CN105885912B - The methanol hydrocarbon method and device of ejection circulation fractional order reaction substep adjustment - Google Patents
The methanol hydrocarbon method and device of ejection circulation fractional order reaction substep adjustment Download PDFInfo
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- CN105885912B CN105885912B CN201610438258.9A CN201610438258A CN105885912B CN 105885912 B CN105885912 B CN 105885912B CN 201610438258 A CN201610438258 A CN 201610438258A CN 105885912 B CN105885912 B CN 105885912B
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- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 323
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 147
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 146
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 76
- 238000000034 method Methods 0.000 title claims abstract description 72
- -1 methanol hydrocarbon Chemical class 0.000 title claims description 26
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 127
- 239000003502 gasoline Substances 0.000 claims abstract description 80
- 230000008569 process Effects 0.000 claims abstract description 44
- 239000000047 product Substances 0.000 claims description 92
- 239000012530 fluid Substances 0.000 claims description 40
- 238000002347 injection Methods 0.000 claims description 36
- 239000007924 injection Substances 0.000 claims description 36
- 229910052799 carbon Inorganic materials 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 238000005899 aromatization reaction Methods 0.000 claims description 20
- 238000006266 etherification reaction Methods 0.000 claims description 17
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 15
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 239000007791 liquid phase Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 9
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 9
- 238000005804 alkylation reaction Methods 0.000 claims description 9
- 229960004217 benzyl alcohol Drugs 0.000 claims description 9
- 239000006227 byproduct Substances 0.000 claims description 8
- 230000029936 alkylation Effects 0.000 claims description 7
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 238000005336 cracking Methods 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 4
- 238000009833 condensation Methods 0.000 claims description 4
- 230000005494 condensation Effects 0.000 claims description 4
- 238000003860 storage Methods 0.000 claims description 3
- 239000008346 aqueous phase Substances 0.000 claims description 2
- 239000000470 constituent Substances 0.000 claims description 2
- 238000007323 disproportionation reaction Methods 0.000 claims description 2
- 230000005611 electricity Effects 0.000 claims 1
- 238000003475 lamination Methods 0.000 claims 1
- 239000002283 diesel fuel Substances 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 230000009467 reduction Effects 0.000 abstract description 7
- 230000004044 response Effects 0.000 abstract description 5
- 238000003541 multi-stage reaction Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 238000005183 dynamical system Methods 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- 239000003337 fertilizer Substances 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 94
- 238000002156 mixing Methods 0.000 description 17
- 239000003921 oil Substances 0.000 description 14
- 150000001336 alkenes Chemical class 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 11
- 238000001816 cooling Methods 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 10
- 238000000926 separation method Methods 0.000 description 9
- 239000012071 phase Substances 0.000 description 8
- SQNZJJAZBFDUTD-UHFFFAOYSA-N durene Chemical compound CC1=CC(C)=C(C)C=C1C SQNZJJAZBFDUTD-UHFFFAOYSA-N 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 238000002207 thermal evaporation Methods 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- 238000010248 power generation Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000006317 isomerization reaction Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 230000005619 thermoelectricity Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000000567 combustion gas Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 239000000112 cooling gas Substances 0.000 description 2
- 150000001924 cycloalkanes Chemical class 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000002737 fuel gas Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 230000035939 shock Effects 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
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
Abstract
The present invention relates to a kind of method and apparatus of preparing hydrocarbon products by methanol conversion, stepwise reaction is carried out in third-stage reactor by pre-reaction system, main reaction system, rear reaction system respectively and substep adjusts response parameter to reduce dry gas, liquefied gas and the yield of heavy petrol, and uses the method for liquefied gas, heavy gasoline components, residue gas recycle reaction to produce the hydrocarbon products such as high-quality gasoline diesel oil.The purpose that reduction power consumption and reduction dynamical system are invested is realized by ejection circulation.The process unit compact conformation, achievable modularization are installed, and the low, target product yield of investment is high, energy-conserving and environment-protective.It is adapted to Methanol Plant, the Chun An coproduction chemical fertilizer factory of various scales, the coke-oven plant of combined production of methanol processes the hydrocarbon products such as high-quality solvent naphtha, gasoline, diesel oil.
Description
Technical field
The invention belongs to a kind of process of preparing hydrocarbon products by methanol conversion.Specifically refer to using methanol or crude carbinol as
Raw material produces the process of the liquid phase hydrocarbon products such as gasoline or gasoline component, solvent naphtha, diesel component, belongs to coal chemical industry or day
Right gas chemical field.
Background technology
By appropriate catalytic process, methanol can be converted into water and a variety of hydrocarbon products, such as alkene, alkane, aromatic hydrocarbons with
And the mixture of above-mentioned hydrocarbon products.According to the difference of purpose product, existing methanol process for producing hydrocarbons includes preparing gasoline by methanol, methanol
The techniques such as alkene and methanol aromatic hydrocarbons processed.
Oil quality is to influence the key factor of motor vehicle exhaust emission.In recent years, haze weather takes place frequently, and vehicle exhaust is recognized
To be the key factor to form haze weather, market is in the urgent need to providing high-quality fuel oil.Obtained with conventional oil petrochemical process
Similar hydrocarbon products compare, by methanol hydrocarbon technology obtain the hydrocarbon products such as gasoline and diesel oil in benzene, alkene, sulphur, nitrogen,
Ash grade objectionable impurities content it is low, can effectively protect vehicle performance, contribution of the reduction Vehicular exhaust to haze meets market pair
The requirement of high standard gasoline, diesel, it is significant for environmental protection.
It is typical methanol hydrocarbon technology that methanol, which converts gasoline (MTG) technology processed, is invented by Mobil companies.From 1974
Rise, the said firm has applied for that multinomial relevant methanol converts the patent of gasoline processed.
Methanol hydrocarbon process is an exothermic process, how controlling reaction temperature be the process concern emphasis.Around temperature
Control problem is spent, has developed kinds of processes and its reaction system, the form of existing reaction system is solid including fixed bed, multitube
Fixed bed, multistage cold shock fixed bed, moving bed, fluid bed etc..
