CN106520187B - Light gasoline hydrocarbon recombination etherification catalytic rectification process and device thereof - Google Patents
Light gasoline hydrocarbon recombination etherification catalytic rectification process and device thereof Download PDFInfo
- Publication number
- CN106520187B CN106520187B CN201510582253.9A CN201510582253A CN106520187B CN 106520187 B CN106520187 B CN 106520187B CN 201510582253 A CN201510582253 A CN 201510582253A CN 106520187 B CN106520187 B CN 106520187B
- Authority
- CN
- China
- Prior art keywords
- hydrocarbon
- catalytic distillation
- catalytic
- light
- etherificate
- 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.)
- Active
Links
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 135
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 111
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 111
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 104
- 238000000034 method Methods 0.000 title claims abstract description 60
- 238000006266 etherification reaction Methods 0.000 title claims abstract description 22
- 238000005215 recombination Methods 0.000 title abstract 6
- 230000006798 recombination Effects 0.000 title abstract 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 99
- 238000004821 distillation Methods 0.000 claims abstract description 93
- 238000006243 chemical reaction Methods 0.000 claims abstract description 71
- 150000001336 alkenes Chemical class 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 50
- 239000000470 constituent Substances 0.000 claims description 30
- 239000002994 raw material Substances 0.000 claims description 28
- 150000001298 alcohols Chemical class 0.000 claims description 26
- 239000007791 liquid phase Substances 0.000 claims description 23
- 239000007788 liquid Substances 0.000 claims description 17
- 239000000126 substance Substances 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 16
- 238000005520 cutting process Methods 0.000 claims description 11
- 238000000926 separation method Methods 0.000 claims description 11
- 238000009835 boiling Methods 0.000 claims description 9
- 238000000605 extraction Methods 0.000 claims description 9
- 239000007792 gaseous phase Substances 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 9
- 238000009833 condensation Methods 0.000 claims description 7
- 230000005494 condensation Effects 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 claims description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 10
- 238000005265 energy consumption Methods 0.000 abstract description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 29
- 239000000047 product Substances 0.000 description 14
- 238000005516 engineering process Methods 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 238000005192 partition Methods 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 102000057593 human F8 Human genes 0.000 description 4
- 229940047431 recombinate Drugs 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- NUMQCACRALPSHD-UHFFFAOYSA-N tert-butyl ethyl ether Chemical compound CCOC(C)(C)C NUMQCACRALPSHD-UHFFFAOYSA-N 0.000 description 4
- 239000000945 filler Substances 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 238000007701 flash-distillation Methods 0.000 description 3
- 238000005194 fractionation Methods 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 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
- 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
- 239000011949 solid catalyst Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 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
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000010586 diagram Methods 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
- -1 ether compound Chemical class 0.000 description 1
- 238000004231 fluid catalytic cracking Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000013589 supplement Substances 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
- 238000005406 washing Methods 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 invention provides a light gasoline hydrocarbon recombination etherification catalytic rectification process and a device thereof. The light gasoline hydrocarbon recombination etherification catalytic distillation process provided by the invention adopts a method combining hydrocarbon recombination and catalytic distillation to lead C5Olefins and C6The olefin is introduced at different height positions of the reaction section of the catalytic distillation tower, so that the olefin is contacted with the catalyst in the same reaction section interval, and simultaneously the methanol is introduced into the catalytic distillation tower from two different heights of the reaction section. The invention also provides a light gasoline hydrocarbon recombination etherification catalytic rectification device for realizing the process. The light gasoline hydrocarbon recombination etherification catalytic distillation process provided by the invention has the advantages of low investment, simple operation, low energy consumption and high olefin etherification conversion rate.
Description
Technical field
The invention belongs to oil product manufacture field, and in particular to a kind of light petrol hydrocarbon restructuring etherificate catalytic rectification process and its dress
Put.
Background technology
Catalytically cracked gasoline is the main blend component of Chinese commodity gasoline.The catalytic cracking gasoline olefine content mistake in China
Height, stability are poor, it is therefore desirable to reduce olefin(e) centent to meet the limitation to gasoline product olefin(e) centent.Contain in light gasoline fraction
There is abundant Tertiary olefin, etherification reaction occurs under acidic catalyst effect using Tertiary olefin and low-carbon alcohols, you can reduce
Olefin(e) centent in gasoline, and can increase octane number.The etherification reaction of alkene and alcohol the limitation of chemical balance be present, it is necessary to
Product ether is constantly removed in course of reaction, the boiling point of product ether is higher than the boiling point of reactant, is adapted to promote using catalytic rectification method
Enter reaction balance to move to positive direction.In addition, etherification reaction thermal discharge is big, using catalytic rectification method by chemical heat release with
Still-process heat absorption is coupled, you can reduces energy consumption, and can avoids reaction zone from overheating.
