tower, is to arrange longitudinal partition in the Partial Height of conversion zone tower section or whole height, every
The side filling solid catalyst of wall, the opposite side in next door only has centrifugation, and rectifying section is identical with conventional rectification tower, stripping
Section is divided into be had partition and not to have two kinds of next door form.C5Hydrocarbon feed and methanol first carry out primary reaction in fixed bed reactors
Reach chemical equilibrium composition, then introduce the fractionation zone of above-mentioned partition wall type catalytic distillation tower.This reactor and partition wall type are urged
Change distillation column group technology and be not suitable for the wider Etherification of Light FCC Gasoline reaction of boiling range, because the etherificate of light gasoline needs C5And C6Live
Property alkene is all contacted with catalyst, and C6 +The presence of component makes C5Component is directly entered rectifying section from the fractional distillation side in next door, and not
The beds of next door opposite side, therefore C can be entered5The total conversion of alkene is not high.
The existing etherificate catalytic rectification process feature improving octane number be all confined to how by catalytic rectifying tower with
The technological process change of combination of reactors, or it is to increase the difference that side line enters out position, the catalytic distillation device knot being adopted
Configuration formula does not then all break through traditional method.For the feature of active olefin in light gasoline and low-carbon alcohols etherification reaction, prior art
Have the following disadvantages, the first reacts the big calorimetric released with catalytic rectifying tower not when the flow process combining using reactor
Can be utilized effectively, be also easy to produce focus simultaneously in beds；Its two be traditional structure catalytic rectifying tower anti-
Section is answered to be difficult to avoid that what the continuous contact with lower catalyst agent when being downward through beds of etherification reaction product was led to
Back reaction.
Content of the invention
It is an object of the invention to provide a kind of etherificate catalytic rectification method improving octane number and device, the method
There is energy-conservation, small investment, simple to operate, mild condition, the advantage effectively suppressing back reaction.
For reaching above-mentioned purpose, the present invention is realized by the following technical programs：
A kind of etherificate catalytic distillation device improving octane number, including the catalysis essence of a nesting-manifold type structure
Evaporate tower body；Tower body includes rectifying section, multi-level unit catalysed fractionation section, shell structure catalysed fractionation section and stripping from top to bottom successively
Section.
A kind of etherificate catalytic distillation device improving octane number, including the catalysis essence of a nesting-manifold type structure
Evaporate tower body；Tower body includes rectifying section, multi-level unit catalysed fractionation section, intermediate fractionation section, shell structure catalysis from top to bottom successively
Distillation stage and stripping section.
The shell structure catalysed fractionation section of described etherificate catalytic distillation device is be 500～3000mm by length one
Vertically inner tube or multiple vertical inner tube arranged side by side and a chuck composition around inner tube, catalyst and fractional distillation filler load respectively
In the pipe with chuck in, the upper end closed of loading catalyst bed and only communicating with the feeding line of catalytic rectifying tower, its lower end
Communicate with stripping section, filling fractional distillation filler side is all penetrating up and down.
The shell structure catalysed fractionation section of described etherificate catalytic distillation device device is to be 500～3000mm by length
One vertical inner tube or multiple vertical inner tube arranged side by side and a chuck composition around inner tube, loading catalyst in inner tube, folder
Fractional distillation filler is loaded, the ratio in inner tube and chuck section is 0.1～1.0, the charging only with catalytic rectifying tower of the lower end of inner tube in set
Pipeline is connected, and the lower end of chuck is connected with stripping section；Inner tube is all connected with intermediate fractionation section with the upper end of chuck, inner tube
Upper end open at liquid guide flow plate is set, to stop the liquid that flows down above it from flowing into the beds in pipe.
The multi-level unit catalysed fractionation section of described etherificate catalytic distillation device is by one or more Reaction Separation units
Rearrange along longitudinally staggered, each Reaction Separation unit is combined by a catalyst structure and a tower tray carrying downspout
Form, catalyst structure is one and has loaded the container of catalyst or tied up by multiple catalyst containers and constitute, catalyst structure
Part is fixedly connected on below tower tray, and covers all gas passage of this tower tray, each catalyst structure and tower below
Disk distance is 50～600mm.
A kind of method improving octane number using described etherificate catalytic distillation device, total hydrocarbon feed and low-carbon alcohols are mixed
Enter catalytic rectifying tower after compound is preheated, and be directly incorporated into Catalyst packing from the upper end of shell structure catalysed fractionation section
Area, is contacted generation chemical reaction, then flows out from the lower end of shell structure catalysed fractionation section, restructuring therein with acidic catalyst
Divide entrance stripping section to separate and remove unreacted C5And C6Hydrocarbon and alcohol, then discharge from bottom of towe；And light component therein enters shell
The fractionation zone of structured catalysis distillation stage, separates through packing layer in uphill process and removes product ether, then go up and urge to multistage
Change the separation that distillation stage carries out depth etherification reaction and etherification product, hydrocarbon is introduced into bottom first order reaction with the steam of alcohol and separates
Unit, carries out depth etherification reaction by described catalyst structure, makes the elevation of boiling point after generating ether, becomes lime set and falls into
Following fractionation zone, unreacted hydrocarbon and alcohol steam pass through catalyst structure tray above, are passed with the liquid on tower tray
Matter and heat exchange, the product ether that further separation removal is carried secretly, then proceed to rise to second level Reaction Separation unit, experience again
Reaction and separation process, the ether of every order reaction conversion each falls within the tower tray of following first order reaction separative element, through downspout by
Level flows down, but does not contact with catalyst；After depth etherification reaction, remaining inertia lighter hydrocarbons and the mixture of alcohol are urged by multistage
The top changing distillation stage enters rectifying section, is stripped of the lighter hydrocarbons of ether and alcohol mixture enters overhead condenser, tower top effluent enters
Enter the segregation apparatuss of alcohol and hydrocarbon.