Methanol converts the technology of hydrocarbon products processed mostly using two sections of conversion process.United States Patent (USP) 3931349 is Mobil public
The methanol for taking charge of alerting bulletin converts the patent of hydro carbons processed, and using two sections of conversion process of fixed bed, wherein first paragraph reaction is methanol
Dewatering preparing dimethy ether, one section outlet material includes the mixture of methanol, dimethyl ether and water, into second stage reactor, in molecular sieve
Gasoline fraction section product is generated in the presence of catalyst.
United States Patent (USP) 4579999 then discloses the skill that another two-stage method methanol converts gasoline fraction section hydrocarbon products processed
Molecular sieve catalyst is loaded in art, one section reactor, methanol is first converted into low-carbon alkene and part hydrocarbon, by C5+Cooling
After separation, low-carbon alkene enters second stage reactor, in the presence of olefin polymerization catalysis, is further converted into gasoline fraction
Section product.
United States Patent (USP) 4689205 discloses the technology that hydrocarbon is produced in a kind of methanol multi-stage conversion.The technology of the patent disclosure with
United States Patent (USP) 4579999 is substantially similar, in first stage reactor, and methanol is converted into C2-C4 under certain temperature and pressure condition
Alkene and part C5+Hydrocarbon, by C5+After hydrocarbon separation, remainder enters second segment reactor, using olefin polymerization catalysis, by the
The low-carbon alkene that one section of reaction is produced further is polymerized to the hydrocarbon product of gasoline fraction.Except that, the skill of the patent disclosure
In art, first paragraph uses fluidized-bed reactor.
Chinese invention patent 200610048298.9 proposes the technique that a kind of methanol by one-step method produces hydrocarbon products, feature
It is to complete three phases in a reactor, has the advantages that technological process is short, compared with two-step method, with technological process
Short advantage, but recycle ratio is big, and course of reaction is difficult to control, and product is gasoline, liquefied gas and heavy petrol etc..
In existing cold shock bed methanol process for producing hydrocarbons, at it per in first order reaction bed, methanol hydrocarbon reaction mistake is completed
The three phases of journey.
The utility model patent of Application No. 200720101511.8 proposes a kind of preparing gasoline by methanol reaction of cold shocking type
Device, the controlling reaction temperature by the way of the cooling gas such as nitrogen is added between level, product is gasoline, liquefied gas and fuel gas, not
Refer to the power resources for circulating cooling gas.
Existing insulation fix bed technique, need to be cooled down by the way of a large amount of recycle hydrocarbons, it is necessary to be equipped with gas compression unit,
Investment is big, and power consumption is big.Meanwhile, because using the type of cooling of recycle hydrocarbons, a large amount of recycle hydrocarbons, which need to heat repeatedly, mixes cold
But, rectifying is separated, and heat exchange amount is big, and piece-rate system and heat-exchange system cost are high.
Fluidized-bed process be characterized in by the three phases of the course of reaction of preparing gasoline by methanol in fluidized-bed reactor it is complete
Into.Cooling can effectively be solved the problems, such as using fluid bed process, but fluidized-bed structure is complicated, it is not easy to operate, cost is high, it is desirable to
Production scale is big, and investment risk is big.
Existing multi-tubular reactor is warm using fused salt as heat transfer medium absorbing reaction and produces steam, but fused salt heat exchange system
Complicated, system start and stop are difficult.
The equal co-production of liquefied gas of technique of existing all kinds of preparing gasoline by methanol and the heavy petrol containing durol, liquefied gas and
The following process of heavy petrol is required to increase equipment investment.
In related field, for example, methanol-to-olefins, the technical process of methanol aromatic hydrocarbons generally wants coproduction part of gasoline to produce
The purification apparatus investment of product, olefin product and aromatic hydrocarbon product is higher.
In summary, existing preparing gasoline by methanol technique there are equipment investment greatly, and the target product yield such as gasoline is low, move
Power consumption is big, the problem of high energy consumption.Although hydrocarbon products such as market in urgent need high-quality gasolines, material benzenemethanol production capacity surplus, because
For existing process and device exist investment greatly with the reason such as energy consumption height, in the low oil price epoch, investment risk is big.
The course of reaction of preparing gasoline by methanol is roughly divided into three phases：Etherification stage；Generate the low-carbon alkene stage；Low-carbon alkene
The stage of the process such as polymerized hydrocarbon and aromatisation.
Fixed bed two-step process be characterized in the first step by the major part of etherification stage in a methyltertiarvbutyl ether reactor
Complete.Second step, is completed the generation low-carbon alkene stage in conversion reactor, the process such as low-carbon alkene polymerization and aromatisation
Etherification procedure of the methanol on aluminum oxide catalyst for etherification is stablized relatively, discharges partial reaction heat, appropriate cooling
After enter back into alkylation reaction device, can suitably reduce the heat exchange load of follow-up alkylation reaction process.
During methanol hydrocarbon, it is necessary to have the generation phase of etherification stage, low-carbon alkene；And it is follow-up for low-carbon alkene
The control of reaction can obtain different target products, for example：Terminating reaction process is preparing low carbon olefin hydrocarbon by methanol；Folded
The more olefin product of carbon number can be obtained by closing reaction；Aromatisation can obtain aromatic product.Aromatization process is producing aromatic hydrocarbons
While also by-product dry gas, excessive aromatisation rises dry gas and liquefied gas yield.
Existing preparing gasoline by methanol technique, it is basic to use ZSM-5 catalyst series.On ZSM-5 catalyst, methanol can be with
Etherification reaction is carried out, generation low-carbon alkene, the course of reaction, reactor such as overlapping, isomerization, aromatisation, alkylation, hydrogenation is carried out
Outlets products are the mixture of hydrogen, alkene, alkane, cycloalkane, aromatic hydrocarbons and water, and fuel gas, liquefied gas, vapour are can obtain after separation
The products such as oil, heavy petrol.This process is the basis of methanol hydrocarbon particularly preparing gasoline by methanol technique.Existing one-step method, two
The technical process such as footwork grow up on this basis.
The content of the invention
Engineering practice and further investigation revealed that, it is many to there is byproduct species in these existing methods, and power consumption is big,
The problem of byproduct for treatment and big power-equipment investment.
High it is an object of the invention to provide a kind of yield of gasoline, power consumption is low, the low preparing gasoline by methanol of equipment investment
Method.
The present invention is three-step reaction process by the process subdivision to above-mentioned methanol liquefaction, is entered respectively in third-stage reactor
Row stepwise reaction simultaneously adjusts response parameter to reduce dry gas, liquefied gas and the yield of heavy petrol, and use by liquefied gas, again step by step
Gasoline component, the method for residue gas recycle reaction realize the purpose for improving yield of gasoline.
The present invention realizes the supercharging of recycle hydrocarbons using injector system.Injector is to utilize jet turbulent diffusion, is entered
Row mass transfer passes the fluid machinery and mix reaction equipment of energy.High pressure draught sprays from nozzle at high speeds, the low pressure around driving nozzle
Gas, two strands of air-flows are mixed in mixing chamber and diffuser, are pressurized, and under conditions of certain high-pressure working gas are consumed, are carried
The high low-pressure gas pressure for entering injector from suction inlet, this equipment is referred to as jet pump.Working fluid is with very high speed
Come out, taken away into the receiving chamber of injector, and the relatively low medium of the pressure before injector from nozzle.The fluid being pulled away
For driving fluid, the pressure of driving fluid is improved without directly consuming mechanical energy, this is the topmost performance of injector.Due to tool
There is this property, under many circumstances, using injector than supercharging equipment (compressor, pump, air blower and the air inducing using machinery
Machine etc.) it is more simple, more reliable.In addition to this body structure is extremely simple, the method that injector is connected with various equipment
It is very simple, manufacture also uncomplicated, be widely applied in engineering.
The reaction system of the present invention includes etherification reaction system, abbreviation pre-reaction system；Low-carbon alkene reaction system, referred to as
Main reaction system；Aromatisation is with overlapping and being alkylated reaction system after combined reaction system abbreviation.
The pre-reaction system of the present invention includes：Pre- injector, pre-reactor.Methanol steam from heat-exchange system is as pre-
The working fluid of injector, the portion of product of injection pre-reactor outlet, is recycled back to pre-reactor.
Product temperatur after etherification reaction is up to more than 400 DEG C, and a part is returned methyltertiarvbutyl ether reactor by pre- injector injection and entered
Mouthful, being mixed with methanol steam makes methanol steam be superheated to reaction temperature to enter methyltertiarvbutyl ether reactor, it is possible to decrease methanol steam superheater
Load.The yield of the accessory substance such as methane in etherification reaction temperature and etherification procedure is reduced simultaneously.The first conduct of another part product
The working fluid of main injector, it is laggard to become owner of reaction system.The reaction temperature of pre-reaction system is 160-420 DEG C, preferably anti-
It is 260-320 DEG C to answer temperature.The reaction velocity of pre-reaction system is 1-70h-1, reaction velocity preferably is 1.25-3h-1.It is pre- anti-
The reaction pressure for answering system is 0.2-3.0MPa, and reaction pressure preferably is 1.5-2.6MPa.Recycle ratio is 0.1-3, preferably
0.5-1.5.This recycle ratio refers to mass ratio of the product with the reactor reaction thing for returning to reactor inlet, and recycle ratio is got over
Greatly, the product of backflow is more.
The main reaction system (low-carbon alkene reaction system) of the present invention is by main injector, main reactor, methanol injector group
Into.The working fluid of methanol injector is to come from material benzenemethanol pump, the portion of product of methanol injector injection main reactor outlet,
Into main injector, Posterior circle returns main reactor.Dimethyl ether and methanol generation low-carbon alkene and water mainly occur for main reaction system
Reaction, the polymerization of part low-carbon alkene and the reaction such as aromatisation.
Main reaction system use compared with low reaction temperatures, higher space velocity to limit aromatisation process, with control reduction dry gas and
Low-carbon alkanes yield.The reaction temperature of main reaction system is 160-420 DEG C, and reaction temperature preferably is 260-350 DEG C.Main reaction
The reaction velocity of system is 1-70h-1, reaction velocity preferably is 2-10h-1.The reaction pressure of main reaction system is 0.2-
3.0MPa, reaction pressure preferably is 1.2-2.4MPa.The recycle ratio of main reaction system is 2-20, preferably 3-6.
The rear reaction system of the present invention includes：Injector, post-reactor, lighter hydrocarbons injector, heat-exchange system, profit qi leel afterwards
From system, water treatment system, booster, de- lighter hydrocarbons tower, de- heavy hydrocarbon tower, product gasoline tank, heavy hydrocarbon surge tank, dry gas system.
Aromatisation is further completed using post-reactor, aromatic disproportion, alkylation, the process such as overlapping.
The outlets products of post-reactor cool by heat-exchange system, into profit gas separating system, by containing more than C3
Component liquefaction separation, it is entered de- lighter hydrocarbons tower after being pressurized with booster, overhead components C3-C4 is by the circulation of lighter hydrocarbons injector
Reaction system is returned, heavy constituent enters de- heavy hydrocarbon tower, and tower top is gasoline component, into product gasoline tank, the weight containing durol
C10 and above heavy aromatics component in gasoline component are recycled back to rear reaction system by lighter hydrocarbons injector, with newly-generated low-carbon
The reaction generation C9 and following light aromatic hydrocarbons such as disproportionation, cracking occurs after the mixing such as alkene, light aromatic hydrocarbons, as boiling point, condensation point it is qualified and
Low octane rating C9 above alkane component in the high gasoline component of octane number, heavy gasoline components occurs cracking reaction and generated compared with Gaoxin
Below the C9 hydrocarbon of alkane value turns into specification gasoline component, constantly circulation so as to realize the purpose of not by-product heavy gasoline components.
The present invention is separated the liquefied gas component liquefaction containing C3-C4 by piece-rate system, is made with booster pump after its supercharging
It is recycled back to rear reaction system.In reaction system, the liquefied gas component and dry gas component being recycled back to and newly-generated low-carbon alkene
The corresponding gasoline component of the reaction generation such as alkylation, aromatisation, overlapping occurs for mixing.The present invention reacts by using substep control
The method of process makes the aromatization degree that aromatization degree is less than routine MTG, therefore olefin(e) centent is higher in lower carbon number hydrocarbons, lower alkanes
Hydrocarbon content is relatively low, is recycled back to that post-reactor is easy to be overlapped, isomerization, aromatization turn into C5+Gasoline component.Utilize
Lower carbon number hydrocarbons overlapping, cyclisation, the liquefied gas low temperature aromatization technology of ZSM-5 catalyst are mature technologies.Using stepwise reaction substep
The method of control, can make recycle hydrocarbons total by controlling recycle ratio, air speed, reaction temperature, pressure and other parameters to control reaction process
Amount, which is maintained, can not only meet cooling needs but also the level of non-excess.The recycle ratio of reaction system is 1-20, preferably 3-5 afterwards.Afterwards
The reaction temperature of reaction system is 160-420 DEG C, and reaction temperature preferably is 300-400 DEG C.The reaction velocity of reaction system afterwards
For 0.5-10h-1, reaction velocity preferably is 1-2h-1.The reaction pressure of reaction system is 0.2-3.0MPa, reaction preferably afterwards
Pressure is 1.2-2.2MPa.A small amount of liquefied gas and dry gas are used for thermoelectricity fuel, to realize not by-product liquefied gas, reduce equipment investment
Purpose.
After the dry gas containing hydrogen, methane, ethene, ethane separated by piece-rate system is pressurized by lighter hydrocarbons injector
Reaction system continues to react generation gasoline component after return.The unreacted dry gas of extension utilizes system as combustion gas feeding combustion gas
Unite for generating and heat supply, the thermoelectricity demand of the present apparatus can be met, realize not by-product combustion gas, improve yield of gasoline, reduce public
The purpose of construction investment.The present apparatus is because can realize that thermoelectricity is confessed, it may have energy-saving, public work is invested low excellent
Gesture.Unnecessary thermoelectricity can be sent outside, improved dry gas value, improved device benefit.
The present invention is used as recycle hydrocarbons by the use of heavy gasoline components, liquefied gas component, dry gas.Heavy petrol, liquefied gas are in liquid phase shape
State is pressurized by liquid hydrocarbon booster pump, and its power consumption is far below carburet hydrogen compressor.Heavy petrol and liquefied gas after supercharging is by inhaling
Dry gas boosting is set to realize circulation as the working fluid injection dry gas of lighter hydrocarbons injector after thermal evaporation heating.Recycle hydrocarbons boost cycle
Without gas compressor, the purpose of reduction power consumption and reduction dynamical system investment is realized.
The present invention's is described in detail as follows：
The present invention provides a kind of reaction unit of methanol hydrocarbon, by 1 methanol feedstock pump, 2 methanol injectors, 3 main injectors,
4 pre-reactors, 5 pre- injectors, 6 main reactors, 7 lighter hydrocarbons injectors, injector, 9 post-reactors, 10 heat-exchange systems, 11 water after 8
Processing system, 12 profit gas separating systems, 13 boosters, 14 de- lighter hydrocarbons towers, 15 de- heavy hydrocarbon towers, 16 heavy hydrocarbon tanks, 17 product gasolines
Tank, 18 dry gas systems composition；
The port of export of methanol feedstock pump 1 is connected by methanol injector 2 with main injector 3 all the way, and another road is through heat-exchange system
The 10 pre- injectors 5 of connection；The arrival end of pre-reactor 4 connects pre- injector 5, and the port of export returns to pre- injector 5, Ling Yilu all the way
Connect the entrance of main injector 3；The outlet of main reactor 6 is divided into two-way, methanol injector 2 is returned to all the way, another road passes through rear
Injector 8 is connected with post-reactor 9；The outlet of post-reactor 9 is connected by heat-exchange system 10 with profit gas separating system 12；Oil
Three tunnels of the outlet point of water vapor separation system 12, aqueous phase connection water treatment system 11, injector after dry gas is returned by the injection of lighter hydrocarbons injector 7
8, another part dry gas is by the power generation and heat supply of dry gas system 18 or sends outside, and the boosted pump 13 of liquid phase oil enters de- lighter hydrocarbons tower after pressurizeing
14, injector 8 after the overhead gas of lighter hydrocarbons tower 14 are returned as the working fluid of lighter hydrocarbons injector 7 is taken off, the tower bottom liquid of lighter hydrocarbons tower 14 is taken off
Into de- heavy hydrocarbon tower 15, the overhead product connection product gasoline storage tank 17 of heavy hydrocarbon tower 15 is taken off, tower bottom product enters heavy hydrocarbon surge tank 16,
Lighter hydrocarbons injector is returned afterwards.
The methanol process for producing hydrocarbons of the present invention comprises the following steps：
1. the pre-reaction stage
Material benzenemethanol is divided into two-way after being boosted by methanol feedstock pump, all the way as the working fluid of methanol injector 2, separately
All the way working fluid injection pre-reaction is used as through heat-exchange system 10 into pre- injector 5 by after the pre- thermal evaporation overheat of high-temperature product
After the portion of product that device 4 is exported, mixing heating enters pre-reactor 4 and carries out etherification reaction.
2. the main reaction stage
The product section that pre-reactor 4 is exported returns its entrance to improve its inlet temperature by injection, it is possible to decrease superheater
Load, another part product enters the mixed gas that the main injection of injector 3 comes from methanol injector 2 as working fluid, enters
Enter main reactor 6 after the mixing of one step, the product come out by main reactor 6 is divided into two-way, mixed all the way by the injection of methanol injector 2
Close cooling, enter back into the mixing boosting heating of main injector 3 and return to entrance to control temperature, another road as rear injector 8 work
Come from as fluid injection and enter post-reactor 9 after the gas of lighter hydrocarbons injector 7.
3. post-reaction period
The outlets products of post-reactor 9 are exchanged heat into heat-exchange system 10 with the material from methanol feedstock pump, cold
But oil-water-gas piece-rate system 12 is entered after cooling, the water isolated enters water treatment system 11.A part of quilt of dry gas isolated
The injection of lighter hydrocarbons injector 7 returns post-reactor, and another part enters the power generation and heat supply of dry gas system 18 as dry gas product or sent outside.Liquid
Phase oil ingredient, which is boosted after pump 13 pressurizes, enters de- lighter hydrocarbons tower 14, takes off the overhead gas of lighter hydrocarbons tower 14 as the work of lighter hydrocarbons injector 7
Make fluid and return to post-reactor.The de- bottom of towe liquid phase of lighter hydrocarbons tower 14 enters de- heavy hydrocarbon tower 15, and the tower bottom product for taking off heavy hydrocarbon tower enters weight
Hydrocarbon surge tank 16, rear to return to lighter hydrocarbons injector, tower top is that gasoline component enters product gasoline tank 17.
Beneficial effects of the present invention：During methanol hydrocarbon, the Liquid Phase Methanol of normal temperature and pressure is increased by material benzenemethanol pump first
Pressure, then overheats the methanol steam to form HTHP by pre- thermal evaporation, because etherification reaction is exothermic reaction, using drawing in advance
Emitter injection partial ethers product, further heats up methanol steam, it is possible to decrease the load of methanol steam superheater.Reduce simultaneously
The yield of the dry gas such as byproduct methane in etherification reaction temperature and etherification procedure.
Reaction refrigerated separation process is completed to be required to consume power.The present invention is pressurizeed using methanol pump to Liquid Phase Methanol, because
Small for liquid compression, methanol pump power consumption is less than the compressor compressed to gas phase.High pressure Liquid Phase Methanol absorbs anti-by heat exchange
Answer thermosetting high temperature and high pressure gas that there is acting ability, the present invention is used as reaction refrigerated separation process fortune by the use of this acting ability
Capable power, can reduce the electric power required for process.
The present invention is used as recycle hydrocarbons circulation power switching mechanism, injector without motion part, with structure letter by the use of injector
It is single reliable, low cost, consume energy low, reliable advantage.Injector has simultaneously makes cold fluid and hot fluid directly mix quick heat exchange
Function, the cost of heat-exchange system can be greatly lowered.
The main reaction system of the present invention has the characteristic that control aromatization degree, limitation dry gas and liquefied gas yield, plus
Strong isomerization reaction, makes dry gas, below C4 alkane low yields, the heavy gasoline components low yield such as heavy aromatics, and circular response, a side
Face can improve liquid receipts, on the other hand can control temperature using recycle hydrocarbons.
Heavy aromatics circular response, can also suppress heavy aromatics yield.Higher boiling non-aromatic component in gasoline is reduced, is conducive to carrying
The octane number of high gasoline.
The piece-rate system of the present invention has the characteristic that：Dry gas, liquefied gas, heavy petrol and gasoline component separation Posterior circle are returned
Reaction system circular response, on the premise of gasoline component is kept in high yield, obtains low C4 contents, low more than C10 components and contains afterwards
The low-steam pressure of amount, it is low do, high-octane high-quality gasoline or gasoline component.
The power circulation system of the present invention has the characteristic that, using ejection circulation, can cancel conventional recyclegas
Compressor, reduction equipment investment and power consumption.
The heat-exchange system of the present invention has the characteristic that：Because using the direct mixed heat transfer mode of cold fluid and hot fluid injection and profit
The characteristics of being cooled with working fluid because of expansion, it is possible to decrease heat-exchange system cost.
By adjusting piece-rate system operational factor, dry gas liquefied gas is returned and set with the heavy gasoline components containing durol
The post-reactor put continues reaction and is converted into gasoline component, liquefied gas product and durol product is not produced, so need not match somebody with somebody
Standby and operation liquefied gas purification apparatus and durol purification apparatus, can reduce equipment manufacturing cost and operating cost.
The refined needs of liquefied gas are equipped with higher rectifying column, and yield is not high, without scale effect, and carrying cost is high, and one
As in the case of, it is difficult to petroleum base liquefied gas compete.Liquefied gas price is less than high-quality gasoline price, and liquefied gas is converted into vapour
Oil ingredient can improve device benefit.It is to return below C4 liquefied gas component and residue gas recycle instead in the technique of the present invention
Device is answered to be converted into gasoline component by the course of reaction such as alkylation, overlapping, aromatisation.While this technology controlling and process post-reactor temperature
Degree, aromatization degree is relatively low, and saturation low-carbon alkanes content is low, and vapour is converted into by overlapping and alkylated reaction in post-reactor
Oil ingredient.Durol subtractive process needs equipment investment big, and market capacity is smaller, and selling cost is high.This technique is by more than C10
Post-reactor is returned after component separation.In post-reactor, durol is disproportionated into C7-C9 aromatic hydrocarbons, and C7-C9 aromatic hydrocarbons is higher octane
It is worth gasoline component.More than C10 alkane alkene is low octane rating component, reduces its content in the oil, is conducive to improving vapour
The octane number of oil, reduces doing for gasoline；Post-reactor endothermic pyrolysis is returned it into, is conducive to improving the yield of gasoline products,
It is also beneficial to control post-reactor temperature rise.
Brief description of the drawings：
Fig. 1 is methanol hydrocarbon device.
1 material benzenemethanol pump in figure, 2 methanol injectors, 3 main injectors, 4 pre-reactors, 5 pre- injectors, 6 main reactors, 7
Lighter hydrocarbons injector, injector, 9 post-reactors, 10 heat-exchange systems, 11 water treatment systems, 12 profit gas separating systems, 13 liters after 8
Press pump, 14 de- lighter hydrocarbons towers, 15 de- heavy hydrocarbon towers, 16 heavy hydrocarbon surge tanks, 17 product gasoline storage tanks, 18 dry gas systems.
Embodiment
The present invention is described in detail below in conjunction with the accompanying drawings.
Material benzenemethanol is divided into two-way after being boosted by methanol feedstock pump 1, all the way as the working fluid of methanol injector 2, separately
All the way working fluid injection pre-reaction is used as through heat-exchange system 10 into pre- injector 5 by after the pre- thermal evaporation overheat of high-temperature product
After the portion of product that device 4 is exported, mixing heating enters pre-reactor 4 and reacts heating.The product section that pre-reactor 4 is exported is drawn
It is emitted back towards its entrance to improve its inlet temperature, it is possible to decrease the load of superheater, another part product enters as working fluid to be led
The injection of injector 3 enters main reactor 6 after coming from the further mixing of mixed gas of methanol injector 2, is gone out by main reactor 6
The product come is divided into two-way, all the way via the hybrid cooling of methanol injector 2, is returned through the mixing boosting heating of main injector 3 main anti-
Device entrance is answered to control temperature, the working fluid injection of another Lu Weihou injectors 8 comes from the gas of the outlet of lighter hydrocarbons injector 7
Enter post-reactor 9 afterwards, the outlets products of post-reactor 9 enter heat-exchange system 10, enter oil-water-gas segregative line after the cooling that is cooled
System 12, the water come out from profit gas separating system 12 enters water treatment system 11, and dry gas reacts after being returned by the injection of hydrocarbon injector 7
Device, liquid phase oil, which is boosted after pump 13 pressurizes, enters de- lighter hydrocarbons tower 14, takes off the overhead gas of lighter hydrocarbons tower 14 as the work of hydrocarbon injector 7
Fluid returns to post-reactor.The de- tower bottom liquid of lighter hydrocarbons tower 14 enters de- heavy hydrocarbon tower 15, takes off the tower bottom product of heavy hydrocarbon tower 16 and enters heavy hydrocarbon tank
16, tower top is product gasoline or gasoline component.Dry gas enters the power generation and heat supply of dry gas system 18 or sent outside.
Embodiment 1：Preparing gasoline by methanol
Gasoline is comprising the mixture that carbon number is many kinds of hydro carbons of C4 to C12, it is allowed to contain appropriate alcohol ether-ether component.Isomeric alkane
Hydrocarbon is high-quality component, and aromatic hydrocarbons octane number is high, and alkene octane number is higher, but alkene arene content is restricted.Lower carbon number hydrocarbons octane number
Height, but vapour pressure is high, should separate conversion.Long chain alkane octane number is low, should separate conversion.High boiling aromatic hydrocarbons components influence vehicle
Can, it should also separate conversion.
The advantage of the invention is that passing through stepwise reaction, the method for substep adjustment, the vapour for being produced preparing gasoline by methanol process
The high-quality gasoline of oily many components containing high-quality, reduces no coupling product yield.
Material benzenemethanol is boosted to by methanol feedstock pump 1 is divided into two-way after 2.5-2.6 MPas, all the way as methanol injector 2
Working fluid；Another road is 160-200 DEG C by temperature is superheated to by the pre- thermal evaporation of high-temperature product through heat-exchange system 10, and pressure is
After 2.3-2.4 MPas, the production of 300-400 DEG C of the part exported into pre- injector 5 as working fluid, injection pre-reactor 4
Mixing is warming up to 230-260 DEG C after thing, and pressure is warming up to 300-400 to be reacted after 2.2-2.3 MPas into pre-reactor 4
℃.Filling aluminum oxide catalyst for etherification, air speed 1-2h in pre-reactor-1.Pre-reactor preferentially selects fixed bed reactors.It is pre- anti-
The product temperatur for answering device 4 to export is 300-400 DEG C, and pressure is 2.1-2.2 MPas.A part returns its entrance to improve it by injection
Inlet temperature, reduces the load of superheater, and another part product comes from methanol as working fluid into the main injection of injector 3
200-230 DEG C of injector 2, pressure for 2.0-2.1 MPas mixed gas and further after mixing with 280-300 DEG C of temperature,
Pressure is 2.1-2.2 MPas and enters main reactor 6.Filling ZSM-5 catalyst, air speed 5-70h in main reactor 6-1, preferably 45-
50h-1.Main reactor can use fixed bed reactors, preferably moving-burden bed reactor.The composition of the product come out by main reactor 6
For low-carbon alkene, water, aromatic hydrocarbons etc., it is allowed to there is a small amount of unreacted methanol.Main reactor outlet temperature is 360-440 DEG C, pressure
It is divided into two-way for 2.0-2.1 MPas of product, all the way first through the hybrid cooling of methanol injector 2 to 200-230 DEG C, then by main injection
The injection mixing boosting of device 3 is warming up to 280-300 DEG C, and pressure is returns to entrance to control temperature after 2.1-2.2 MPas, another road is
The working fluid injection of injector 8 comes from after the 50-80 DEG C of gas mixing that lighter hydrocarbons injector 7 is exported with 220-260 DEG C afterwards
Temperature, 1.9-2.0 MPas of pressure enters post-reactor 9, and the outlets products temperature of post-reactor 9 is 280-360 DEG C, 1.8-1.9
MPa pressure enter heat-exchange system 10, cooled be cooled to after 40-80 DEG C enters oil-water-gas piece-rate system 12, from profit qi leel
Enter water treatment system 11 from the water that system 12 comes out, gas phase returns post-reactor by the injection of lighter hydrocarbons injector 7, and liquid phase oil is boosted
Pump 13, which is forced into after 2.4-2.6 MPas, enters de- lighter hydrocarbons tower 14, and it is 2.2-2.4 MPas to take off the tower top pressure of lighter hydrocarbons tower 14, and temperature is
40-60 DEG C of gas returns to post-reactor 9 as the working fluid of lighter hydrocarbons injector 7.The de- tower bottom liquid of lighter hydrocarbons tower 14 enters de- weight
Hydrocarbon tower 15, the de- tower bottom product of heavy hydrocarbon tower 15 is cached into heavy hydrocarbon tank 16, then returns to post-reactor 9 through lighter hydrocarbons injector 7.De- heavy hydrocarbon
The tower top of tower 15 is product gasoline or gasoline component.Dry gas enters the power generation and heat supply of dry gas system 18 or sent outside.Loaded in post-reactor 9
ZSM-5 catalyst, air speed 0.5-2h-1.Post-reactor can select fixed bed reactors or moving-burden bed reactor.In post-reactor 9
Interior, a small amount of unreacted methanol continue to react, and control 200-300 DEG C of temperature, and air speed is relatively low to ensure post-reactor outlets products
Without methanol.In post-reactor, the processes such as overlapping, hydrogenation, alkylation, isomerization, the aromatic disproportion of low-carbon alkene are also completed.Respectively
The yield of product is as shown in table 1.