Report about alkene and etherified catalytic distillation technology is as follows：
CN1348945 discloses a kind of ether product production method, and the etherificate of lighter hydrocarbons and alcohol containing tertiary olefin constituents is anti-
It should first reach to enter again in catalytic distillation tower after certain conversion ratio in (pre-) methyltertiarvbutyl ether reactor and be reacted and separated, product ether
Discharged from catalytic distillation bottom of towe, and unreacted lighter hydrocarbons and alcohol are discharged from tower top, into alcohol recovery tower.In alcohol recovery tower top outflow
Be the azeotropic mixture of alcohol and lighter hydrocarbons, and recycle, and tower reactor is unreacted lighter hydrocarbons fraction, a portion light ends fractionation is made
Returned for the backflow of catalytic distillation tower, another part is discharged as product or the raw material being processed further.CN1634832 is upper
On the basis of stating technique, one side line mixed material for containing alcohol, ether, hydrocarbon is produced from position below catalytic distillation tower charging aperture,
Pre-reactor entrance is recycled to, to improve tower reactor ETBE product purities, while recycles 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 inhaled
The integrated etherification method of systems stabilisation is received, catalyst for etherification is loaded in Fcc Stabilizer, catalyst is selected from highly acid sun
One or more in ion exchange resin, molecular sieve catalyst and heteropolyacid catalyst.Hydro carbons raw material of etherification mixes with fatty alcohol
Enter Fcc Stabilizer after conjunction, Fcc Stabilizer conversion zone and catalyst for etherification haptoreaction and divided
Evaporate, separating obtained liquefied gas is obtained by the tower top of stabilizer, and the stabilization containing ether compound is obtained in the bottom of towe of stabilizer
Gasoline.
US5188725 discloses a kind of fluid catalytic cracking process and etherification reaction combined method, is mainly urged including fluidisation
Change cracking, the fractionation of crackate and C4Three parts of etherificate of alkene and methanol, etherificate unit therein is by two fluidizations
Reactor and a catalytic distillation tower composition, the first fluidized bed use zeolite catalyst, and second fluidized bed is urged using sulfonate resin
Agent, catalytic distillation use method disclosed in US5000837.
In technology disclosed in US5679872, side line is drawn from the position below catalytic distillation tower charging aperture, is sent into point of alcohol
Unreacted alcohol is reclaimed from tower.By adjusting side line flow velocity, the ether of high-purity is obtained from the bottom of towe of catalytic distillation tower, the technical staff
Skill complex operation, equipment investment and high energy consumption.Technology is disclosed in US5607557, the side line thing that will be produced from catalytic distillation tower
Material introduces a membrane separator, separates ethanol and recycles, and remaining hydrocarbon is returned into catalytic distillation tower.
Flow disclosed in US5248836 is made up of a fixed bed pre-reactor and a catalytic distillation tower, by reacting
The material of device outflow is fed below catalytic distillation tower conversion zone, ethanol is supplemented above reaction zone, liquid is arranged at conversion zone bottom
Reception device, the liquid of collection from side take-off and is delivered into tubular reactor, tower reactor produces ETBE, and overhead extraction is unreacted
C4With the azeotropic mixture of ethanol, recovery alcohol is washed with water.US6107526 discloses a kind of methyltertiarvbutyl ether reactor and etherificate catalytic distillation combination
The technique for producing ETBE, raw material first pass through two-stage methyltertiarvbutyl ether reactor after pretreatment, enter back into catalytic distillation tower, tower reactor extraction
The mixture of ETBE, overhead extraction alcohol and hydrocarbon is, it is necessary to wash and be distilled to recover unreacted ethanol.
US5243102 discloses a kind of two-stage catalytic distillation flow, and C is substantially carried out in first order catalytic distillation tower5Alkene
The etherificate of hydrocarbon, the material of overhead extraction are divided into two strands, and therein one is passed through a methyltertiarvbutyl ether reactor, allow unreacted alkene with
Alcohol further reacts, and then loops to the stripping section of catalytic distillation tower, and tower bottoms and the methanol of supplement are concomitantly introduced into the second catalysis
Destilling tower, C is substantially carried out in after-fractionating tower6The etherificate of alkene, tower top outflow material is methanol and C6The mixture of hydrocarbon.
Method disclosed in US5015782 is with C4And C4More than isomeric olefine be raw material, two fixed bed reactions connected
Device and a catalytic distillation tower, mesoporous molecular sieve is loaded in reactor, sulfonate resin is loaded in tower.Raw material is by washing, one section
Etherificate, two sections of etherificates, finally obtain MTBE in catalytic distillation tower reactor.
Catalytic distillation tower is also disclosed in multiple patents to combine with boiling point reactors, or catalytic distillation tower and fixed bed
The flow of pre-reactor combination, i.e. alkene in raw material are introduced into a reactor with methanol, and it is anti-that liquid phase occurs in the reactor
Should, the effluent of reactor is fed in catalytic distillation tower, and unreacted alkene continues to react with alcohol, excessive methanol 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, US5003124 and US4950803.