A kind of method improving octane number using described etherificate catalytic distillation device, total hydrocarbon feed is mixed with low-carbon alcohols
Enter catalytic rectifying tower after conjunction preheating, and be directly incorporated into beds and acidity from the lower end of shell structure catalysed fractionation section
There is chemical reaction in catalyst contact, then flow out from the upper end of shell structure catalysed fractionation section, and heavy constituent therein is entered successively
Enter fractionation zone and the stripping section of shell structure catalysed fractionation section, separate and remove unreacted C5And C6Hydrocarbon and alcohol, then arrange from bottom of towe
Go out；The light component flowing out from shell structure catalysed fractionation section upper end enters intermediate fractionation section and separates removal product ether, then goes up
Carry out the separation of depth etherification reaction and etherification product to multistage catalysed fractionation section, the steam of hydrocarbon and alcohol is introduced into multistage catalytic and divides
Evaporate the bottom first order reaction separative element of section, depth etherification reaction is carried out by catalyst structure, after generating ether, makes boiling
Point raises, and becoming lime set falls into following fractionation zone, and unreacted hydrocarbon and alcohol steam pass through catalyst structure tray above, with
Liquid on tower tray carries out mass transfer and heat exchange, the product ether that further separation removal is carried secretly, then proceedes to rise to the second level anti-
Answer separative element, again experience reaction and separation process, the ether of every order reaction conversion each falls within following first order reaction separative element
Tower tray in, flow down step by step through downspout, but do not contact with catalyst；After depth etherification reaction remaining inertia lighter hydrocarbons with
The mixture of alcohol enters rectifying section by the top of multistage catalytic distillation stage, is stripped of the lighter hydrocarbons of ether and alcohol mixture steam from rectification
Duan Shangduan enters overhead condenser, and tower top effluent enters the segregation apparatuss of alcohol and hydrocarbon.
The catalyst container of described device is cylindricality net basket, fiber woven bags, stainless steel wave card are urged with having loaded solid
One or more of the sandwich sandwich of cloth bag composition of agent, stainless (steel) wire bundle volume structure.
The tower tray of described device is one or more of float valve structure, blister configuration, tongued structures, sieve-plate structure.
The multistage catalytic distillation stage of described device is 2～15 grades.
Hereinafter present invention is elaborated：
A kind of improve octane number etherificate catalytic distillation device, be by condenser, reboiler and one have nesting-
The catalytic distillation tower body composition of manifold type structure, tower body includes：Rectifying section, multi-level unit catalysed fractionation section, shell structure is catalyzed
Distillation stage, stripping section；Described multi-level unit catalysed fractionation section is along longitudinally staggered row by one or more Reaction Separation units
Row composition, each Reaction Separation unit is combined by a catalyst structure and a tower tray carrying downspout, catalyst
Component is one and has loaded the container of catalyst or tied up by multiple catalyst containers and constitute, catalyst container is cylindricality net basket
Or fiber woven bags, catalyst structure is fixedly connected on below tower tray, and covers all gas passage of this tower tray, and each is urged
Agent component is 50～600mm with tower tray distance below, and the multistage catalytic distillation stage construction of the present invention solves reaction and produces
Thing ether under with liquid flow during touch catalyst cause back reaction problem；Described shell structure catalysed fractionation
A vertical inner tube or multiple vertical inner tube arranged side by side and a chuck around inner tube that section is is 500～3000mm by length
Composition, catalyst and fractional distillation filler fill in pipe and in chuck respectively, the upper end closed of loading catalyst bed and only with urge
The feeding line changing rectifying column communicates, and its lower end is communicated with stripping section, and filling fractional distillation filler side is all penetrating up and down, this
The shell structure catalysed fractionation section method to set up of invention solves the beds that heat release during initial etherification reaction is led to soon
Focus and the problem of thermal waste.
Described catalytic rectifying tower, can set up between multi-level unit catalysed fractionation section and shell structure catalysed fractionation section
Intermediate fractionation section, now loading catalyst in the inner tube of shell structure catalysed fractionation section, in chuck load fractional distillation filler, inner tube with
The ratio in chuck section be 0.1～1.0, the lower end of inner tube is only connected with the feeding line of catalytic rectifying tower, the lower end of chuck with
Stripping section is connected；Inner tube is all connected with intermediate fractionation section with the upper end of chuck, and at the upper end open of inner tube, setting liquid is led
Stream plate, to stop the liquid flowing down above it from flowing into the beds in pipe.