Embodiment 2：Methanol diesel component
Diesel oil is comprising the mixture that carbon number is a variety of hydro carbons of more than C10 to C22, it is allowed to contain appropriate alcohol ether-ether component.
Long chain alkane is high-quality component, and Cetane number is high, but condensation point is also high.Monocyclic long side chain aromatic hydrocarbons and cycloalkane have moderate 16
Alkane value and condensation point.Compared with preparing gasoline by methanol technique, post-reactor uses polymerization catalyst.
Material benzenemethanol is boosted to by methanol feedstock pump 1 is divided into two-way after 2.5-2.6 MPas, all the way as methanol injector 2
Working fluid；It is 160-200 DEG C that another road is superheated to temperature through heat-exchange system 10 by the pre- thermal evaporation of high-temperature product, and pressure is
Enter the product for 300-400 DEG C of the part that pre- injector 5 is exported as working fluid injection pre-reactor 4 after 2.3-2.4 MPas
Mixing is warming up to 230-260 DEG C afterwards, and pressure is warming up to 300-400 DEG C to enter the reaction of pre-reactor 4 after 2.2-2.3 MPas.In advance
Filling aluminum oxide catalyst for etherification, air speed 1-2h in reactor-1.Pre-reactor preferentially selects fixed bed reactors.Pre-reactor 4
The product temperatur of outlet is 300-400 DEG C, and pressure is 2.1-2.2 MPas.A part returns its entrance to improve its entrance by injection
Temperature, reduces the load of superheater, and another part product comes from methanol injection as working fluid into the main injection of injector 3
200-230 DEG C of device 2, pressure for 2.0-2.1 MPas mixed gas and further after mixing with 280-300 DEG C of temperature, pressure
Enter main reactor 6 for 2.1-2.2 MPas.Filling ZSM-5 catalyst, air speed 5-70h in main reactor 6-1, preferably 45-50h-1.Main reactor can use fixed bed reactors, preferably moving-burden bed reactor.The composition of the product come out by main reactor 6 is low
Carbon olefin, water, aromatic hydrocarbons etc., it is allowed to have a small amount of unreacted methanol.Main reactor outlet temperature is 360-440 DEG C, and pressure is
2.0-2.1 MPas of product is divided into two-way, all the way first via the hybrid cooling of methanol injector 2 to 200-230 DEG C, then by main injection
The injection mixing boosting of device 3 is warming up to 280-300 DEG C, and pressure is returns to entrance to control temperature after 2.1-2.2 MPas, another road is
The working fluid injection of injector 8 comes from after the 50-80 DEG C of gas mixing that lighter hydrocarbons injector 7 is exported with 150-180 DEG C afterwards
Temperature, 1.9-2.0 MPas of pressure enters post-reactor 9, and the outlets products temperature of post-reactor 9 is 250-300 DEG C, 1.8-1.9
MPa enter heat-exchange system 10, cooled be cooled to after 40-80 DEG C enters oil-water-gas piece-rate system 12, from profit gas separating system
12 water out enters water treatment system 11, and gas phase returns post-reactor by the injection of lighter hydrocarbons injector 7, and liquid phase oil is boosted pump 13 and added
It is depressed into after 2.4-2.6 MPas and enters de- lighter hydrocarbons tower 14, it is 2.2-2.4 MPas to take off the tower top pressure of lighter hydrocarbons tower 14, temperature is 40-60 DEG C
Gas as hydrocarbon injector 7 working fluid return post-reactor.The de- tower bottom liquid of lighter hydrocarbons tower 14 enters de- heavy hydrocarbon tower 15, takes off weight
Hydrocarbon tower tower bottom product is cached into heavy hydrocarbon tank 16, or returns to post-reactor through lighter hydrocarbons injector 7.Tower top is product diesel oil or diesel oil
Component.Dry gas enters the power generation and heat supply of dry gas system 18 or sent outside.Filling polymerization catalyst, air speed 0.5-2h in post-reactor 9-1。
In post-reactor 9, a small amount of unreacted methanol continue to react, and control 200-300 DEG C of temperature, and air speed is relatively low with reaction after ensuring
Device outlets products are without methanol.In post-reactor, the etherificate of low-carbon alkene, overlapping, cracking, hydrogenation, alkylation, isomery are also completed
The processes such as change.The yield of each product is as shown in table 1.
Embodiment described above is only that the preferred embodiment of the present invention is described, not to the scope of the present invention
It is defined, on the premise of design spirit of the present invention is not departed from, those of ordinary skill in the art are to technical scheme
In the various modifications made and improvement, the protection domain that claims of the present invention determination all should be fallen into.
The product of table 1 is constituted
| Composition | Embodiment 1 | Embodiment 2 |
| Dry gas | 2.8% | 2.0% |
| Gasoline | 41.0% | |
| Diesel oil | 41.8% | |
| Water | 56.2% | 56.2% |
| It is total | 100% | 100% |
Claims (5)
1. a kind of reaction unit of methanol hydrocarbon, it is characterised in that by methanol feedstock pump (1), methanol injector (2), main injection
Device (3), pre-reactor (4), pre- injector (5), main reactor (6), lighter hydrocarbons injector (7), rear injector (8), post-reactor
(9), heat-exchange system (10), water treatment system (11), profit gas separating system (12), booster (13) takes off lighter hydrocarbons tower (14), takes off
Heavy hydrocarbon tower (15), heavy hydrocarbon surge tank (16), product gasoline tank (17), dry gas system (18) composition；
Methanol feedstock pump (1) outlet is connected by methanol injector (2) with main injector (3) all the way, and another road is through heat exchange
System (10) connects pre- injector (5)；The arrival end of pre-reactor (4) connects pre- injector (5), and the port of export returns to pre- draw all the way
Emitter (5), another road connects the entrance of main injector (3)；The outlet of main reactor (6) is divided into two-way, and methanol is returned all the way and is drawn
Emitter (2), another road is connected by rear injector (8) with post-reactor (9)；Heat-exchange system is passed through in the outlet of post-reactor (9)
(10) it is connected with profit gas separating system (12)；Three tunnels of profit gas separating system (12) outlet point, aqueous phase connection water treatment system
(11) injector (8) after, dry gas is returned by lighter hydrocarbons injector (7) injection, another part dry gas generates electricity by dry gas system (18) and supplied
Heat is sent outside, and the boosted pump of liquid phase oil (13) is connected with de- lighter hydrocarbons tower (14), takes off lighter hydrocarbons tower (14) tower top connection lighter hydrocarbons injector
(7) the de- heavy hydrocarbon tower (15) of lighter hydrocarbons tower (14) bottom of towe connection, is taken off, heavy hydrocarbon tower (15) tower top connection product gasoline storage tank (17), tower is taken off
Bottom connection heavy hydrocarbon surge tank (16).
2. the device described in a kind of usage right requirement 1 carries out the process of methanol hydrocarbon, comprise the following steps：
(1) the pre-reaction stage：Pre-reaction system includes pre- injector, pre-reactor, the methanol steam conduct from heat-exchange system
The working fluid of pre- injector, the portion of product of injection pre-reactor outlet, is recycled back to pre-reactor, occurs in pre-reactor
A product part after etherification reaction is recycled back to pre-reactor entrance by pre- injector, and being mixed with methanol steam makes methanol steam mistake
Heat enters methyltertiarvbutyl ether reactor to reaction temperature, and another part product first as the working fluid of main injector, enters main reaction afterwards
System；
(2) the main reaction stage：Main reaction system is made up of main injector, main reactor, methanol injector；The work of methanol injector
As fluid be come from material benzenemethanol pump, methanol injector injection main reactor outlet portion of product, into main injector, after follow
The reaction of dimethyl ether and methanol generation low-carbon alkene and water occurs for loopback main reactor, the main reaction stage, and part low-carbon alkene gathers
Close and aromatization；
(3) post-reaction period：Reaction system includes rear injector, post-reactor, lighter hydrocarbons injector, heat-exchange system, oil-water-gas afterwards
Piece-rate system, water treatment system, booster, de- lighter hydrocarbons tower, de- heavy hydrocarbon tower, product gasoline tank, heavy hydrocarbon surge tank, dry gas system；
Aromatisation, aromatic disproportion, alkylation, lamination process are further completed using post-reactor.
3. the process of methanol hydrocarbon according to claim 2, it is characterised in that the reaction temperature of pre-reaction system is
160-420 DEG C, reaction velocity is 1-70h-1, reaction pressure is 0.2-3.0MPa, and recycle ratio is 0.1-3；
The reaction temperature of main reaction system is 160-420 DEG C, and reaction velocity is 1-70h-1, reaction pressure is 0.2-3.0MPa, is followed
Ring ratio is 2-20；
The reaction temperature of reaction system is 160-420 DEG C afterwards, and reaction velocity is 0.5-10h-1, reaction pressure is 0.2-3.0MPa,
Recycle ratio is 1-20.
4. the process of methanol hydrocarbon according to claim 3, it is characterised in that：
The reaction temperature of pre-reaction system is 260-320 DEG C, and reaction velocity is 1.25-3h-1, reaction pressure is 1.5-2.6MPa,
Recycle ratio is 0.5-1.5；
The reaction temperature of main reaction system is 260-350 DEG C, and reaction velocity is 2-10h-1, reaction pressure is 1.2-2.4MPa, is followed
Ring ratio is 3-6；
The reaction temperature of reaction system is 300-400 DEG C afterwards, and reaction velocity is 1-2h-1, reaction pressure is 1.2-2.2MPa, circulation
Than for 3-5.
5. the process of methanol hydrocarbon according to claim 2, it is characterised in that the outlets products of the post-reactor
Cool by heat-exchange system, into profit gas separating system, by containing more than C3 component liquefaction separate, make it with booster
Enter de- lighter hydrocarbons tower after supercharging, overhead components C3-C4 reaction systems after lighter hydrocarbons injector is recycled back to, heavy constituent enters de- weight
Hydrocarbon tower, tower top is gasoline component, into product gasoline tank, C10 and above weight virtue in the heavy gasoline components containing durol
Hydrocarbon component is recycled back to rear reaction system by lighter hydrocarbons injector, after being mixed with newly-generated low-carbon alkene, light aromatic hydrocarbons occur disproportionation,
Cracking reaction generates C9 and following light aromatic hydrocarbons, as boiling point, the gasoline component that condensation point is qualified and octane number is high, in heavy gasoline components
Low octane rating C9 above alkane component occur cracking reaction generation higher octane below C9 hydrocarbon turn into specification gasoline component,
Constantly circulation is so as to realize not by-product heavy gasoline components.
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Effective date of registration: 20170725 Address after: 250000 Shandong Province Flyover District of Ji'nan City Road northbound No. 2131 Xinyuan Sangzi town Applicant after: Ji'nan Longkai Energy Technology Co Ltd Address before: 250000 Shandong Province Flyover District of Ji'nan City Road northbound No. 2131 Xinyuan Sangzi town Applicant before: Ma Yanchun |
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Inventor after: Qu Yantao Inventor after: Ma Yanchun Inventor before: Ma Yanchun |
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Effective date of registration: 20181024 Address after: 250000 1818 Xinyuan Road, sang Zi Dian Town, Tianqiao District, Ji'nan, Shandong Patentee after: Qu Yantao Address before: 250000 No. 2131 North Xinyuan Road, sang zi Town, Tianqiao District, Ji'nan, Shandong Patentee before: Ji'nan Longkai Energy Technology Co Ltd |
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Effective date of registration: 20181213 Address after: 262737 New Material Project Area of Green Chemical Industry Park East of Lanhai Road, South of Dawa West Street of Yangtze River, Weifang Binhai District, Shandong Province Patentee after: Weifang Hongrun New Materials Co., Ltd. Address before: 250000 1818 Xinyuan Road, sang Zi Dian Town, Tianqiao District, Ji'nan, Shandong Patentee before: Qu Yantao |