Boiling point reactors disclosed in US20060030741 are by the addition of methanol with the characteristics of catalytic distillation tower combination technique
Amount is controlled in the scope less than stoichiometric proportion, makes alcohol reaction 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 monitoring the concentration of methanol in reaction zone, otherwise
Just occur that methanol content is exceeded in low-conversion or the low etherification product of tower, in addition, polymerisation easily occurs for excessive alkene.
US6930206, US20040210090 and WO2003104168 disclose a kind of for synthesizing tertiary amyl-methyl ether
(TAME) partition wall type catalytic distillation tower, be conversion zone tower section Partial Height or all longitudinal partition is highly set, every
The side filling solid catalyst of wall, the opposite side in next door only have centrifugation, and rectifying section is identical with conventional rectification tower, stripping
Section, which is divided into, to be had partition and not to have two kinds of next door form.C5Hydrocarbon feed and methanol first carry out primary anti-in a fixed bed reactors
Should, the product formed close to chemical balance is then introduced into one of above-mentioned partition wall type catalytic distillation tower without filling solid catalyst
Side is fractionated.It is anti-that this reactor with partition wall type catalytic distillation tower group technology is not suitable for the wider Etherification of Light FCC Gasoline of boiling range
Should, because the etherificate of light petrol needs C5And C6Active olefin all contacts with catalyst, and C6 +The presence of component makes C5Component from every
The fractionation side of wall is directly entered rectifying section, the beds without entering next door opposite side, therefore C5Total conversion of alkene
Rate is not high.
There are 2 weak points in prior art, one is anti-when the flow combined using reactor with catalytic distillation tower
The big calorimetric that should be released can not be utilized effectively, while be also easy to produce focus in beds；The second is due to C5
Hydrocarbon and C6The boiling point difference of hydrocarbon is larger to be result in it and is distributed in the different height of catalytic distillation tower, thus reaction temperature difference compared with
Greatly, it is not easy to control C5Alkene and C6Alkene is in catalyst optimum reaction condition simultaneously, therefore it is bad to be etherified effect.
The content of the invention
To overcome above mentioned problem, it is an object of the invention to provide a kind of light petrol hydrocarbon to recombinate etherificate catalytic rectification process.Should
Technique can better meet the suitable use temperature range of catalyst, and the technology investment is few, and simple to operate, energy consumption is low, alkene
Etherification conversion rate is high.
It is a further object of the present invention to provide a kind of light petrol hydrocarbon to recombinate etherificate catalytic distillation device, and the device can be used for upper
State light petrol hydrocarbon restructuring etherificate catalytic rectification process.
To reach above-mentioned purpose, the invention provides a kind of light petrol hydrocarbon to recombinate etherificate catalytic rectification process, the technique bag
Include following steps：
Hydrocarbon raw material is separated into light component and heavy constituent；
Light component and heavy constituent are introduced to the conversion zone of catalytic distillation tower respectively, and make the feed entrance point of light component less than weight
The feed entrance point of component；
Alcohols feedstock is divided into the conversion zone that two stocks do not introduce catalytic distillation tower, the position of wherein one alcohol charging is anti-
The bottom of section is answered, the position of another burst of alcohol charging is between the light component and the heavy constituent feed entrance point；
The light component, heavy constituent, alcohols feedstock are in conversion zone and catalyst for etherification haptoreaction, and gaseous substance is from catalysis
Overhead produces, and liquid phase substance produces from bottom of towe；
The light component is cut from hydrocarbon raw material initial boiling point to cutting temperature, the restructuring be divided into from cutting temperature to
The cut of the end point of distillation, the cutting temperature are 40-65 DEG C；
The hydrocarbon raw material includes the hydrocarbon mixture containing iso-amylene and dissident's alkene or catalytic gasoline and cuts≤75 DEG C light
Gasoline fraction；
The alcohols feedstock includes the combination of one or both of methanol and ethanol.
What light petrol hydrocarbon restructuring etherificate catalytic rectification process provided by the invention was combined using hydrocarbon restructuring with catalytic distillation
Method, C5Alkene (being primarily present in light component) and C6Reaction of the alkene (being primarily present in heavy constituent) in catalytic distillation tower
The different height position of section introduces, so as in identical altitude range and catalyst haptoreaction, while by alcohols feedstock from
Two different heights of conversion zone are introduced into catalytic distillation tower.Based on These characteristics, can reach technique provided by the invention with
Lower effect：First, pre- methyltertiarvbutyl ether reactor need not be set before catalytic distillation；Second, exothermic heat of reaction can be made full use of in distillation
Process, and C6Cut need not undergo vaporescence, greatly reduce energy consumption；Third, utilize C5Hydrocarbon and low-carbon alcohols form azeotropic
The high concentration alcohol reaction environment that thing is formed, makes C6Alkene is under the conditions of excessive alfin ratio of the determining alcohol far above stoichiometric proportion
Etherification reaction is carried out, improves equilibrium conversion；Fourth, reducing the thermograde of reaction zone, meeting catalyst activity temperature
Under conditions of avoid catalyst be heated sulfonic acid group be lost in.