A kind of etherificate catalytic rectification method improving octane number of the present invention, is with containing iso-amylene and/or dissident's alkene
Hydrocarbon mixture or light gasoline fraction be total hydrocarbon feed, this total hydrocarbon feed and low-carbon alcohols are with 1:1～20:1 mass ratio mixing
It is added in the catalytic distillation device of the present invention as reaction raw materials, complete pre- etherificate and depth etherification reaction in a tower,
Generate the product containing ether, catalytic rectifying tower operating pressure 0.1～0.6Mpa, 45～75 DEG C of tower top temperature, bottom temperature 90～
150 DEG C, reflux ratio is 1～10；The technological process of the inventive method is that total hydrocarbon feed enters institute mix preheating with low-carbon alcohols after
State catalytic rectifying tower, and be directly incorporated into beds from the lower end of shell structure catalysed fractionation section and contact with acidic catalyst
There is chemical reaction, then flow out from the upper end of shell structure catalysed fractionation section, heavy constituent therein sequentially enters shell structure
The fractionation zone of catalysed fractionation section and stripping section, separate and remove unreacted C5And C6Hydrocarbon and alcohol, then discharge from bottom of towe；From shell
The light component that structured catalysis distillation stage upper end is flowed out enters intermediate fractionation section and separates removal product ether, then goes up to multistage catalytic
Distillation stage carries out the separation of depth etherification reaction and etherification product, the steam of hydrocarbon and alcohol be introduced into multistage catalytic distillation stage under
Face first order reaction separative element, carries out depth etherification reaction by described catalyst structure, makes boiling point liter after generating ether
Height, becomes lime set and falls into following fractionation zone, unreacted hydrocarbon and alcohol steam pass through catalyst structure tray above, with tower tray
On liquid carry out mass transfer and heat exchange, the product ether that further separation removal is carried secretly, then proceed to rise to the second order reaction and divide
From unit, experience reaction and separation process again, the ether of every order reaction conversion each falls within the tower of following first order reaction separative element
In disk, flow down step by step through downspout, but do not contact with catalyst；Remaining inertia lighter hydrocarbons and alcohol after depth etherification reaction
Mixture enters rectifying section by the top of multistage catalytic distillation stage, is stripped of the lighter hydrocarbons of ether and alcohol mixture steam from rectifying section
End enters overhead condenser, and tower top effluent enters the segregation apparatuss of alcohol and hydrocarbon, and segregation apparatuss adopt side disclosed in CN1348945
Method disclosed in method or US5792891, the alcohol isolated removes alcohol with newly supplementary methanol mixed Posterior circle to the charging aperture of tower
The logistics of heavy constituent containing ether that flows out with bottom of towe of light hydrocarbon mixture mix as putting forward high-octane gasoline product.
Of the present invention improve octane number etherificate catalytic rectification method another kind of technological process be, hydrocarbon mixture
Raw material and the preheated rear entrance catalytic rectifying tower of low-carbon (LC) alcohol mixture, and directly introduce from the upper end of shell structure catalysed fractionation section
To catalyst filling zone, contact generation chemical reaction with acidic catalyst, then flow from the lower end of shell structure catalysed fractionation section
Go out, heavy constituent therein enters stripping section separation and removes unreacted C5And C6Hydrocarbon and alcohol, then discharge from bottom of towe；And it is therein
Light component enters the fractionation zone of shell structure catalysed fractionation section, separates through packing layer and removes product ether, so in uphill process
Rise to the separation that multistage catalytic distillation stage carries out depth etherification reaction and etherification product afterwards, under the steam of hydrocarbon and alcohol is introduced into
Face first order reaction separative element, carries out depth etherification reaction by described catalyst structure, makes boiling point liter after generating ether
Height, becomes lime set and falls into following fractionation zone, unreacted hydrocarbon and alcohol steam pass through catalyst structure tray above, with tower tray
On liquid carry out mass transfer and heat exchange, the product ether that further separation removal is carried secretly, then proceed to rise to the second order reaction and divide
From unit, experience reaction and separation process again, the ether of every order reaction conversion each falls within the tower of following first order reaction separative element
In disk, flow down step by step through downspout, but do not contact with catalyst；Remaining inertia lighter hydrocarbons and alcohol after depth etherification reaction
Mixture enters rectifying section by the top of multistage catalytic distillation stage, is stripped of the lighter hydrocarbons of ether and alcohol mixture enters overhead condensation
Device, tower top effluent enters the segregation apparatuss of alcohol and hydrocarbon, segregation apparatuss adopt method disclosed in CN1348945 or
Method disclosed in US5792891, the alcohol isolated removes the lighter hydrocarbons of alcohol with newly supplementary methanol mixed Posterior circle to the charging aperture of tower
The logistics of heavy constituent containing ether that mixture is flowed out with tower reactor mixes conduct and puies forward high-octane gasoline product.
Tower tray in described multistage catalytic distillation stage is float valve structure, blister configuration, tongued structures, in sieve-plate structure
One or more.
Catalyst structure in described multistage catalytic distillation stage be by stainless steel wave card with loaded solid catalyst
The sandwich sandwich of cloth bag composition or stainless (steel) wire bundle one or more of volume structure.
Preferred multistage catalytic distillation stage is that the Reaction Separation unit described in 5～15 rearranges along longitudinally staggered.
Preferably low-carbon alcohols are methanol.
The present invention has the following advantages and effect：
1. the reactant concentration in initial etherification reaction stage is far longer than production concentration, and positive reaction speed is high, and thermal discharge is big,
Now do not need to remove product in time, but need to remove reaction liberated heat from beds in time.The present invention is etherified
Being configured to tube side (or chuck) exothermic heat of reaction and chuck (or pipe of the shell structure catalysed fractionation section of catalytic distillation device
Journey) fractional distillation heat absorption carries out thermal coupling, effectively inhibits the rising of reaction bed temperature, it is to avoid beds are overheated, and
Natural contral reaction is carried out under bubble point temperature, also makes full use of reaction heat in fractional distillation process simultaneously, at utmost reduces energy
Consumption；
2. the reactant concentration in depth etherification reaction stage is relatively low, needs in time product ether to be removed catalyst zone, in case
Only there is back reaction.Catalyst structure is fixedly connected on by the multi-level unit catalysed fractionation segment structure of catalytic distillation device of the present invention
Below tower tray, and cover all gas passage of this tower tray, the ether of every order reaction conversion can fall directly into following first order reaction
In the tower tray of separative element, flow down step by step through downspout, but do not contact with catalyst, this is beneficial to shorten product ether in catalysis
The time of staying in agent, and avoid contacting again of product ether and catalyst, solve reaction present in prior art
Product ether under with liquid flow during the caused back reaction of multiple-contact catalyst problem；
3. do not need to arrange pre- methyltertiarvbutyl ether reactor before catalytic rectifying tower, save investment；
4. the fractionation zone setting of shell structure catalysed fractionation section can save stripping section theoretical stage, reduces tower height degree.
Brief description
Fig. 1 is the process flow diagram of the embodiment of the present invention 1；
Fig. 2 is the process flow diagram of the embodiment of the present invention 2；
Fig. 3 is the process flow diagram of the embodiment of the present invention 3；
In figure：100 catalytic rectifying towers；11 rectifying sections；12 multi-level unit catalysed fractionation sections；13 intermediate fractionation sections；14 shells
Structured catalysis distillation stage；15 stripping sections；16 catalyst structures；17 tower trays；18 downspouts；19 liquid guide flow plates；20 inner tubes；21 urge
Agent；22 fractional distillation fillers；23 complete condensers；24 reboilers；25 alcohol and the segregation apparatuss of hydrocarbon；101 light gasoline feed line；102 first
Alcohol pipeline；103 methanol feed pipelines；201 overhead vapours extraction pipelines；202 tower top discharging pipelines；203 methanol loop pipelines；
204 lighter hydrocarbons extraction pipelines；205 bottom of towe extraction pipelines.
Specific embodiment
The present invention will be further described with reference to the accompanying drawings and examples, but is not intended to limit the protection model of the present invention
Enclose.
Embodiment 1
The present embodiment adopt catalytic distillation device as shown in Figure 1, a diameter of 100mm of catalytic rectifying tower, tower body is by essence
Evaporate section (11), multi-level unit catalysed fractionation section (12), intermediate fractionation section (13), shell structure catalysed fractionation section (14) and stripping section
(15) form, rectifying section has 2 pieces of jet trays, and multistage catalytic distillation stage includes 8 order reaction separative elements, Reaction Separation lists at different levels
Unit by the bubble cap tray (17) with downspout (18) and is fixed on catalyst structure (16) below tower tray and forms, catalyst
Component ties up filling macropore sulfuric acid resin catalyst inside fiber woven bags for stainless (steel) wire, and each catalyst structure is with below
Tower tray distance be 80mm, intermediate fractionation section (13) haves three layers float valve tray, and the height of shell structure catalysed fractionation section (14) is
2000mm, the vertical inner tube by 1 a diameter of 40mm and the chuck around inner tube form, and in inner tube, filling macropore sulfuric acid resin is urged
Agent (21), loads in chuckThe feedstock pipeline of rustless steel θ ring filler (22), the lower end of inner tube and catalytic rectifying tower
(101) it is connected, 1 draining plate (19) is set at the upper end open of inner tube, chuck upper end is communicated with intermediate fractionation section (13), under
End is communicated with stripping section (15), and stripping section has 3 pieces of sieve trays.Light gasoline feed line (101) and methanol feed pipeline (103)
Connect with the bottom of shell structure catalysed fractionation section inner tube (20) of catalytic rectifying tower after converging.Tower top passes through pipeline (201) even
Connect complete condenser (23).Complete condenser outlet line (202) is connected with the segregation apparatuss (25) of alcohol and hydrocarbon.Segregation apparatuss from alcohol and hydrocarbon
(25) methanol out is connected with methanol line (102) through pipeline (203).From the segregation apparatuss (25) of alcohol and hydrocarbon lighter hydrocarbons out
It is connected with bottom of towe discharging pipeline (205) through pipeline (204).
Catalytic rectifying tower is entered through pipeline (101), by shell structure catalysed fractionation after gasoline stocks and methanol mixed preheating
The bottom of section enters inner tube (20), contacts with catalyst (21) during up, subsequently flows out from inner tube top, therein heavy
Component overflow enters the fractional distillation packing area (22) of shell structure catalysed fractionation section, and the mixture of product ether and heavy hydrocarbon comes downwards to stripping
Section (15), then produces from bottom of towe through pipeline (205)；Light component vaporization entrance intermediate fractionation section (13) therein is isolated and is carried secretly
Ether, remaining C5And C6Hydrocarbon rises to multistage catalytic distillation stage (12) with the admixture of gas of alcohol, enters catalyst structure (16)
In carry out depth etherification reaction, the ether boiling point of generation improves, and becomes lime set and falls into following fractionation zone, unreacted hydrocarbon and alcohol mix
Gas passage from tower tray for the compound steam passes through tower tray (17), rises to second level Reaction Separation unit, the ether of every grade of generation
Each fall within the tower tray of following primary unit, flow down step by step through downspout (18), remaining inertia is light after depth etherification reaction
The mixture of hydrocarbon and alcohol enters rectifying section (11) by the upper end of multistage catalytic distillation stage and removes the ether carried secretly further, then by managing
Line (201) enters overhead condenser, condensed fluid partial reflux, partly introduces the segregation apparatuss (25) of alcohol and hydrocarbon through pipeline (202),
Segregation apparatuss adopt method disclosed in CN1348945, and the alcohol isolated is recycled to methanol line (102) through pipeline (203), and new
Fresh methanol mixed recycling, the light hydrocarbon mixture of removing alcohol is through pipeline (204) and containing from tower reactor effluent pipeline (205)
Ether heavy hydrocarbon mixes, as etherified gasoline product.
Gasoline stocks are the FCC light gasoline of boiling range 29-65 DEG C, wherein C5Active tertiary olefin content is 14.72wt%, C6Live
Property tertiary olefin content be 6.13wt%.Gasoline stocks are 12: 1 with the mass ratio of methanol charging, air speed 2.0h-1, catalytic rectifying tower
Operating pressure 0.23MPa, reflux ratio 3,57.5 DEG C of tower top temperature, 104.7 DEG C of bottom temperature, the gasoline product octane number obtaining increases
Plus 3.3 units.
Embodiment 2
The present embodiment adopt catalytic distillation device as shown in Figure 2, a diameter of 100mm of catalytic rectifying tower, tower body is by essence
Evaporate section (11), multi-level unit catalysed fractionation section (12), shell structure catalysed fractionation section (14) and stripping section (15) composition, rectifying section
The JWB-700Y filler of filling 500mm.Multistage catalytic distillation stage includes 15 order reaction separative elements, and Reaction Separation units at different levels are equal
It is made up of with the catalyst structure (16) that is fixed on below tower tray the jet tray (17) with downspout (18), catalyst structure
For loading macropore sulfuric acid resin catalyst inside cylindrical stainless steel net basket, each catalyst structure with tower tray distance is below
50mm, the height of shell structure catalysed fractionation section (14) is 800mm, by the vertical inner tube (20) of 1 diameter 80mm with around interior
The chuck composition of pipe, the upper end closed of chuck simultaneously only communicated with the feeding line (101) of catalytic rectifying tower, the lower end of chuck with carry
Evaporate section to communicate, in chuck, load filling in macropore sulfuric acid resin catalyst, inner tube (20)Rustless steel θ ring filler (22), inner tube
Upper end communicate with multi-level unit catalysed fractionation section (12), the lower end of inner tube is communicated with stripping section (15), and stripping section has 15 pieces of sieves
Plate tower tray.Light gasoline feed line (101) and methanol feed pipeline (103) converge rear and catalytic rectifying tower shell structure catalysis
The top connection of distillation stage chuck.Tower top connects complete condenser (23) by pipeline (201).Complete condenser outlet line (202) and alcohol
Connect with the segregation apparatuss (25) of hydrocarbon.From the segregation apparatuss (25) of alcohol and hydrocarbon methanol out through pipeline (203) and methanol line
(102) connect.It is connected with bottom of towe discharging pipeline (205) through pipeline (204) from the segregation apparatuss (25) of alcohol and hydrocarbon lighter hydrocarbons out
Connect.
Catalytic rectifying tower is entered through pipeline (101), by shell structure catalysed fractionation after gasoline stocks and methanol mixed preheating
Section top enter loading catalyst chuck, contact with macropore sulfuric acid resin catalyst (21) during descending, subsequently from
Bottom is flowed out, and heavy constituent therein is directly entered stripping section (15) and carries out concentration, then produces through pipeline (205)；And it is therein
Light component enters inner tube from the bottom of inner tube (20), carries out, through filler (22), the product that fractional distillation removal carries in uphill process
Ether, then goes up to multistage catalysed fractionation section (12), gas phase enters in catalyst structure (16) and carries out depth etherification reaction, generates
Ether boiling point improve, become lime set and fall into following fractionation zone, the unreacted hydrocarbon and alcohol mixture steam gas from tower tray
Passage passes through tower tray (17), rises to second level Reaction Separation unit, and the ether of every grade of generation each falls within the tower of following primary unit
Disk, flows down step by step through downspout (18), and after depth etherification reaction, remaining inertia lighter hydrocarbons and the mixture of alcohol are urged by multistage
Upper end entrance rectifying section (11) changing distillation stage removes the ether carried secretly further, then enters overhead condenser by pipeline (201),
Condensed fluid partial reflux, partly introduces the segregation apparatuss (25) of alcohol and hydrocarbon, segregation apparatuss adopt US5792891 through pipeline (202)
Disclosed method, the alcohol isolated is recycled to methanol line (102) through pipeline (203), mixes recycling with fresh methanol, takes off
Light hydrocarbon mixture except alcohol is mixed with the heavy hydrocarbon containing ether from tower reactor effluent pipeline (205) through pipeline (204), as etherificate vapour
Oily product.
The composition of gasoline stocks is 9: 1 with embodiment 1, gasoline stocks with the mass ratio of methanol charging, air speed 1.2h-1, urge
Change rectifying column operating pressure 0.3MPa, reflux ratio 6,66.2 DEG C of tower top temperature, 118.3 DEG C of bottom temperature, the gasoline product obtaining
Octane number increases by 3.5 units.
Embodiment 3
The present embodiment adopt catalytic distillation device as shown in Figure 3, a diameter of 100mm of catalytic rectifying tower, tower body is by essence
Evaporate section (11), multi-level unit catalysed fractionation section (12), intermediate fractionation section (13), shell structure catalysed fractionation section (14) and stripping section
(15) form, rectifying section loads the JWB-700Y filler of 500mm, multistage catalytic distillation stage includes 10 order reaction separative elements, respectively
Order reaction separative element by the float valve tray with downspout (18) (17) and is fixed on the catalyst structure (16) below tower tray
Composition, catalyst structure is the Sanming City being made up of with the cloth bag having loaded solid macropore sulfuric acid resin catalyst stainless steel wave card
Control sandwich, each catalyst structure is 100mm with tower tray distance below, intermediate fractionation section (13) loads 500mm's
JWB-700Y filler, the height of shell structure catalysed fractionation section (14) is 1000mm, vertically parallel interior by 7 a diameter of 25mm
Pipe (20) and 1 chuck composition around inner tube, filling macropore sulfuric acid resin catalyst (21) in inner tube, load in chuck
Rustless steel θ ring filler (22), the lower end of all inner tubes is all connected with the feedstock pipeline (101) of catalytic rectifying tower, each
Respectively there is 1 draining plate (19), chuck upper end is communicated with intermediate fractionation section (13), lower end and stripping section at the upper end open of inner tube
(15) communicate, stripping section has 3 pieces of jet trays.Light gasoline feed line (101) and methanol feed pipeline (103) converge after with urge
The bottom changing the inner tube (20) of shell structure catalysed fractionation section of rectifying column connects.Tower top connects complete condenser by pipeline (201)
(23).Complete condenser outlet line (202) is connected with the segregation apparatuss (25) of alcohol and hydrocarbon.From the segregation apparatuss (25) of alcohol and hydrocarbon out
Methanol be connected with methanol line (102) through pipeline (203).From the segregation apparatuss (25) of alcohol and hydrocarbon lighter hydrocarbons out through pipeline
(204) it is connected with bottom of towe discharging pipeline (205).
Catalytic rectifying tower is entered through pipeline (101), by shell structure catalysed fractionation after gasoline stocks and methanol mixed preheating
The bottom of section enters inner tube (20), contacts with catalyst (21) during up, subsequently flows out from inner tube top, therein heavy
Component overflow enters the fractional distillation packing area (22) of shell structure catalysed fractionation section, and the mixture of product ether and heavy hydrocarbon comes downwards to stripping
Section (15), then produces from bottom of towe through pipeline (205)；Light component vaporization entrance intermediate fractionation section (13) therein is isolated and is carried secretly
Ether, remaining C5And C6Hydrocarbon rises to multistage catalytic distillation stage (12) with the admixture of gas of alcohol, enters catalyst structure (16)
In carry out depth etherification reaction, the ether elevation of boiling point of generation, become lime set and fall into following fractionation zone, unreacted hydrocarbon and alcohol mix
Compound steam passes through tower tray (17), rises to second level Reaction Separation unit, and the ether of every grade of generation each falls within following primary unit
Tower tray, flow down step by step through downspout (18), after depth etherification reaction, remaining inertia lighter hydrocarbons and the mixture of alcohol are by many
The upper end of level catalysed fractionation section enters rectifying section (11) and removes the ether carried secretly further, then enters tower top by pipeline (201) cold
Condenser, condensed fluid partial reflux, partly introduce the segregation apparatuss (25) of alcohol and hydrocarbon through pipeline (202), segregation apparatuss adopt
Method disclosed in CN1348945, the alcohol isolated is recycled to methanol line (102) through pipeline (203), mixes weight with fresh methanol
Multiple utilization, the light hydrocarbon mixture of removing alcohol is mixed with the heavy hydrocarbon containing ether from tower reactor effluent pipeline (205) through pipeline (204),
As etherified gasoline product.
Gasoline stocks are the FCC light gasoline of boiling range 29-60 DEG C, wherein C5Active tertiary olefin content is 16.64wt%, C6Live
Property tertiary olefin content be 5.85wt%.Gasoline stocks are 10: 1 with the mass ratio of methanol charging, air speed 1.5h-1, catalytic rectifying tower
Operating pressure 0.25MPa, reflux ratio 8,59.1 DEG C of tower top temperature, 105.5 DEG C of bottom temperature, the gasoline product octane number obtaining increases
Plus 3.5 units.
Embodiment 4
The raw material that the present embodiment adopts and operating condition are same as Example 2, different from the device that embodiment 2 adopts
It is that the diameter of inner pipe of shell structure catalysed fractionation section is 60mm, loads macropore sulfuric acid resin catalyst in inner tube, loads in chuckRustless steel θ ring filler, the upper end closed of inner tube is simultaneously only communicated with the feeding line (101) of catalytic rectifying tower, the lower end of inner tube
It is connected with stripping section, the upper/lower terminal of chuck is all penetrating.Gasoline product octane number increases by 3.7 units.
Embodiment 5
The raw material that the present embodiment adopts and operating condition are same as Example 3, different from the device that embodiment 3 adopts
It is, a diameter of 1200mm of catalytic rectifying tower, rectifying section has 3 sieve trays, intermediate fractionation section has 5 float valve trays, stripping section
There are 3 sieve trays, multistage catalytic distillation stage includes 5 order reaction separative elements, and Reaction Separation units at different levels are by with downspout
Sieve tray and the catalyst structure being fixed on below tower tray form, and catalyst structure is stainless (steel) wire bundle volume internal filling macropore
Azochlorosulfonate acid resin catalyst, each catalyst structure is 500mm with tower tray distance below, the height of shell structure catalysed fractionation section
Spend for 3000mm, the vertical parallel inner tube by 41 a diameter of 100mm and 1 chuck around inner tube form, load in inner tube
Macropore sulfuric acid resin catalyst, loads in chuckRustless steel Pall ring filler.Gasoline product octane number increases by 2.8 lists
Position.
Present invention disclosure and all methods proposing and technology of preparing, those skilled in the art can be interior herein by using for reference
Hold, the link such as suitable feed change and process route is realized, although the method for the present invention and technology of preparing have passed through preferable enforcement
Example is described, and person skilled substantially can be to as herein described in without departing from present invention, spirit and scope
Methods and techniques route is modified or reconfigures, and to realize final technology of preparing.Specifically, Suo Youxiang
Similar replacement and change are apparent to those skilled in the art, and they are considered as including in present invention essence
In god, scope and content.
Claims (8)
1. a kind of etherificate catalytic distillation device improving octane number, is characterized in that including a nesting-manifold type structure
Catalytic distillation tower body, tower body includes rectifying section, multi-level unit catalysed fractionation section, shell structure catalysed fractionation section from top to bottom successively
And stripping section；A vertical inner tube that described shell structure catalysed fractionation section is is 500～3000mm by length or multiple simultaneously
The vertical inner tube of row and a chuck composition around inner tube, catalyst and fractional distillation filler fill in pipe and in chuck respectively,
The upper end closed of loading catalyst bed and only communicating with the feeding line of catalytic rectifying tower, its lower end is communicated with stripping section, dress
Fill out fractional distillation filler side is all penetrating up and down；Described multi-level unit catalysed fractionation section is by one or more Reaction Separation
Unit rearranges along longitudinally staggered, and each Reaction Separation unit is by a catalyst structure and a tower tray carrying downspout
Combine, catalyst structure is one and has loaded the container of catalyst or tied up by multiple catalyst containers and constitute, catalysis
Agent component is fixedly connected on below tower tray, and covers all gas passage of this tower tray.
2. a kind of etherificate catalytic distillation device improving octane number, is characterized in that including a nesting-manifold type structure
Catalytic distillation tower body, tower body includes rectifying section, multi-level unit catalysed fractionation section, intermediate fractionation section, shell knot from top to bottom successively
Structure catalysed fractionation section and stripping section；Described shell structure catalysed fractionation section is by length be 500～3000mm one vertically
Inner tube or multiple vertical inner tube arranged side by side and a chuck composition around inner tube, loading catalyst in inner tube, load in chuck
The ratio in fractional distillation filler, inner tube and chuck section is 0.1～1.0, and the lower end of inner tube is only connected with the feeding line of catalytic rectifying tower
Logical, the lower end of chuck is connected with stripping section, and inner tube is all connected with intermediate fractionation section with the upper end of chuck, and the upper end of inner tube is opened
Liquid guide flow plate is set at mouthful, to stop the liquid flowing down above it from flowing into the beds in pipe；Described multi-level unit
Catalysed fractionation section is to be rearranged along longitudinally staggered by one or more Reaction Separation units, and each Reaction Separation unit is by one
The tower tray that catalyst structure and one carry downspout combines, catalyst structure be a container having loaded catalyst or
Person is tied up by multiple catalyst containers and constitutes, and catalyst structure is fixedly connected on below tower tray, and covers the whole of this tower tray
Gas passage.
3. a kind of device using claim 1 carries out the method being etherified catalytic distillation, it is characterized in that：Total hydrocarbon feed and low-carbon (LC)
Enter catalytic rectifying tower after alcohol mixture is preheated, and be directly incorporated into catalyst dress from the upper end of shell structure catalysed fractionation section
Fill out area, contact generation chemical reaction with acidic catalyst, then flow out from the lower end of shell structure catalysed fractionation section, therein heavy
Component enters stripping section separation and removes unreacted C5And C6Hydrocarbon and alcohol, then discharge from bottom of towe；And light component therein enters pipe
The fractionation zone of shell structure catalysed fractionation section, separates through packing layer in uphill process and removes product ether, then goes up to multistage
Unit catalysed fractionation section carries out the separation of depth etherification reaction and etherification product, and it is anti-that the steam of hydrocarbon and alcohol is introduced into bottom one-level
Answer separative element, depth etherification reaction is carried out by described catalyst structure, after generating ether, make the elevation of boiling point, become solidifying
Liquid falls into following fractionation zone, and unreacted hydrocarbon and alcohol steam pass through the liquid in catalyst structure tray above, with tower tray
Carry out mass transfer and heat exchange, the product ether that further separation removal is carried secretly, then proceed to rise to second level Reaction Separation unit, then
Secondary experience reaction and separation process, the ether of every order reaction conversion each falls within the tower tray of following first order reaction separative element, through fall
Liquid pipe flows down step by step, but does not contact with catalyst；After depth etherification reaction the mixture of remaining inertia lighter hydrocarbons and alcohol by
The top of multi-level unit catalysed fractionation section enters rectifying section, is stripped of the lighter hydrocarbons of ether and alcohol mixture enters overhead condenser, tower
Top effluent enters the segregation apparatuss of alcohol and hydrocarbon.
4. a kind of device using claim 2 carries out the method being etherified catalytic distillation, it is characterized in that：Total hydrocarbon feed and low-carbon (LC)
Enter catalytic rectifying tower after alcohol mixing preheating, and directly from the lower end of shell structure catalysed fractionation section be incorporated into beds with
Acidic catalyst contact occur chemical reaction, then from the upper end of shell structure catalysed fractionation section flow out, heavy constituent therein according to
The secondary fractionation zone entering shell structure catalysed fractionation section and stripping section, separate and remove unreacted C5And C6Hydrocarbon and alcohol, then from tower
Bottom is discharged；The light component flowing out from shell structure catalysed fractionation section upper end enters intermediate fractionation section and separates removal product ether, then
Rise to the separation that multi-level unit catalysed fractionation section carries out depth etherification reaction and etherification product, the steam of hydrocarbon and alcohol is introduced into many
The bottom first order reaction separative element of level unit catalysed fractionation section, carries out depth etherification reaction by catalyst structure, generates
Make the elevation of boiling point after ether, become lime set and fall into following fractionation zone, unreacted hydrocarbon and alcohol steam pass through catalyst structure
Liquid in tray above, with tower tray carries out mass transfer and heat exchange, the product ether that further separation removal is carried secretly, then proceedes to
Rise to second level Reaction Separation unit, again experience reaction and separation process, the ether of every order reaction conversion each falls within following one-level
In the tower tray of Reaction Separation unit, flow down step by step through downspout, but do not contact with catalyst；Remaining after depth etherification reaction
The mixture of inertia lighter hydrocarbons and alcohol rectifying section is entered by the top of multi-level unit catalysed fractionation section, be stripped of lighter hydrocarbons and the alcohol of ether
Mixture steam enters overhead condenser from rectifying section upper end, and tower top effluent enters the segregation apparatuss of alcohol and hydrocarbon.
5. device as claimed in claim 1 or 2, is characterized in that each catalyst structure in described multi-level unit catalysed fractionation section
Part is 50～600mm with tower tray distance below.
6. device as claimed in claim 1 or 2, it is characterized in that described catalyst container be cylindricality net basket, fiber woven bags,
Tie in volume structure by the sandwich sandwich forming, stainless (steel) wire with the cloth bag having loaded solid catalyst for stainless steel wave card
One or more.
7. device as claimed in claim 1 or 2, it is characterized in that described tower tray be float valve structure, blister configuration, tongue shape knot
One or more of structure, sieve-plate structure.
8. device as claimed in claim 1 or 2, is characterized in that described multi-level unit catalysed fractionation section is 5～15 grades.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510130724.2A CN104694150B (en) | 2015-03-24 | 2015-03-24 | A kind of etherificate catalytic rectification method improving octane number and device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510130724.2A CN104694150B (en) | 2015-03-24 | 2015-03-24 | A kind of etherificate catalytic rectification method improving octane number and device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104694150A CN104694150A (en) | 2015-06-10 |
| CN104694150B true CN104694150B (en) | 2017-03-08 |
Family
ID=53341716
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510130724.2A Expired - Fee Related CN104694150B (en) | 2015-03-24 | 2015-03-24 | A kind of etherificate catalytic rectification method improving octane number and device |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104694150B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102019207540B4 (en) * | 2019-05-23 | 2023-07-06 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Process for preparing polyoxymethylene dimethyl ether |
| CN114452901B (en) * | 2020-10-21 | 2023-03-07 | 中国石油化工股份有限公司 | Catalytic reaction unit and reactive distillation column |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4471154A (en) * | 1983-06-10 | 1984-09-11 | Chevron Research Company | Staged, fluidized-bed distillation-reactor and a process for using such reactor |
| US5130102A (en) * | 1990-06-11 | 1992-07-14 | Chemical Research & Licensing Company | Catalytic distillation reactor |
| CN1074680C (en) * | 1998-07-17 | 2001-11-14 | 中国石化齐鲁石油化工公司 | Shell and tube type catalytic distillation equipment |
| CN101245255B (en) * | 2007-02-14 | 2012-05-30 | 中国石油化工股份有限公司 | Etherification method for producing clean gasoline |
| CN204714756U (en) * | 2015-03-24 | 2015-10-21 | 天津大学 | A kind of etherificate catalytic distillation device improving gasoline octane rating |
-
2015
- 2015-03-24 CN CN201510130724.2A patent/CN104694150B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN104694150A (en) | 2015-06-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102690185B (en) | For being hydrolyzed methyl acetate to obtain the reactive distillation method and apparatus of acetic acid and alcohol | |
| CN106631684B (en) | A method of sec-butyl alcohol is prepared with sec-butyl acetate hydrolysis | |
| CN102276402B (en) | Combined reaction apparatus for producing low-carbon olefin | |
| CN102516036B (en) | Process method for preparing methyl tert-butyl ether by differential reaction rectification and equipment for same | |
| CN104694150B (en) | A kind of etherificate catalytic rectification method improving octane number and device | |
| CN107827692A (en) | A kind of method that ethylbenzene is produced with high concentration ethylene gas | |
| CN101293801A (en) | Method for preparing dimethyl ether, low carbon olefin hydrocarbon with combination of methanol dehydration catalytic pyrolysis | |
| CN204714756U (en) | A kind of etherificate catalytic distillation device improving gasoline octane rating | |
| CN111073691B (en) | Method for removing isobutene from carbon-tetrad hydrocarbon and method for producing 1-butene and 2-butene | |
| CN103333040A (en) | Low energy consumption propylene production technology | |
| CN101659588A (en) | Method and device of combined process for producing ethylene by ethanol dehydration and catalytic cracking | |
| CN106520187B (en) | A kind of light petrol hydrocarbon restructuring etherificate catalytic rectification process and its device | |
| CN108774100A (en) | A kind of tert-butyl alcohol and methanol prepare the integrated processes of methyl tertiary butyl ether(MTBE) and isobutene | |
| CN102276404A (en) | Reaction device for producing lower olefins from methanol | |
| CN104478642B (en) | Device and method for producing olefin from methanol | |
| CN107778123B (en) | Method for preparing isobutene | |
| CN104250204B (en) | A kind of complex etherified technique | |
| CN100582071C (en) | Process and apparatus for catalytic distillations | |
| CN102276389B (en) | Reaction and regeneration device for catalyzing and converting methanol and naphtha into lower olefins | |
| CN105218288B (en) | High-efficiency rapid gas-solid separation and settlement method for methanol-to-olefin | |
| CN206308287U (en) | The etherificate ether solution combined unit of production methyl tertiary butyl ether(MTBE) and high-purity isobutene | |
| CN110551002A (en) | Method for preparing tert-butyl alcohol by hydrating carbon tetraisobutylene component and preparation system thereof | |
| CN111423313B (en) | Process method and process device for preparing methyl tertiary butyl ether | |
| CN107022375B (en) | A kind of Etherification of Light FCC Gasoline system and Etherification of Light FCC Gasoline technique | |
| CN114478194A (en) | Sec-butyl alcohol refining method and device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CP02 | Change in the address of a patent holder |
Address after: 300350 District, Jinnan District, Tianjin Haihe Education Park, 135 beautiful road, Beiyang campus of Tianjin University Patentee after: Tianjin University Address before: 300072 Tianjin City, Nankai District Wei Jin Road No. 92, Tianjin University Patentee before: Tianjin University |
|
| CP02 | Change in the address of a patent holder | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170308 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |