CN105885912A - Methanol-hydrocarbon method and device through ejecting circulation, fractional reaction and step-by-step adjustment - Google Patents
Methanol-hydrocarbon method and device through ejecting circulation, fractional reaction and step-by-step adjustment Download PDFInfo
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- CN105885912A CN105885912A CN201610438258.9A CN201610438258A CN105885912A CN 105885912 A CN105885912 A CN 105885912A CN 201610438258 A CN201610438258 A CN 201610438258A CN 105885912 A CN105885912 A CN 105885912A
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 109
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 73
- 238000000034 method Methods 0.000 title claims abstract description 73
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 311
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 142
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 125
- 239000003502 gasoline Substances 0.000 claims abstract description 88
- 239000000047 product Substances 0.000 claims description 92
- 230000004044 response Effects 0.000 claims description 41
- 230000008569 process Effects 0.000 claims description 39
- 239000012530 fluid Substances 0.000 claims description 38
- 238000002347 injection Methods 0.000 claims description 38
- 239000007924 injection Substances 0.000 claims description 38
- 229910052799 carbon Inorganic materials 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- -1 methanol hydrocarbon Chemical class 0.000 claims description 23
- 238000005899 aromatization reaction Methods 0.000 claims description 20
- 238000006266 etherification reaction Methods 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 16
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 15
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 13
- 239000007791 liquid phase Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 9
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 8
- 239000006227 byproduct Substances 0.000 claims description 8
- SQNZJJAZBFDUTD-UHFFFAOYSA-N durene Chemical compound CC1=CC(C)=C(C)C=C1C SQNZJJAZBFDUTD-UHFFFAOYSA-N 0.000 claims description 8
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 7
- 229960004217 benzyl alcohol Drugs 0.000 claims description 7
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 238000010248 power generation Methods 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 4
- 238000009833 condensation Methods 0.000 claims description 4
- 230000005494 condensation Effects 0.000 claims description 4
- 238000005336 cracking Methods 0.000 claims description 4
- 239000000470 constituent Substances 0.000 claims description 3
- 238000003860 storage Methods 0.000 claims description 3
- 239000008346 aqueous phase Substances 0.000 claims description 2
- 206010030113 Oedema Diseases 0.000 claims 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 claims 1
- 208000035475 disorder Diseases 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 2
- 238000004939 coking Methods 0.000 abstract 1
- 239000003337 fertilizer Substances 0.000 abstract 1
- 230000003319 supportive effect Effects 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 95
- 238000005516 engineering process Methods 0.000 description 12
- 150000001336 alkenes Chemical class 0.000 description 11
- 238000001816 cooling Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 9
- 238000005804 alkylation reaction Methods 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 9
- 239000012071 phase Substances 0.000 description 9
- 239000003921 oil Substances 0.000 description 8
- 230000029936 alkylation Effects 0.000 description 7
- 230000008901 benefit Effects 0.000 description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 238000006317 isomerization reaction Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000003213 activating effect Effects 0.000 description 4
- 239000002283 diesel fuel Substances 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 238000004519 manufacturing process 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
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000000567 combustion gas Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000003541 multi-stage reaction Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 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
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000002737 fuel gas Substances 0.000 description 2
- 150000002431 hydrogen Chemical group 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000002994 raw material 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
- 239000000126 substance Substances 0.000 description 2
- 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
- 239000005977 Ethylene Substances 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
- 238000005276 aerator Methods 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- 150000001875 compounds Chemical class 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
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005183 dynamical system Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/42—Catalytic treatment
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/60—Controlling or regulating the processes
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method and a device of converting methanol to prepare hydrocarbon products. The method includes that a pre-reaction system, a main reaction system and a post-reaction system are used for fractional reaction in a three-stage reactor respectively, reaction parameters are adjusted step by step to lower yield of dry gas, liquefied gas and heavy gasoline, and a method of enabling the liquefied gas, heavy gasoline components and the dry gas to be in circulating reaction is adopted to produce the hydrocarbon products like high-quality gasoline and diesel. Through ejecting circulation, the objectives of lowering power consumption and lowering investment of a power system are achieved. The device is compact in structure, supportive of modularized mounting, low in investment, high in target product yield, energy-saving, environment-friendly and suitable for methanol plants, alcohol-ammonium co-producing fertilizer plants and methanol-co-producing coking plants on various scales to produce the hydrocarbon products like high-quality solvent oil, gasoline and diesel.
Description
Technical field
The invention belongs to the process of a kind of preparing hydrocarbon products by methanol conversion.Specifically refer to methanol or thick
Methanol is the technique side of the hydrocarbon liquid phase series products such as raw material production gasoline or gasoline component, solvent naphtha, diesel component
Method, belongs to Coal Chemical Industry or gas chemical industry field.
Background technology
By suitable catalytic process, methanol can be converted into water and hydrocarbons series products, as alkene, alkane,
Aromatic hydrocarbons and the mixture of above-mentioned hydrocarbon products.According to the difference of purpose product, existing methanol process for producing hydrocarbons bag
Include the techniques such as preparing gasoline by methanol, methanol-to-olefins and methanol aromatic hydrocarbons.
Oil quality is the key factor affecting motor vehicle exhaust emission.In recent years, haze weather takes place frequently, automobile
Tail gas is considered as the key factor forming haze weather, and market is in the urgent need to providing high-quality fuel oil.With often
The similar hydrocarbon products that rule petroleum and petrochemical industry method obtains is compared, and obtains gasoline and diesel oil by methanol hydrocarbon technology
Low Deng the grade content of objectionable impurities of the benzene in hydrocarbon products, alkene, sulfur, nitrogen, ash, can effectively protect car
Performance, reduces the Vehicular exhaust contribution to haze, meets the market requirement to high standard gasoline, diesel, right
Significant in protection environment.
It is typical methanol hydrocarbon technology that methanol converts gasoline processed (MTG) technology, Mobil company invent.From
Within 1974, rising, the said firm has applied for that multinomial relevant methanol converts the patent of gasoline processed.
Methanol hydrocarbon process is an exothermic process, and how controlling reaction temperature is the emphasis that this process is paid close attention to.
Around climate control issues, kinds of processes and response system thereof are developed, the form bag of existing response system
Include fixed bed, multitube fixed bed, multistage cold shock fixed bed, moving bed, fluid bed etc..
Methanol converts the technology of hydrocarbon products processed and mostly uses two sections of conversion process.United States Patent (USP) 3931349 is
The methanol of Mobil company alerting bulletin converts the patent of hydro carbons processed, uses two sections of conversion process of fixed bed, wherein
First paragraph reaction is preparing dimethyl ether by dewatering methanol, one section outlet material, mixing including methanol, dimethyl ether and water
Compound, enters second stage reactor, generates gasoline fraction section product under the effect of molecular sieve catalyst.
United States Patent (USP) 4579999 then discloses another two-stage method methanol and converts gasoline fraction section hydro carbons processed product
The technology of product, in one section reactor load molecular sieve catalyst, methanol is first converted into low-carbon alkene and
Part hydrocarbon, by C5+After refrigerated separation, low-carbon alkene enters second stage reactor, at the work of olefin polymerization catalysis
Under with, it is converted into gasoline fraction section product further.
United States Patent (USP) 4689205 discloses a kind of methanol multi-stage and converts the technology producing hydrocarbon.This patent disclosure
Technology and United States Patent (USP) 4579999 basic simlarity, in first stage reactor, methanol is at uniform temperature and pressure
Under the conditions of be converted into C2-C4 alkene and part C5+Hydrocarbon, by C5+After hydrocarbon separates, remainder enters second
Section reactor, uses olefin polymerization catalysis, is polymerized to further by the low-carbon alkene that first paragraph reaction produces
The hydrocarbon product of gasoline fraction.Except that, in the technology of this patent disclosure, first paragraph uses fluidisation
Bed reactor.
Chinese invention patent 200610048298.9 proposes a kind of methanol by one-step method and produces the technique of hydrocarbon products,
Feature is to be completed in a reactor by three phases, has the advantage that technological process is short, with two-step method phase
Ratio, has the short advantage of technological process, but recycle ratio is big, and course of reaction is wayward, and product is gasoline, liquid
Activating QI and heavy petrol etc..
In existing cold shock bed methanol process for producing hydrocarbons, in its every first order reaction bed, complete methanol hydrocarbon
The three phases of course of reaction.
The utility model patent of Application No. 200720101511.8 proposes the preparing gasoline by methanol of a kind of cold shocking type
Reactor, the mode using inter-stage to add the cooling gases such as nitrogen controls reaction temperature, and product is gasoline, liquid
Activating QI and fuel gas, the not mentioned power resources making cooling gas circulate.
Existing insulation fix bed technique, need to use the mode of a large amount of recycle hydrocarbons to cool down, and needs to be equipped with gas pressure
Contracting unit, investment is big, and power consumption is big.Meanwhile, because using the type of cooling of recycle hydrocarbons, circulate in a large number
Hydrocarbon needs repeatedly to heat combination cooling, and rectification separates, and heat exchange amount is big, and piece-rate system and heat-exchange system cost are high.
The feature of fluidized-bed process is at fluidized-bed reactor by the three phases of the course of reaction of preparing gasoline by methanol
Inside complete.Use fluid bed process can effectively solve cooling problem, but fluidized-bed structure be complicated, it is not easy to
Operation, cost is high, it is desirable to production scale is big, and investment risk is big.
Existing multi-tubular reactor absorbs reaction heat using fused salt as heat transfer medium and produces steam, but fused salt changes
Hot systems structure is complicated, system start and stop difficulty.
The technique equal co-production of liquefied gas of existing all kinds of preparing gasoline by methanol and the heavy petrol containing durol, liquid
The following process of activating QI and heavy petrol is required to increase equipment investment.
In relevant field, such as, methanol-to-olefins, the technical process of methanol aromatic hydrocarbons generally wants coproduction portion
Dividing gasoline products, the purification apparatus investment of olefin product and aromatic hydrocarbon product is higher.
In sum, the target products such as it is big that existing preparing gasoline by methanol technique there are equipment investment, gasoline are received
Rate is low, and power consumption is big, the problem that energy consumption is high.Although hydrocarbon productss such as market in urgent need high-quality gasolines, former
Material methanol production capacity surplus, but invest the reasons such as big and energy consumption height because of existing technique and device existence, at low oil
In the valency 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；
The stage of the processes such as low-carbon alkene polymerization and aromatisation.
The feature of fixed bed two-step process be the first step by the major part of etherification stage at an etherification reaction
Complete in device.Second step, conversion reactor complete generate the low-carbon alkene stage, low-carbon alkene polymerization and
The processes such as aromatisation.
Methanol etherification procedure on aluminium oxide catalyst for etherification is the most stable, discharges partial reaction heat, suitable
When entering back into alkylation reaction device after cooling, 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 for low-carbon (LC)
The control of alkene subsequent reactions can obtain different target products, such as: termination reaction process is methanol system
Low carbon olefin hydrocarbon；Carry out building-up reactions and can obtain the olefin product that carbon number is more；Aromatisation can obtain
Aromatic product.Aromatization process is producing while aromatic hydrocarbons also by-product dry gas, and excessive aromatisation makes dry gas and liquid
Activating QI productivity rises.
Existing preparing gasoline by methanol technique, basic employing ZSM-5 catalyst series.On ZSM-5 catalyst,
Methanol can carry out etherification reaction, carry out generate low-carbon alkene, overlapping, isomerization, aromatisation, alkylation,
The courses of reaction such as hydrogenation, reactor outlet product is hydrogen, alkene, alkane, cycloalkane, aromatic hydrocarbons and water
Mixture, can get the products such as fuel gas, liquefied gas, gasoline, heavy petrol after separation.This process is first
The basis of alcohol hydrocarbon particularly preparing gasoline by methanol technique.The technical processs such as existing one-step method, two-step method are all
Grow up on this basis.
Summary of the invention
Engineering practice and further investigation revealed that, it is many to there is side-product kind in these methods existing, power
Consuming big, big problem invested by byproduct for treatment and power-equipment.
It is an object of the invention to provide a kind of yield of gasoline high, power consumption is low, the methanol that equipment investment is low
The method of gasoline processed.
The present invention is by being three-step reaction process to the process subdivision of above-mentioned methanol liquefaction, respectively in third-order reaction
Carry out stepwise reaction in device and substep adjust response parameter to reduce dry gas, liquefied gas and the productivity of heavy petrol,
And use the purpose that the method that liquefied gas, heavy gasoline components, residue gas recycle react realizes improving yield of gasoline.
The present invention uses injector system to realize the supercharging of recycle hydrocarbons.Injector is to utilize jet turbulent fluctuation diffusion to make
With, carry out mass transfer and pass fluid machinery and the mix reaction equipment of energy.High pressure draught sprays from nozzle at high speeds, draws
Penetrating the low-pressure gas around nozzle, two strands of air-flows mix in mixing chamber and diffuser, supercharging, are consuming
Under conditions of certain high-pressure working gas, improve the low-pressure gas pressure entering injector from suction inlet, this
The equipment of kind is referred to as jet pump.Working fluid with the highest speed from nozzle out, enters the receiving chamber of injector,
And medium relatively low for the pressure before injector is taken away.The fluid being pulled away is driving fluid, improves injection
The pressure of fluid and the most directly consume mechanical energy, this is the topmost performance of injector.Owing to having this property
Matter, under many circumstances, use injector than use machinery supercharging equipment (compressor, pump, aerator and
Air-introduced machine etc.) the most simply, the most reliable.In addition to this body structure is extremely simple, injector sets with various
The standby method connected is the simplest, manufactures the most uncomplicated, is widely applied in engineering.
The response system of the present invention includes etherification reaction system, is called for short pre-reaction system；Low-carbon alkene reaction is
System, is called for short primary response system；Aromatisation and overlapping and alkylation combined reaction system be called for short after response system.
The pre-reaction system of the present invention includes: pre-injector, pre-reactor.Methanol from heat-exchange system steams
Vapour, as the working fluid of pre-injector, the portion of product of injection pre-reactor outlet, loops back pre-reactor.
Product temperatur after etherification reaction is up to more than 400 DEG C, and a part is returned etherification reaction by pre-injector injection
Device entrance, mixes with methanol steam and makes methanol steam be superheated to reaction temperature entrance methyltertiarvbutyl ether reactor, it is possible to decrease
The load of methanol steam superheater.Reduce the by-products such as methane in etherification reaction temperature and etherification procedure simultaneously
Productivity.Another part product, first as the working fluid of main injector, laggard becomes owner of response system.Pre-reaction
The reaction temperature of system is 160-420 DEG C, and preferred reaction temperature is 260-320 DEG C.Pre-reaction system anti-
Answering air speed is 1-70h-1, preferred reaction velocity is 1.25-3h-1.The reaction pressure of pre-reaction system is
0.2-3.0MPa, preferred reaction pressure is 1.5-2.6MPa.Recycle ratio is 0.1-3, preferably 0.5-1.5.This
Recycle ratio refers to the mass ratio of product and this reactor reaction thing returning to reactor inlet, and recycle ratio is the biggest,
The product of backflow is the most.
The primary response system (low-carbon alkene response system) of the present invention is by main injector, main reactor, methanol
Injector forms.The working fluid of methanol injector is from material benzenemethanol pump, and injector injection master is anti-for methanol
Answering the portion of product that device exports, enter main injector, Posterior circle returns main reactor.Primary response system is mainly sent out
Raw dimethyl ether and methanol generate the reactions such as low-carbon alkene and the reaction of water, the polymerization of part low-carbon alkene and aromatisation.
Primary response system uses relatively low reaction temperatures, and higher space velocity is to limit aromatisation process, to control to reduce
Dry gas and low-carbon alkanes productivity.The reaction temperature of primary response system is 160-420 DEG C, and preferred reaction temperature is
260-350℃.The reaction velocity of primary response system is 1-70h-1, preferred reaction velocity is 2-10h-1.Main anti-
The reaction pressure answering system is 0.2-3.0MPa, and preferred reaction pressure is 1.2-2.4MPa.Primary response system
Recycle ratio be 2-20, preferably 3-6.
The rear response system of the present invention includes: rear injector, post-reactor, lighter hydrocarbons injector, heat-exchange system,
Oil-water-gas 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.
Post-reactor is used to complete the processes such as aromatisation, aromatic disproportion, alkylation, overlapping further.
The outlets products of post-reactor is lowered the temperature through heat-exchange system, enters oil-water-gas piece-rate system, by contain
The component liquefaction of more than C3 separates, and enters de-lighter hydrocarbons tower, overhead components C3-C4 after making its supercharging with booster
Looping back response system through lighter hydrocarbons injector, heavy constituent enters de-heavy hydrocarbon tower, and tower top is gasoline component, enters
Entering product gasoline tank, C10 and above heavy aromatics component in the heavy gasoline components containing durol are passed through light
Hydrocarbon injector loops back rear response system, be disproportionated after mixing with newly-generated low-carbon alkene, light aromatic hydrocarbons etc.,
The reactions such as cracking generate C9 and following light aromatic hydrocarbons, become boiling point, condensation point is qualified and octane number is high gasoline group
Point, the low octane rating C9 above alkane component generation cracking reaction in heavy gasoline components generates higher octane
Below C9 hydrocarbon become specification gasoline component, constantly circulation thus realize the purpose of not by-product heavy gasoline components.
Liquefied gas component liquefaction containing C3-C4 is separated by the present invention by piece-rate system, makes it with booster pump
Supercharging Posterior circle returns rear response system.In response system, the liquefied gas component looped back and dry gas component with
Newly-generated low-carbon alkene mixing occurs the reactions such as alkylation, aromatisation, overlapping to generate corresponding gasoline component.
The method that the present invention controls course of reaction by using substep makes aromatization degree be less than the aromatization of conventional MTG
Change degree, therefore in lower carbon number hydrocarbons, olefin(e) centent is higher, and low-carbon alkanes content is relatively low, loops back post-reactor easy
In carrying out overlapping, isomerization, aromatization become C5+Gasoline component.Utilize the low of ZSM-5 catalyst
Carbon hydrocarbon overlapping, cyclisation, liquefied gas low temperature aromatization technology are mature technologies.Stepwise reaction substep is used to control
Method, can by control recycle ratio, air speed, reaction temperature, pressure and other parameters control reaction process, can
Make recycle hydrocarbons total amount maintain not only and can meet cooling needs but also the level of non-excess.The recycle ratio of rear response system
For 1-20, preferably 3-5.The reaction temperature of rear response system is 160-420 DEG C, and preferred reaction temperature is
300-400℃.The reaction velocity of rear response system is 0.5-10h-1, preferred reaction velocity is 1-2h-1.Rear anti-
The reaction pressure answering system is 0.2-3.0MPa, and preferred reaction pressure is 1.2-2.2MPa.Liquefied gas in a small amount
With dry gas for thermoelectricity fuel, to realize not by-product liquefied gas, reduce the purpose of equipment investment.
By piece-rate system separate containing hydrogen, methane, ethylene, ethane dry gas by lighter hydrocarbons injection
After returning after device supercharging, response system continues reaction generation gasoline component.Extension unreacted dry gas conduct
Combustion gas is sent into combustion gas and is utilized system for generating and heat supply, can meet the thermoelectricity demand of this device, it is achieved the most secondary
Produce combustion gas, improve yield of gasoline, reduce the purpose of public work investment.This device is because being capable of thermoelectricity
Confession, it may have the advantage energy-saving and cost-reducing, public work investment is low.Unnecessary thermoelectricity can be sent outside, improves
Dry gas is worth, and improves device benefit.
The present invention utilizes heavy gasoline components, liquefied gas component, dry gas as recycle hydrocarbons.Heavy petrol, liquefied gas
It is far below carburet hydrogen compressor by liquid hydrocarbon booster pump supercharging, its power consumption at liquid phase state.Weight after supercharging
Gasoline and liquefied gas make dry gas as the working fluid injection dry gas of lighter hydrocarbons injector after being heated up by endothermic gasification
Boosting realizes circulation.Recycle hydrocarbons boost cycle is without gas compressor, it is achieved that reduce power consumption and reduction
The purpose of dynamical system investment.
The present invention is described in detail as follows:
The present invention provides the reaction unit of a kind of methanol hydrocarbon, by 1 methanol feedstock pump, and 2 methanol injectors, 3
Main injector, 4 pre-reactors, 5 pre-injectors, 6 main reactors, 7 lighter hydrocarbons injectors, injector after 8,
9 post-reactors, 10 heat-exchange systems, 11 water treatment systems, 12 oil-water-gas piece-rate systems, 13 boosters, 14
De-lighter hydrocarbons tower, 15 take off heavy hydrocarbon tower, 16 heavy hydrocarbon tanks, 17 product gasoline tanks, 18 dry gas system compositions；
Methanol feedstock pump 1 port of export is leaded up to methanol injector 2 and is connected with main injector 3, another road warp
Heat-exchange system 10 connects pre-injector 5；The arrival end of pre-reactor 4 connects pre-injector 5, the port of export one
Road returns pre-injector 5, and another road connects the entrance of main injector 3；The outlet of main reactor 6 is divided into two-way,
One tunnel returns methanol injector 2, and rear injector 8 of separately leading up to is connected with post-reactor 9；Post-reactor 9
Outlet be connected with oil-water-gas piece-rate system 12 through heat-exchange system 10；Oil-water-gas piece-rate system 12 outlet point
Three tunnels, aqueous phase connects water treatment system 11, and dry gas is returned rear injector 8 by lighter hydrocarbons injector 7 injection, another
Part dry gas is through dry gas system 18 power generation and heat supply or sends outside, enters de-after the pressurization of liquid phase oil boosted pump 13
Lighter hydrocarbons tower 14, de-lighter hydrocarbons tower 14 overhead gas return as the working fluid of lighter hydrocarbons injector 7 after injector 8,
De-lighter hydrocarbons tower 14 tower bottom liquid enters de-heavy hydrocarbon tower 15, and de-heavy hydrocarbon tower 15 overhead product connects product gasoline storage tank
17, tower bottom product enters heavy hydrocarbon surge tank 16, rear return lighter hydrocarbons injector.
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, and a road is as the work of methanol injector 2
Making fluid, another road, after heat-exchange system 10 is overheated by high-temperature product preheating evaporation, enters pre-injector 5 and makees
After portion of product for the outlet of working fluid injection pre-reactor 4, mixing intensification enters pre-reactor 4 and carries out
Etherification reaction.
2. the primary response stage
The product section of pre-reactor 4 outlet is returned its entrance to improve its inlet temperature by injection, it is possible to decrease mistake
The load of hot device, another part product enters main injector 3 injection as working fluid and comes from methanol injection
The mixed gas of device 2, further mixing laggard enter main reactor 6, main reactor 6 product out be divided into
Two-way, a road, by methanol injector 2 injection hybrid cooling, enters back into the mixing boosting intensification of main injector 3 and returns
Backing into mouth to control temperature, another road comes from lighter hydrocarbons injector 7 as the working fluid injection of rear injector 8
Gas after enter post-reactor 9.
3. post-reaction period
The outlets products of post-reactor 9 enters heat-exchange system 10 and carries out heat exchange with the material from methanol feedstock pump,
Entering oil-water-gas piece-rate system 12 after cooled cooling, isolated water enters water treatment system 11.Isolate
A dry gas part returned post-reactor by lighter hydrocarbons injector 7 injection, another part enters dry as dry gas product
Gas system 18 power generation and heat supply or send outside.De-lighter hydrocarbons tower 14 is entered after the pressurization of liquid phase oil component boosted pump 13,
De-lighter hydrocarbons tower 14 overhead gas returns post-reactor as the working fluid of lighter hydrocarbons injector 7.De-lighter hydrocarbons tower 14
Tower bottom liquid enters de-heavy hydrocarbon tower 15 mutually, and the tower bottom product of de-heavy hydrocarbon tower enters heavy hydrocarbon surge tank 16, and rear return is light
Hydrocarbon 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 first by raw material first
Alcohol pump supercharging, is then passed through preheating the methanol steam of vaporized thermosetting High Temperature High Pressure, owing to etherification reaction is
Exothermic reaction, utilizes pre-injector injection partial ethers product, makes methanol steam further heat up, it is possible to decrease
The load of methanol steam superheater.Reduce in etherification reaction temperature and etherification procedure byproduct methane etc. dry simultaneously
The productivity of gas.
Complete to react refrigerated separation process to be required to consume power.The present invention uses methanol pump to add to Liquid Phase Methanol
Pressure, because liquid compression is little, methanol pump power consumption is less than the compressor to gas phase compression.High-pressure liquid phase methanol
Absorbing reaction heat formation high temperature and high pressure gas by heat exchange and have acting ability, the present invention utilizes this acting
Ability, as the power of reaction refrigerated separation process operation, can reduce the electric power required for process.
The present invention utilizes injector, to have without movement parts as recycle hydrocarbons circulation power shifter, injector
Simple and reliable for structure, cost is low, consumes energy low, reliable advantage.Injector has simultaneously makes hot and cold stream
Body directly mixes the function of quick heat exchange, and the cost of heat-exchange system can be greatly lowered.
The primary response system of the present invention has the characteristic that control aromatization degree, limits dry gas and liquefied gas produces
The heavy gasoline components productivity such as rate, strengthens isomerization reaction, make dry gas, below C4 alkane productivity low, heavy aromatics
Low, and circular response, on the one hand can improve liquid and receive, recycle hydrocarbons on the other hand can be utilized to control temperature.
Heavy aromatics circular response, it is possible to suppression heavy aromatics productivity.Reduce high boiling point non-aromatic component in gasoline,
Be conducive to improving the octane number of gasoline.
The piece-rate system of the present invention has the characteristic that: dry gas, liquefied gas, heavy petrol separate with gasoline component
Posterior circle returns rear response system circular response, on the premise of keeping gasoline component height yield, it is thus achieved that low C4 contains
Amount, the low-steam pressure of low more than C10 constituent content, low do, high-octane high-quality gasoline or gasoline
Component.
The power circulation system of the present invention has the characteristic that, uses ejection circulation, can cancel following of routine
Ring gas compressor, reduces equipment investment and power consumption.
The heat-exchange system of the present invention has the characteristic that: because using the direct mixed heat transfer side of cold fluid and hot fluid injection
Formula and the feature utilizing working fluid to lower the temperature because of expansion, it is possible to decrease heat-exchange system cost.
By adjusting piece-rate system operational factor, by dry gas liquefied gas and the heavy gasoline components containing durol
Return the post-reactor continuation reaction arranged and be converted into gasoline component, do not produce liquefied gas product and durol
Product, so liquefied gas purification apparatus and durol purification apparatus need not be equipped with and run, can reduce and set
Standby cost and operating cost.
The refined needs of liquefied gas are equipped with higher rectifying column, and yield is the highest, does not has scale effect, and accumulating becomes
This height, generally, is difficult to compete with petroleum base liquefied gas.Liquefied gas price is less than high-quality gasoline valency
Lattice, are converted into liquefied gas gasoline component and can improve device benefit.In the technique of the present invention, it is by C4
Following liquefied gas component and residue gas recycle return reactor by courses of reaction such as alkylation, overlapping, aromatisation
It is converted into gasoline component.This technology controlling and process post-reactor temperature simultaneously, aromatization degree is relatively low, saturated low-carbon (LC)
Determination of Alkane Content is low, is converted into gasoline component by overlapping and alkylated reaction in post-reactor.Durol
Subtractive process needs equipment investment big, and market capacity is less, and selling cost is high.This technique is by more than C10 group
Post-reactor is returned after separating.In post-reactor, durol is disproportionated into C7-C9 aromatic hydrocarbons, C7-C9
Aromatic hydrocarbons is high octane gasoline component.The alkane alkene of more than C10 is low octane rating component, reduces it at gasoline
In content, be conducive to improving the octane number of gasoline, reduce the doing of gasoline；Return it into post-reactor to inhale
Thermal cracking, is conducive to improving the yield of gasoline products, is also beneficial to control post-reactor temperature rise.
Accompanying drawing illustrates:
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 injectors, injector after 8,9 post-reactors, 10 heat-exchange systems, 11 water process
System, 12 oil-water-gas piece-rate systems, 13 boosters, 14 take off lighter hydrocarbons tower, and 15 take off heavy hydrocarbon tower, and 16 heavy hydrocarbons delay
Rush tank, 17 product gasoline storage tanks, 18 dry gas systems.
Detailed description of the invention
Below in conjunction with the accompanying drawings the present invention is described in detail.
Material benzenemethanol is divided into two-way after being boosted by methanol feedstock pump 1, and a road is as the work of methanol injector 2
Fluid, another road, after heat-exchange system 10 is overheated by high-temperature product preheating evaporation, enters the conduct of pre-injector 5
After the portion of product of working fluid injection pre-reactor 4 outlet, mixing intensification enters pre-reactor 4 reaction and rises
Temperature.The product section of pre-reactor 4 outlet is returned its entrance to improve its inlet temperature by injection, it is possible to decrease mistake
The load of hot device, another part product enters main injector 3 injection as working fluid and comes from methanol injection
The mixed gas of device 2 mix further laggard enter main reactor 6, main reactor 6 product out be divided into two
Road, via methanol injector 2 hybrid cooling, heats up through the mixing boosting of main injector 3 and returns primary response in a road
Device entrance is to control temperature, and the working fluid injection of another Lu Weihou injector 8 comes from lighter hydrocarbons injector 7
Entering post-reactor 9 after the gas of outlet, post-reactor 9 outlets products enters heat-exchange system 10, cooled
Enter oil-water-gas piece-rate system 12 after cooling, enter water treatment system from oil-water-gas piece-rate system 12 water out
11, dry gas is returned post-reactor by hydrocarbon injector 7 injection, enters de-lighter hydrocarbons after the pressurization of liquid phase oil boosted pump 13
Tower 14, de-lighter hydrocarbons tower 14 overhead gas returns post-reactor as the working fluid of hydrocarbon injector 7.De-lighter hydrocarbons
Tower 14 tower bottom liquid enters de-heavy hydrocarbon tower 15, and de-heavy hydrocarbon tower 16 tower bottom product enters heavy hydrocarbon tank 16, and tower top is for producing
Product gasoline or gasoline component.Dry gas enters dry gas system 18 power generation and heat supply or sends outside.
Embodiment 1: preparing gasoline by methanol
Gasoline is to comprise the mixture that carbon number is many kinds of hydro carbons of C4 to C12, it is allowed to containing appropriate alcohol ether-ether component.
Isoparaffin is high-quality component, and aromatic hydrocarbons octane number is high, and alkene octane number is higher, but alkene arene content is subject to
Limit.Lower carbon number hydrocarbons octane number is high, but vapour pressure is high, should separate conversion.Long chain alkane octane number is low, should divide
From conversion.High boiling aromatic hydrocarbons components influence vehicle performance, also should separate conversion.
It is an advantage of the current invention that, by stepwise reaction, the method that substep adjusts, to make preparing gasoline by methanol process institute
The many high-quality gasolines containing high-quality component of gasoline produced, reduce no coupling product productivity.
Material benzenemethanol is divided into two-way after being boosted to 2.5-2.6 MPa by methanol feedstock pump 1, and a road is drawn as methanol
The working fluid of emitter 2；Another road is superheated to temperature through heat-exchange system 10 by high-temperature product preheating evaporation
160-200 DEG C, after pressure is 2.3-2.4 MPa, enter pre-injector 5 as working fluid, injection pre-reaction
After the product of part 300-400 DEG C of device 4 outlet, mixing is warming up to 230-260 DEG C, and pressure is 2.2-2.3 MPa
Rear entrance pre-reactor 4 reacts and is warming up to 300-400 DEG C.Filling aluminium oxide etherificate catalysis in pre-reactor
Agent, air speed 1-2h-1.Pre-reactor preferentially selects fixed bed reactors.The product temperatur of pre-reactor 4 outlet
For 300-400 DEG C, pressure is 2.1-2.2 MPa.A part is returned its entrance to improve its inlet temperature by injection,
Reducing the load of superheater, another part product enters main injector 3 injection as working fluid and comes from first
200-230 DEG C of alcohol injector 2, pressure be 2.0-2.1 MPa mixed gas and further mixing after with temperature
280-300 DEG C, pressure is 2.1-2.2 MPa and enters main reactor 6.Filling ZSM-5 catalysis in main reactor 6
Agent, air speed 5-70h-1, preferably 45-50h-1.Main reactor can use fixed bed reactors, preferably moving bed anti-
Answer device.It is low-carbon alkene, water, aromatic hydrocarbons etc. by the composition of main reactor 6 product out, it is allowed to have in a small amount
Unreacted methanol.Main reactor outlet temperature is 360-440 DEG C, and pressure is that the product of 2.0-2.1 MPa is divided into
Two-way, a road first through methanol injector 2 hybrid cooling to 200-230 DEG C, then mixed by main injector 3 injection
Be warming up to 280-300 DEG C, pressure be 2.1-2.2 MPa after return entrance to control temperature, another Lu Weihou
The working fluid injection of injector 8 come from after 50-80 DEG C of gas mixing of lighter hydrocarbons injector 7 outlet with
The temperature of 220-260 DEG C, the pressure of 1.9-2.0 MPa enters post-reactor 9, post-reactor 9 outlets products temperature
Degree is 280-360 DEG C, and the pressure of 1.8-1.9 MPa enters heat-exchange system 10, is cooled after being cooled to 40-80 DEG C
Enter oil-water-gas piece-rate system 12, enter water treatment system 11 from oil-water-gas piece-rate system 12 water out,
Gas phase is returned post-reactor by lighter hydrocarbons injector 7 injection, after the boosted pump of liquid phase oil 13 is forced into 2.4-2.6 MPa
Entering de-lighter hydrocarbons tower 14, de-lighter hydrocarbons tower 14 tower top pressure is 2.2-2.4 MPa, and temperature is the gas of 40-60 DEG C
Working fluid as lighter hydrocarbons injector 7 returns post-reactor 9.De-lighter hydrocarbons tower 14 tower bottom liquid enters de-heavy hydrocarbon
Tower 15, de-heavy hydrocarbon tower 15 tower bottom product enters heavy hydrocarbon tank 16 and caches, more anti-after lighter hydrocarbons injector 7 returns
Answer device 9.De-heavy hydrocarbon tower 15 tower top is product gasoline or gasoline component.Dry gas enters dry gas system 18 generating and supplies
Heat or send outside.Filling ZSM-5 catalyst, air speed 0.5-2h in post-reactor 9-1.Post-reactor can be selected for solid
Fixed bed reactor or moving-burden bed reactor.In post-reactor 9, the most unreacted methanol continues reaction,
Controlling temperature 200-300 DEG C, air speed is relatively low to guarantee that post-reactor outlets products is without methanol.In post-reactor,
Also complete the processes such as the overlapping of low-carbon alkene, hydrogenation, alkylation, isomerization, aromatic disproportion.Each product
Yield is as shown in table 1.
Embodiment 2: methanol diesel component
Diesel oil is to comprise the mixture that carbon number is the multiple hydro carbons of more than C10 to C22, it is allowed to containing appropriate alcohol ether
Ester component.Long chain alkane is high-quality component, and Cetane number is high, but condensation point is the highest.Monocycle long side chain aromatic hydrocarbons and
Cycloalkane has moderate Cetane number and condensation point.Compared with preparing gasoline by methanol technique, post-reactor uses folded
Close catalyst.
Material benzenemethanol is divided into two-way after being boosted to 2.5-2.6 MPa by methanol feedstock pump 1, and a road is drawn as methanol
The working fluid of emitter 2；Another road is superheated to temperature through heat-exchange system 10 by high-temperature product preheating evaporation
160-200 DEG C, pressure enters pre-injector 5 as working fluid injection pre-reactor 4 after being 2.3-2.4 MPa
Outlet part 300-400 DEG C product after mixing be warming up to 230-260 DEG C, pressure be 2.2-2.3 MPa laggard
Enter pre-reactor 4 reaction and be warming up to 300-400 DEG C.Filling aluminium oxide catalyst for etherification, air speed in pre-reactor
1-2h-1.Pre-reactor preferentially selects fixed bed reactors.The product temperatur of pre-reactor 4 outlet is
300-400 DEG C, pressure is 2.1-2.2 MPa.A part is returned its entrance to improve its inlet temperature by injection, fall
The load of low superheater, another part product enters main injector 3 injection as working fluid and comes from methanol
200-230 DEG C of injector 2, pressure be 2.0-2.1 MPa mixed gas and further mixing after with temperature
280-300 DEG C, pressure is 2.1-2.2 MPa and enters main reactor 6.Filling ZSM-5 catalysis in main reactor 6
Agent, air speed 5-70h-1, preferably 45-50h-1.Main reactor can use fixed bed reactors, preferably moving bed anti-
Answer device.It is low-carbon alkene, water, aromatic hydrocarbons etc. by the composition of main reactor 6 product out, it is allowed to have in a small amount
Unreacted methanol.Main reactor outlet temperature is 360-440 DEG C, and pressure is that the product of 2.0-2.1 MPa is divided into
Two-way, a road first via methanol injector 2 hybrid cooling to 200-230 DEG C, then mixed by main injector 3 injection
Close boosting be warming up to 280-300 DEG C, pressure be 2.1-2.2 MPa after return entrance to control temperature, another road is
The working fluid injection of rear injector 8 come from after 50-80 DEG C of gas mixing of lighter hydrocarbons injector 7 outlet with
The temperature of 150-180 DEG C, the pressure of 1.9-2.0 MPa enters post-reactor 9, post-reactor 9 outlets products temperature
Degree is 250-300 DEG C, and 1.8-1.9 MPa enters heat-exchange system 10, is cooled after being cooled to 40-80 DEG C and enters oil
Water vapor separation system 12, enters water treatment system 11, gas phase quilt from oil-water-gas piece-rate system 12 water out
Lighter hydrocarbons injector 7 injection returns post-reactor, and the boosted pump of liquid phase oil 13 enters de-after being forced into 2.4-2.6 MPa
Lighter hydrocarbons tower 14, de-lighter hydrocarbons tower 14 tower top pressure is 2.2-2.4 MPa, and temperature is that the gas of 40-60 DEG C is as hydrocarbon
The working fluid of injector 7 returns post-reactor.De-lighter hydrocarbons tower 14 tower bottom liquid enters de-heavy hydrocarbon tower 15, de-weight
Hydrocarbon tower tower bottom product enters heavy hydrocarbon tank 16 and caches, or returns post-reactor through lighter hydrocarbons injector 7.Tower top is for producing
Product diesel oil or diesel component.Dry gas enters dry gas system 18 power generation and heat supply or sends outside.Filling in post-reactor 9
Polymerization catalyst, air speed 0.5-2h-1.In post-reactor 9, the most unreacted methanol continues reaction, control
Temperature 200-300 DEG C processed, air speed is relatively low to guarantee that post-reactor outlets products is without methanol.In post-reactor,
Also complete low-carbon alkene etherificate, overlap, crack, be hydrogenated with, alkylation, the process such as isomerization.Each product
Yield as shown in table 1.
Embodiment described above is only to be described, the preferred embodiment of the present invention not to the present invention
Scope be defined, on the premise of designing spirit without departing from the present invention, those of ordinary skill in the art couple
Various deformation that technical scheme is made and improvement, all should fall into what claims of the present invention determined
In protection domain.
Table 1 product forms
| Composition | Embodiment 1 | Embodiment 2 |
| Dry gas | 2.8% | 2.0% |
| Gasoline | 41.0% | |
| Diesel oil | 41.8% | |
| Water | 56.2% | 56.2% |
| Add up to | 100% | 100% |
Claims (5)
1. the reaction unit of a methanol hydrocarbon, it is characterised in that by methanol feedstock pump (1), methanol injector (2),
Main injector (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 edema caused by disorder of QI
From system (12), booster (13), de-lighter hydrocarbons tower (14), de-heavy hydrocarbon tower (15), heavy hydrocarbon surge tank (16),
Product gasoline tank (17), dry gas system (18) forms；
The outlet of described methanol feedstock pump (1) is leaded up to methanol injector (2) and is connected with main injector (3),
Another road connects pre-injector (5) through heat-exchange system (10)；The arrival end of pre-reactor (4) connects and draws in advance
Emitter (5), the port of export one tunnel returns pre-injector (5), and another road connects the entrance of main injector (3)；
The outlet of main reactor (6) is divided into two-way, and a road returns methanol injector (2), separately leads up to rear injection
Device (8) is connected with post-reactor (9)；The outlet of post-reactor (9) is through heat-exchange system (10) and oil
Water vapor separation system (12) connects；Oil-water-gas piece-rate system (12) outlet point three tunnels, aqueous phase connects at water
Reason system (11), dry gas is returned rear injector (8), another part dry gas warp by lighter hydrocarbons injector (7) injection
Cross dry gas system (18) power generation and heat supply or send outside, the boosted pump of liquid phase oil (13) and de-lighter hydrocarbons tower (14)
Connecting, de-lighter hydrocarbons tower (14) tower top connects lighter hydrocarbons injector (7), connects de-at the bottom of de-lighter hydrocarbons tower (14) tower
Heavy hydrocarbon tower (15), de-heavy hydrocarbon tower (15) tower top connects product gasoline storage tank (17), connects heavy hydrocarbon and delay at the bottom of tower
Rush tank (16).
2. a process for methanol hydrocarbon, comprises the following steps:
(1) the pre-reaction stage: pre-reaction system includes pre-injector, pre-reactor, from the first of heat-exchange system
Alcohol steam as the working fluid of pre-injector, the portion of product of injection pre-reactor outlet, loop back pre-instead
Answering device, the product part after there is etherification reaction in pre-reactor is looped back pre-reactor by pre-injector
Entrance, mixes with methanol steam and makes methanol steam be superheated to reaction temperature entrance methyltertiarvbutyl ether reactor, another part
Product, first as the working fluid of main injector, laggard becomes owner of response system；
(2) the primary response stage: primary response system is made up of main injector, main reactor, methanol injector；Methanol
The working fluid of injector is from material benzenemethanol pump, and the part of methanol injector injection main reactor outlet is produced
Thing, enters main injector, and Posterior circle returns main reactor, and the primary response stage occurs dimethyl ether and methanol to generate low
Carbon olefin and the reaction of water, the polymerization of part low-carbon alkene and aromatisation etc. are reacted；
(3) post-reaction period: rear response system includes rear injector, post-reactor, lighter hydrocarbons injector, heat exchange system
System, oil-water-gas 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；Post-reactor is used to complete aromatisation, aromatic disproportion, alkane further
Base, the process such as overlapping.
The process of methanol hydrocarbon the most according to claim 2, it is characterised in that pre-reaction system anti-
Answering temperature to be 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 primary response system is 160-420 DEG C, and reaction velocity is 1-70h-1, reaction pressure is
0.2-3.0MPa, recycle ratio is 2-20；
The reaction temperature of rear response system is 160-420 DEG C, and reaction velocity is 0.5-10h-1, reaction pressure is
0.2-3.0MPa, recycle ratio is 1-20.
The process of methanol hydrocarbon the most 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 primary response system is 260-350 DEG C, and reaction velocity is 2-10h-1, reaction pressure is
1.2-2.4MPa, recycle ratio is 3-6；
The reaction temperature of rear response system is 300-400 DEG C, and reaction velocity is 1-2h-1, reaction pressure is
1.2-2.2MPa, recycle ratio is 3-5.
The process of methanol hydrocarbon the most according to claim 2, it is characterised in that described post-reactor
Outlets products is lowered the temperature through heat-exchange system, enters oil-water-gas piece-rate system, the component liquid of more than C3 that will contain
Changing and separate, enter de-lighter hydrocarbons tower after making its supercharging with booster, overhead components C3-C4 is through lighter hydrocarbons injector
Looping back rear response system, heavy constituent enters de-heavy hydrocarbon tower, and tower top is gasoline component, enters product gasoline tank,
C10 and above heavy aromatics component in heavy gasoline components containing durol are looped back by lighter hydrocarbons injector
Rear response system, be disproportionated after mixing with newly-generated low-carbon alkene, light aromatic hydrocarbons etc., cracking etc. reacts raw
Become C9 and following light aromatic hydrocarbons, become boiling point, condensation point is qualified and octane number is high gasoline component, heavy gasoline components
In low octane rating C9 above alkane component generation cracking reaction generate higher octane below C9 hydrocarbon become
Specification gasoline component, constantly circulates thus realizes not by-product heavy gasoline components.
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| US4689205A (en) * | 1985-05-14 | 1987-08-25 | Mobil Oil Corporation | Multi-stage system for converting oxygenates to liquid hydrocarbons with aliphatic recycle |
| CN101802138A (en) * | 2007-09-21 | 2010-08-11 | 卢尔吉有限公司 | Method and installation for the production of hydrocarbons |
| CN102190546A (en) * | 2010-03-03 | 2011-09-21 | 中国石油化工股份有限公司 | Method for preparing propylene and aromatic hydrocarbon by virtue of conversion of methanol |
| CN103254924A (en) * | 2013-03-28 | 2013-08-21 | 中国海洋石油总公司 | Technological process for synthesizing gasoline from methanol by multistage cold shock method |
| CN205953924U (en) * | 2016-06-20 | 2017-02-15 | 马延春 | Reaction unit of methyl alcohol system hydrocarbon |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113274951A (en) * | 2021-05-21 | 2021-08-20 | 济南隆凯能源科技有限公司 | Double-steam injection circulating hydrocarbon partial oxidation system and method |
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