In above-mentioned light petrol hydrocarbon recombinates etherificate catalytic rectification process, the composition of the gaseous substance is including unreacted light
The azeotropic mixture that hydrocarbon and alcohols feedstock are formed, the composition of the liquid phase substance include etherification product and remaining liquid.
In above-mentioned light petrol hydrocarbon recombinates etherificate catalytic rectification process, it is preferable that the feed entrance point of the light component is anti-
Middle part to the bottom of section is answered, the feed entrance point of the heavy constituent is middle part to the top of conversion zone；It is it is further preferred that described light
The feed entrance point of component is conversion zone bottom.The feed entrance point of the heavy constituent can determine conversion zone according to the situation of actual motion
Middle part to some position between top.
In above-mentioned light petrol hydrocarbon recombinates etherificate catalytic rectification process, it is preferable that the cutting temperature is 50-55 DEG C.
In above-mentioned light petrol hydrocarbon recombinates etherificate catalytic rectification process, it is preferable that the catalyst for etherification is urged for solid acid
Agent；More preferably macropore sulfuric acid resin catalyst.
In above-mentioned light petrol hydrocarbon recombinates etherificate catalytic rectification process, it is preferable that the process conditions of the catalytic distillation tower
For：Pressure is 0.1MPa-0.5MPa, and conversion zone temperature is 60 DEG C -90 DEG C, liquid quality air speed 0.1h-1-10h-1。
In above-mentioned light petrol hydrocarbon recombinates etherificate catalytic rectification process, it is preferable that the hydrocarbon raw material separation includes flash distillation
Separation or rectifying separation；More preferably flash separation.Flash separation can simplify equipment, and the gaseous component through flash separation is
The light component, liquid phase component are the heavy constituent.
In above-mentioned light petrol hydrocarbon recombinates etherificate catalytic rectification process, it is preferable that the technique is further comprising the steps of：It will urge
Separated after changing the gaseous substance condensation of overhead extraction, isolated alcohol is then filled into alcohols feedstock, and will
The liquid phase substance that isolated other components produce with bottom of towe mixes, and mix products draw battery limit (BL) as etherified gasoline.It is above-mentioned
Condensation operation can be that partial condensation can also be whole condensations.
In above-mentioned light petrol hydrocarbon recombinates etherificate catalytic rectification process, it is preferable that the gaseous substance by overhead extraction
The operation separated, using the method in US5792891.
In above-mentioned light petrol hydrocarbon recombinates etherificate catalytic rectification process, it is preferable that separated to the hydrocarbon raw material
Before operation, in addition to the step of pre-processed to remove basic nitrogen.
In above-mentioned light petrol hydrocarbon recombinates etherificate catalytic rectification process, in the liquid phase substance of catalytic distillation tower bottom of towe extraction
A part returns to catalytic distillation tower stripping section after reboiler gasifies.
Present invention also offers a kind of light petrol hydrocarbon to recombinate etherificate catalytic distillation device, suitable for above-mentioned technique, the device
Include the separator of catalytic distillation tower, alcohol and hydrocarbon；
The catalytic distillation tower includes stripping section, the conversion zone at middle part and the rectifying section at top of bottom, in the reaction
Section is provided with light component feeding line, heavy constituent feeding line, the first alcohols feedstock feeding line and the second alcohols feedstock feed pipe
Line, the position of the light component feeding line are less than the position of the feeding line of the heavy constituent, and first alcohols feedstock is entered
Expects pipe line is located at the bottom of conversion zone, and the second alcohols feedstock feeding line is located at the light component feeding line and described heavy
Between component feed lines；
The gaseous phase outlet pipeline of catalytic distillation top of tower connects with the entrance of the evaporator overhead condenser of catalytic distillation tower, described cold
The outlet of condenser slips out liquid pipe line with overhead reflux liquid pipeline, tower top respectively and connected, and the overhead reflux liquid pipeline is urged with described
Change and connected at the top of the rectifying section of destilling tower, the tower top slips out liquid pipe line and connected with the alcohol with the entrance of the separator of hydrocarbon；
The top of the catalytic distillation tower is provided with gaseous phase outlet pipeline, and bottom is provided with liquid-phase outlet pipeline；
The first alcohols feedstock feeding line, the second alcohols feedstock feeding line connect with alcohols feedstock main pipe line respectively
It is logical；
The separator of the alcohol and hydrocarbon is provided with alcohol outlet pipeline and hydrocarbon outlet line, the alcohol outlet pipeline and the alcohol
Class raw material main pipe line connects, and the hydrocarbon outlet line, the liquid-phase outlet pipeline of catalytic distillation tower connect with etherified gasoline pipeline respectively
It is logical.
In above-mentioned light petrol hydrocarbon recombinates etherificate catalytic distillation device, it is preferable that the device includes hydrocarbon raw material separator,
The light fraction outlet pipeline of the hydrocarbon raw material separator, heavy constituent the outlet line light component with the catalytic distillation tower respectively
Feeding hole pipeline connects with heavy constituent feeding hole pipeline.
In above-mentioned light petrol hydrocarbon recombinates etherificate catalytic distillation device, it is preferable that the hydrocarbon raw material separator is flash distillation
Tank or rectifying column；More preferably flash tank.
The catalytic distillation tower is in addition to the stripping section including main part, conversion zone and rectifying section, of course including tower
Condenser and tower bottom reboiler are pushed up, the liquid-phase outlet pipeline of catalytic distillation tower is provided with the branch road connected with the reboiler, described
The outlet line of reboiler connects with the stripping section of the catalytic distillation tower.
When hydrocarbon raw material separator is flash tank, the flash tank include hydrocarbon feed inlet line, gaseous phase outlet pipeline and
Liquid-phase outlet pipeline；The gaseous phase outlet pipeline connects with the light component feeding line, the liquid-phase outlet pipeline with it is described
Heavy constituent feeding line.Hydrocarbon feed after purification enters flash tank by hydrocarbon feed inlet line.
In above-mentioned light petrol hydrocarbon recombinates etherificate catalytic distillation device, condenser can be complete condenser or half condenser, preferably
For complete condenser.
In above-mentioned light petrol hydrocarbon recombinates etherificate catalytic distillation device, it is preferable that the device also includes preprocessor, described
Preprocessor is connected by the hydrocarbon feed inlet line with the hydrocarbon raw material separator.
Light petrol hydrocarbon restructuring etherificate catalytic rectification process small investment provided by the invention, simple to operate, energy consumption is low, alkene ether
Change high conversion rate.
Brief description of the drawings
Fig. 1 is the schematic device of the embodiment of the present invention 1.
Drawing reference numeral explanation：
10 preprocessors；101 light petrol feed lines；102 flash tank feeding lines；20 flash tanks；103 light components are fed
Pipeline；104 heavy constituent feeding lines；105 methanol main pipe lines；106 second methanol feed lines；107 first methanol feed lines；
30 catalytic distillation towers；31 rectifying sections；32 conversion zones；33 stripping sections；34 complete condensers；35 reboilers；201 gaseous phase outlet pipelines；202
Overhead distillate pipeline；203 liquid-phase outlet pipelines；The separator of 40 alcohol and hydrocarbon；204 methanol outlet pipelines；205 hydrocarbon outlets
Line.
Embodiment
In order to which technical characteristic, purpose and the beneficial effect of the present invention is more clearly understood, now to the skill of the present invention
Art scheme carry out it is described further below, but it is not intended that to the present invention can practical range restriction.
Embodiment 1
Present embodiments providing a kind of light petrol hydrocarbon restructuring etherificate catalytic distillation device, (Fig. 1 is the dress of the embodiment of the present invention 1
Put schematic diagram), the device is included with lower part：
Preprocessor 10, flash tank 20, catalytic distillation tower 30, the separator 40 of alcohol and hydrocarbon；Catalytic distillation tower 30 includes
Rectifying section 31, conversion zone 32, the stripping section 33 of complete condenser 34, reboiler 35 and main part；
Light petrol feed line 101 connects with the entrance of preprocessor 10, and the outlet of preprocessor 10 passes through located at flash distillation
Flash tank feeding line 102 in the middle part of tank connects with the entrance of flash tank 20；
The top of flash tank 20 is connected by light component feeding line 103 with the bottom of the conversion zone 32 of catalytic distillation tower,
The bottom of flash tank 20 is connected by heavy constituent feeding line 104 with the middle part of the conversion zone 32 of catalytic distillation tower；
The top of catalytic distillation tower 30 is connected by gaseous phase outlet pipeline 201 with the entrance of complete condenser 34, complete condenser 34
Outlet slips out liquid pipe line 202 with overhead reflux liquid pipeline, tower top respectively and connected, and overhead reflux liquid pipeline connects with rectifying section 31,
Tower top slips out liquid pipe line 202 and connected with alcohol with the entrance of the separator 40 of hydrocarbon；
Methanol main pipe line 105 connects with the first methanol feed line 107 and the second methanol feed line 106 respectively；Second
Methanol feed line 106 connects with the bottom of conversion zone 32, and the first methanol feed line 107 connects with the middle part of conversion zone 37,
And between light component feeding line 103 and heavy constituent feeding line 104；
Alcohol is connected with the separator 40 of hydrocarbon by methanol outlet pipeline 204 with methanol main pipe line 105, the separation of alcohol and hydrocarbon
Device 40 is connected by hydrocarbon outlet line 205 with the liquid-phase outlet pipeline 203 of the bottom of catalytic distillation tower 30, liquid-phase outlet pipeline
203 are provided with the branch road connected with the entrance of reboiler 35, and the outlet line of reboiler 35 connects with stripping section 33.
Embodiment 2
A kind of light petrol hydrocarbon restructuring etherificate catalytic rectification process is present embodiments provided, in technology utilization embodiment 1
Light petrol hydrocarbon restructuring etherificate catalytic distillation device.
30 a diameter of 50mm of catalytic rectifying tower, 31 a height of 800mm of rectifying section filling stainless steel ripple wire packing, conversion zone
32 a height of 1600mm fillings macropore sulfuric acid resin catalyst structures, 33 a height of 900mm of stripping section fillingsStainless steel θ ring fillers；
The light petrol hydrocarbon restructuring etherificate catalytic rectification process that the present embodiment provides comprises the following steps：
First preprocessed device 10 removes basic nitrogen to light petrol raw material, is then entered by flash tank feeding line 102 and flashed
Tank 20, flash tank pressure 0.32MPa, adiabatic operation, cutting temperature are 50 DEG C, and the gaseous component come out by flash tank passes through light group
Feeding line 103 is divided to introduce the bottom of catalytic distillation tower conversion zone 32；The liquid phase component come out by flash tank is entered by heavy constituent
Expects pipe line 104 introduces catalytic distillation tower 30 from the middle part of catalytic distillation tower conversion zone 32；
Methanol feedstock is divided into two strands after being introduced by methanol main pipe line 105, one by the second methanol feed line 106 draw from
The middle part of catalytic distillation tower conversion zone 32, another the first methanol feed line of stock-traders' know-how 107 introduce catalytic distillation tower conversion zone 32
Bottom；
The gaseous component of catalytic distillation column overhead enters the total condensation of complete condenser 34, condensation by gaseous phase outlet pipeline 201
A part in liquid passes back into rectifying section 31 by overhead reflux liquid pipeline, and another part is as distillate through overhead distillate pipe
Line 202 introduces the separator 40 of alcohol and hydrocarbon, and the methanol isolated imports methanol main pipe line 105 through methanol outlet pipeline 204, its
Its component is mixed by hydrocarbon outlet line 205 with the liquid phase substance that the bottom of towe in liquid-phase outlet pipeline 203 produces, and mix products are made
Battery limit (BL) is drawn for etherified gasoline, the liquid phase substance of part bottom of towe extraction returns to the stripping section of catalytic distillation tower by reboiler 35
33。
Gasoline stocks are the catalytic light gasoline of 29-60 DEG C of boiling range, and the mass ratio of catalytic light gasoline and methanol is 7：1, air speed
For 1.5h-1, catalytic rectifying tower operating pressure is 0.24MPa, and the reflux ratio of complete condenser is 3, and tower top temperature is 60.5 DEG C, tower reactor temperature
109.7 DEG C of degree, conversion zone temperature range are 71-84 DEG C, C5Conversion ratio 91%, C6Conversion ratio 68%, octane number increase by 2.9 lists
Position, loss-rate traditional handicraft save 21%.
Embodiment 3
Present embodiments provide a kind of light petrol hydrocarbon restructuring etherificate catalytic rectification process, the light petrol hydrocarbon weight that the technique uses
Group etherificate catalytic distillation device differs only in the device in embodiment 1：The bottom of flash tank 20 is fed by heavy constituent
Pipeline 104 connects with the top of the conversion zone 32 of catalytic distillation tower.
Light petrol hydrocarbon restructuring etherificate catalytic rectification process flow in the present embodiment with identical in embodiment 2, difference
The liquid phase component come out in flash tank 20 is in introduce from the top of the conversion zone 32 of catalytic distillation tower, and rectifying section, reaction
Relative altitude and the technological parameter change of section and stripping section, it is specially：
30 a diameter of 50mm of catalytic rectifying tower, 31 a height of 400mm of rectifying section are loadedStainless steel θ ring fillers, conversion zone 32
A height of 1800mm loads macropore sulfuric acid resin catalyst, 33 a height of 1100mm of stripping section fillingsStainless steel θ ring fillers；
The mass ratio of gasoline stocks and methanol is 9：1, air speed 1.0h-1, catalytic rectifying tower operating pressure is 0.30MPa,
Reflux ratio is 5, and tower top temperature is 66.3 DEG C, and bottom temperature is 114.5 DEG C, and conversion zone temperature range is 74-88 DEG C, C5Conversion ratio
96%, C6Conversion ratio 75%, octane number increase by 3.2 units, and observable index traditional handicraft saves 17%.
Claims (15)
1. a kind of light petrol hydrocarbon restructuring etherificate catalytic rectification process, the technique comprise the following steps：
Hydrocarbon raw material is separated into light component and heavy constituent；
Light component and heavy constituent are introduced to the conversion zone of catalytic distillation tower respectively, and the feed entrance point of light component is less than heavy constituent
Feed entrance point；
Alcohols feedstock is divided into the conversion zone that two stocks do not introduce catalytic distillation tower, the position of wherein one alcohol charging is conversion zone
Bottom, the position of another strand of alcohol charging is between the light component and the heavy constituent feed entrance point；
The light component, heavy constituent, alcohols feedstock are in conversion zone and catalyst for etherification haptoreaction, and gaseous substance is from catalytic distillation
Column overhead produces, and liquid phase substance produces from bottom of towe；
The light component is the cut from hydrocarbon raw material initial boiling point to cutting temperature, and the restructuring, which is divided into from cutting temperature to whole, to be evaporated
The cut of point, the cutting temperature are 40-65 DEG C；
The hydrocarbon raw material includes the hydrocarbon mixture containing iso-amylene and dissident's alkene or the light petrol of≤75 DEG C of catalytic gasoline cutting
Cut；
The alcohols feedstock includes the combination of one or both of methanol and ethanol.
2. light petrol hydrocarbon restructuring etherificate catalytic rectification process according to claim 1, wherein, the feed position of the light component
Middle part to the bottom of conversion zone is set to, the feed entrance point of the heavy constituent is middle part to the top of conversion zone.
3. light petrol hydrocarbon restructuring etherificate catalytic rectification process according to claim 2, wherein, the feed position of the light component
It is set to conversion zone bottom.
4. light petrol hydrocarbon restructuring etherificate catalytic rectification process according to claim 1, wherein, the cutting temperature is 50-
55℃。
5. light petrol hydrocarbon restructuring etherificate catalytic rectification process according to claim 2, wherein, the cutting temperature is 50-
55℃。
6. the light petrol hydrocarbon restructuring etherificate catalytic rectification process according to claim 1-5 any one, wherein, the catalysis
The process conditions of destilling tower are：Pressure is 0.1MPa-0.5MPa, and conversion zone temperature is 60 DEG C -90 DEG C, and liquid quality air speed is
0.1h-1-10h-1。
7. the light petrol hydrocarbon restructuring etherificate catalytic rectification process according to claim 1-5 any one, wherein, the hydro carbons
Raw material separation includes flash separation or rectifying separation.
8. the light petrol hydrocarbon restructuring etherificate catalytic rectification process according to claim 1-5 any one, wherein, the hydro carbons
Raw material is separated into flash separation.
9. the light petrol hydrocarbon restructuring etherificate catalytic rectification process according to claim 1-5 any one, wherein, the technique is also
Comprise the following steps：
It will be separated after the gaseous substance condensation of catalytic distillation tower overhead extraction, isolated alcohol then filled into alcohols original
Material, and isolated other components are mixed with the liquid phase substance that bottom of towe produces, mix products draw boundary as etherified gasoline
Area.
10. the light petrol hydrocarbon restructuring etherificate catalytic rectification process according to claim 1-5 any one, wherein, to institute
State before hydrocarbon raw material carries out lock out operation, in addition to the step of pre-processed to remove basic nitrogen.
11. a kind of light petrol hydrocarbon restructuring etherificate catalytic distillation device of technique for described in claim 1-10 any one,
Characterized in that, the device includes the separator of catalytic distillation tower, alcohol and hydrocarbon；
The catalytic distillation tower includes stripping section, the conversion zone at middle part and the rectifying section at top of bottom, is set in the conversion zone
There are light component feeding line, heavy constituent feeding line, the first alcohols feedstock feeding line and the second alcohols feedstock feeding line, institute
The position of light component feeding line is stated less than the position of the feeding line of the heavy constituent, the first alcohols feedstock feeding line
Located at the bottom of conversion zone, the second alcohols feedstock feeding line enters located at the light component feeding line and the heavy constituent
Between expects pipe line；
The gaseous phase outlet pipeline of catalytic distillation top of tower connects with the entrance of the evaporator overhead condenser of catalytic distillation tower, the condenser
Outlet connected respectively with overhead reflux liquid pipeline, overhead distillate pipeline, the overhead reflux liquid pipeline with it is described catalysis steam
Evaporate and connected at the top of the rectifying section of tower, the overhead distillate pipeline connects with the alcohol with the entrance of the separator of hydrocarbon；
The top of the catalytic distillation tower is provided with gaseous phase outlet pipeline, and bottom is provided with liquid-phase outlet pipeline；
The first alcohols feedstock feeding line, the second alcohols feedstock feeding line connect with alcohols feedstock main pipe line respectively；
The separator of the alcohol and hydrocarbon is provided with alcohol outlet pipeline and hydrocarbon outlet line, and the alcohol outlet pipeline is former with the alcohols
Expect main pipe line connection, the hydrocarbon outlet line, the liquid-phase outlet pipeline of catalytic distillation tower connect with etherified gasoline pipeline respectively.
12. device according to claim 11, it is characterised in that the device includes hydrocarbon raw material separator, the hydro carbons
The light fraction outlet pipeline of material separator, heavy constituent outlet line the light component charging aperture pipe with the catalytic distillation tower respectively
Line connects with heavy constituent feeding hole pipeline.
13. device according to claim 11, it is characterised in that the hydrocarbon raw material separator is flash tank or rectifying
Tower.
14. device according to claim 11, it is characterised in that the hydrocarbon raw material separator is flash tank.
15. device according to claim 14, it is characterised in that the device includes preprocessor, and the preprocessor leads to
Hydrocarbon feed inlet line is crossed to connect with the hydrocarbon raw material separator.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510582253.9A CN106520187B (en) | 2015-09-14 | 2015-09-14 | Light gasoline hydrocarbon recombination etherification catalytic rectification process and device thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510582253.9A CN106520187B (en) | 2015-09-14 | 2015-09-14 | Light gasoline hydrocarbon recombination etherification catalytic rectification process and device thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106520187A CN106520187A (en) | 2017-03-22 |
| CN106520187B true CN106520187B (en) | 2018-04-06 |
Family
ID=58348236
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510582253.9A Active CN106520187B (en) | 2015-09-14 | 2015-09-14 | Light gasoline hydrocarbon recombination etherification catalytic rectification process and device thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106520187B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107686745B (en) * | 2017-09-26 | 2020-06-12 | 丹东明珠特种树脂有限公司 | Light gasoline etherification system and light gasoline etherification process method thereof |
| CN116251373A (en) * | 2023-01-31 | 2023-06-13 | 安徽比特海新材料股份有限公司 | Energy-saving consumption-reducing rectifying tower with adjustable tower plate distance and process flow thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1136552A (en) * | 1995-01-16 | 1996-11-27 | 中国石油化工总公司 | Catalytic synthesizing process for ethers |
| JP3669340B2 (en) * | 2002-03-27 | 2005-07-06 | 株式会社日立製作所 | Oil refining method and refiner, and power plant |
| CN203333598U (en) * | 2013-06-27 | 2013-12-11 | 正和集团股份有限公司 | Processing device for modifying light hydrocarbons |
| CN103484154A (en) * | 2013-09-06 | 2014-01-01 | 中国石油化工股份有限公司 | Condensed water stripped crude oil stabilization method and special device thereof |
-
2015
- 2015-09-14 CN CN201510582253.9A patent/CN106520187B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1136552A (en) * | 1995-01-16 | 1996-11-27 | 中国石油化工总公司 | Catalytic synthesizing process for ethers |
| JP3669340B2 (en) * | 2002-03-27 | 2005-07-06 | 株式会社日立製作所 | Oil refining method and refiner, and power plant |
| CN203333598U (en) * | 2013-06-27 | 2013-12-11 | 正和集团股份有限公司 | Processing device for modifying light hydrocarbons |
| CN103484154A (en) * | 2013-09-06 | 2014-01-01 | 中国石油化工股份有限公司 | Condensed water stripped crude oil stabilization method and special device thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106520187A (en) | 2017-03-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100410223C (en) | Process for the preparation of tert.-butanol from isobutene containing hydrocarbon mixtures | |
| CN205235935U (en) | A equipment for following oxygen compound produces alkene | |
| CN109012504B (en) | Method for preparing raw material by preparing high-content butene-1 from carbon four by co-production method and system device thereof | |
| CN102659514A (en) | Method for producing sec-butyl alcohol | |
| CN105175211B (en) | Device and method for preparing high-purity isobutene through tert-butyl alcohol dehydration by means of catalytic distillation structured packing | |
| CN102884027A (en) | Production of jet and other heavy fuels from isobutanol | |
| CN101659588B (en) | Method and device of combined process for producing ethylene by ethanol dehydration and catalytic cracking | |
| CN102516036B (en) | Process method for preparing methyl tert-butyl ether by differential reaction rectification and equipment for same | |
| CN106520187B (en) | Light gasoline hydrocarbon recombination etherification catalytic rectification process and device thereof | |
| CN103382145A (en) | Preparation process for propylene from methanol or dimethyl ether | |
| CN111073691B (en) | Method for removing isobutene from carbon-tetrad hydrocarbon and method for producing 1-butene and 2-butene | |
| CN108002995A (en) | A kind of method and its equipment of acetone two-step method synthesizing methyl isobutyl ketone | |
| CN102351629B (en) | Method for producing propylene and high-octane gasoline from methanol | |
| CN108558590A (en) | Integrated approach for the method for the cracking production high-purity isobutylene by MTBE or ETBE and for producing related ether | |
| CN102276452B (en) | Production equipment for sec-butyl acetate | |
| CN104250204B (en) | A kind of complex etherified technique | |
| CN111018644B (en) | Method for improving comprehensive utilization value of mixed C4 | |
| CN105218288B (en) | High-efficiency rapid gas-solid separation and settlement method for methanol-to-olefin | |
| CN106927989A (en) | A kind of process for improving alkylated reaction efficiency and reducing product separating energy consumption | |
| CN104694150B (en) | A kind of etherificate catalytic rectification method improving octane number and device | |
| CN204714756U (en) | A kind of etherificate catalytic distillation device improving gasoline octane rating | |
| CN103420752B (en) | Separation refinement method for ethylene preparation through biomass ethanol dehydration | |
| CN102701918A (en) | Method for producing MTBE (Methyl Tert Butyl Ether) by taking gas phase isobutene as raw material | |
| Arpornwichanop et al. | Hybrid process of reactive distillation and pervaporation for the production of tert-amyl ethyl ether | |
| CN114478194A (en) | Sec-butyl alcohol refining method and device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |