CN110420603A - Composite heat-exchange combines fixed bed methanol hydrocarbon reaction system - Google Patents
Composite heat-exchange combines fixed bed methanol hydrocarbon reaction system Download PDFInfo
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- CN110420603A CN110420603A CN201910741017.5A CN201910741017A CN110420603A CN 110420603 A CN110420603 A CN 110420603A CN 201910741017 A CN201910741017 A CN 201910741017A CN 110420603 A CN110420603 A CN 110420603A
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- heat
- fixed bed
- methanol
- catalyst bed
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- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 314
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 147
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 137
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 123
- -1 methanol hydrocarbon Chemical class 0.000 title claims abstract description 65
- 239000002131 composite material Substances 0.000 title claims abstract description 31
- 239000003054 catalyst Substances 0.000 claims abstract description 177
- 239000000047 product Substances 0.000 claims abstract description 83
- 239000013589 supplement Substances 0.000 claims abstract description 23
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 150000002430 hydrocarbons Chemical class 0.000 claims description 76
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 49
- 239000000463 material Substances 0.000 claims description 32
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 16
- 238000006555 catalytic reaction Methods 0.000 claims description 15
- 239000012530 fluid Substances 0.000 claims description 13
- 230000008676 import Effects 0.000 claims description 11
- 239000004411 aluminium Substances 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- 239000000945 filler Substances 0.000 claims description 10
- 229910052573 porcelain Inorganic materials 0.000 claims description 10
- 229910000975 Carbon steel Inorganic materials 0.000 claims description 5
- 239000010962 carbon steel Substances 0.000 claims description 5
- 239000004519 grease Substances 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 239000007787 solid Substances 0.000 abstract description 34
- 238000012546 transfer Methods 0.000 abstract description 28
- 239000003208 petroleum Substances 0.000 abstract description 4
- 239000003245 coal Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 238000004134 energy conservation Methods 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 230000005619 thermoelectricity Effects 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 81
- 238000000034 method Methods 0.000 description 42
- 230000008569 process Effects 0.000 description 29
- 239000003921 oil Substances 0.000 description 26
- 239000003502 gasoline Substances 0.000 description 18
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 10
- 229960004217 benzyl alcohol Drugs 0.000 description 10
- 238000012545 processing Methods 0.000 description 10
- 238000000926 separation method Methods 0.000 description 10
- 239000007795 chemical reaction product Substances 0.000 description 9
- 239000008187 granular material Substances 0.000 description 9
- 238000002347 injection Methods 0.000 description 9
- 239000007924 injection Substances 0.000 description 9
- 238000011084 recovery Methods 0.000 description 9
- 238000005338 heat storage Methods 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- 239000007790 solid phase Substances 0.000 description 8
- 230000004087 circulation Effects 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 150000001336 alkenes Chemical class 0.000 description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 238000012423 maintenance Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000009825 accumulation Methods 0.000 description 3
- 238000004939 coking Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- ULSIYEODSMZIPX-UHFFFAOYSA-N phenylethanolamine Chemical compound NCC(O)C1=CC=CC=C1 ULSIYEODSMZIPX-UHFFFAOYSA-N 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000005899 aromatization reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000000112 cooling gas Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 150000003839 salts Chemical class 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
- 239000002028 Biomass Substances 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- SQNZJJAZBFDUTD-UHFFFAOYSA-N durene Chemical compound CC1=CC(C)=C(C)C=C1C SQNZJJAZBFDUTD-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/009—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping in combination with chemical reactions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
- B01D3/32—Other features of fractionating columns ; Constructional details of fractionating columns not provided for in groups B01D3/16 - B01D3/30
- B01D3/322—Reboiler specifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/0278—Feeding reactive fluids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
- B01J8/0446—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical
- B01J8/0461—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical in two or more cylindrical annular shaped beds
- B01J8/0469—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical in two or more cylindrical annular shaped beds the beds being superimposed one above the other
-
- 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
- C10G3/54—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids characterised by the catalytic bed
-
- 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
- C10G2400/30—Aromatics
-
- 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
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of composite heat-exchanges to combine fixed bed methanol hydrocarbon reaction system, combination fixed bed is formed by setting up major catalyst bed and supplement catalyst bed in main reactor, solid conductive heat part heat exchange structure is set in radial flow major catalyst bed, the direct mixed heat transfer of injector system, form composite heat-exchange mode, it realizes the high efficient heat exchanging between product and raw material, controls the temperature of reactor bed.Apparatus cost is low, occupied area is small, and operating cost is low, highly-safe.The reaction unit energy conservation and environmental protection is suitable for coal chemical industry, petroleum and petrochemical industry, thermoelectricity industry etc..
Description
Technical field
The invention belongs to a kind of reaction units of preparing hydrocarbon products by methanol conversion.Specifically refer to be with methanol or crude carbinol
Raw material produces the reaction system of the hydrocarbon products such as fuel components, alkene, the aromatic hydrocarbons such as hydrocarbon mixture, belongs to coal chemical industry or gas chemical industry
Field.
Background technique
Disclosing the information of the background technology part, it is only intended to increase understanding of the overall background of the invention, without certainty
It is considered as recognizing or implying in any form that information composition has become existing skill well known to persons skilled in the art
Art.
By catalytic process appropriate, methanol can be converted into water and a variety of hydrocarbon products, 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.
Methanol feedstock is from a wealth of sources, and coal, petroleum, natural gas, biomass etc. can utilize methanol due to producing methanol
Instead of the petrochemical materials such as the fuel components such as Petroleum Production gasoline, diesel and alkene aromatic hydrocarbons, there is weight for world oil supply security
Want meaning.
It is typical methanol hydrocarbon technology that methanol, which converts gasoline (MTG) technology processed, is invented by Mobil company.From 1974
It rises, the said firm has applied for that multinomial related methanol converts the patent of gasoline processed.
Methanol-to-olefins (MTO, MTP), the techniques such as methanol aromatic hydrocarbons (MTA) have been realized in industrialization.
Methanol hydrocarbon process is an exothermic process, how to control the emphasis that reaction temperature is process concern.Around temperature
Control problem is spent, has developed kinds of processes and its reaction system, the form of existing reaction system includes insulation fix bed, multitube
Formula fixed bed, multistage cold shock fixed bed, moving bed, fluidized bed etc..
United States Patent (USP) 3931349 is that the methanol of Mobil company alerting bulletin converts the patent of hydro carbons processed, using fixed bed two
Section conversion process, wherein first segment reaction is preparing dimethyl ether by dewatering methanol, one section outlet material, including methanol, dimethyl ether and water
Mixture gasoline fraction section product is generated under the action of molecular sieve catalyst into second stage reactor.
United States Patent (USP) 4579999 then discloses the skill that another two-stage method methanol converts gasoline fraction section hydrocarbon products processed
Art loads molecular sieve catalyst in one section reactor, methanol is first converted into low-carbon alkene and part hydrocarbon, by C5+It is cooling
After separation, low-carbon alkene enters second stage reactor, under the action 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 conversion of methanol multi-stage.The technology of the patent disclosure with
United States Patent (USP) 4579999 is substantially similar, and in first stage reactor, 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 generates further is polymerized to the hydrocarbon product of gasoline fraction.The difference is that the skill of the patent disclosure
In art, first segment is using 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, compared with two-step method, has the advantages that process flow is short.Reaction system itself is tied
Structure is simple, and with gas phase hydrocarbon loop control reaction temperature, recycle ratio is big, and heat-exchange system and separation system investment are big, and power consumption is big.
Product is gasoline, liquefied gas and heavy petrol etc..
Application No. is 200720101511.8 utility model patents to propose a kind of preparing gasoline by methanol reaction of cold shocking type
Device, controls reaction temperature by the way of the cooling gas such as nitrogen are added between grade, and product is gasoline, liquefied gas and fuel gas, not
Refer to the power resources for recycling cooling gas.
Fluidized-bed process is characterized in the three phases of the reaction process of preparing gasoline by methanol are complete in fluidized-bed reactor
At.It can effectively solve the problems, such as to cool down using fluid bed process, but fluidized-bed structure is complicated, cost is high, and catalyst abrasion is big, urges
Agent powder is difficult to separate, and operating cost is high.
Absorbing reaction is hot as a heat transfer medium and produces steam, but fused salt heat exchange system with fused salt for existing multi-tubular reactor
Structure is complicated, and system start and stop are difficult, and equipment investment is big.
Insulation fix bed reactor, structure is simple, is easy to amplify, be widely applied.In order to control catalyst bed temperature
Degree, existing insulation fix bed reactor have by the way of recycle hydrocarbons and methanol feedstock mixed feeding.Reaction product is through changing
It is sent after hot device is cooling to oil water separator, after dry gas, oil, water separation, liquid phase oil product is further divided into product, pair through distillation system
Product, recycle hydrocarbons etc..Recycle hydrocarbons need to return again to reactor inlet after compressor boost heats.Recycle ratio up to 5-20 times,
Therefore, in whole device, including reaction, heat exchange, separation, purification whole treatment processes in, object including recycle hydrocarbons
Expect that treating capacity is 10 times or so of material benzenemethanol, be 20 times of product gasoline or so, produces the methanol vapour of 10 10,000 tons gasoline per year
Oily device, the specification investment of separation and purification equipment are equivalent to the petroleum base refinery of megaton.Device power consumption is big, heat exchange amount
Greatly, high equipment cost.It is connected between reactor product outlet and product exchanger with heavy caliber high pressure high temperature valve and flange etc.,
Durings parking, starting, operation, regeneration etc., temperature, pressure variation range is big, high temperature and pressure flammable explosive gas risk of leakage
Greatly, safety, sealing maintenance workload are big.
In order to reduce the power consumption and equipment investment of methanol hydrocarbon device, the present inventor is in patent of invention " ejection circulation
The methanol hydrocarbon method and device of fractional order reaction substep adjustment ", (patent No.: 201610438258.9), provide a kind of injection
The methanol hydrocarbon method and device of circulation classification reaction substep adjustment, has target product yield high, power consumption is low, and equipment is thrown
Provide low feature.The invention includes 3 sections of reactors, high-temperature product heat exchanger and 5 sets of injector systems.Engineering practice and into one
Step the study found that the power consumption of the device is greatly lowered, and product yield mentions compared to traditional fixed-bed reactor
Height, but still there are probelem in two aspects, first there is debugging difficulty in device, wherein being main original using more set injectors
Cause.Secondly maintenance workload is big, is primarily due to use multistage reactor, high-temperature product heat exchanger and covers injector more, needs
The components such as the higher high-temperature high pressure valve of many prices, flange, although bore is reduced relative to conventional apparatus, quantity
Increase, under the different operating conditions such as device starting, operation, parking, regeneration, the range of temperature of these high temperature and pressure components can
With from room temperature to 550 DEG C or more, pressure can be more than from normal pressure to 3.0 megapascal, and temperature, pressure variation range is big, seal request
Height, maintenance workload are big.
In conclusion methanol hydrocarbon is compared with strong exothermal reaction, controlling reaction temperature is that methanol process for producing hydrocarbons has to examine
The problem of worry.Fixed-bed reactor is widely used methanol hydrocarbon device.The methanol hydrocarbon such as existing fluidized bed, fixed bed
The problems such as that there is power consumptions is big for reaction system, and equipment investment is big.
Summary of the invention
In order to overcome the above problem, the present invention provides a kind of composite heat-exchanges to combine fixed bed methanol hydrocarbon reaction system.
The existing existing methanol of methanol process for producing hydrocarbons is solved by using the combination fixed bed methanol hydrocarbon reaction system of composite heat-exchange mode
Power consumption present in hydrocarbon reaction system processed is big, the big problem of equipment investment.
To realize the above-mentioned technical purpose, The technical solution adopted by the invention is as follows:
A kind of composite heat-exchange combination fixed bed methanol hydrocarbon reaction system, comprising: fixed bed, rectifying column 8, the fixed bed
The first caching room 3 is followed successively by shell 17 from top to bottom, catalyst bed 5, second caches room 20, medial compartment 19, supplement catalysis
Agent bed 18；The catalyst bed 5 is symmetrical arranged relative to the nozzle 4 that the first caching room 3 exports, the catalyst bed 5
Import and the second caching room 20 between be additionally provided with heat-conducting piece 22, the material outlet and 8 tower of rectifying column of the fixed bed bottom
Bottom reboiler 14, oil water separator 12 are sequentially connected, and the oil water separator 12 utilizes system 11 and water with dry gas caching respectively
Processing system 13 is connected.
The study found that in the reaction process of existing fixed bed methanol hydrocarbon, methanol in catalyst bed, first into
Row etherificate and the process for generating low-carbon alkene, on HZSM-5 catalyst, this process can be higher when temperature is more than 200 DEG C
Air speed carry out, and release most of reaction heat, this process is in the relatively thin catalyst bed of the arrival end of catalyst bed
It can be completed.The second half section of catalyst bed, processes, the thermal discharges such as mainly the reaction was continued to ensure unreacted methanol are smaller.
In the case where needing the conditions such as aromatic hydrocarbon product or temperature and catalyst to permit, aromatization process is completed.
Using this feature of methanol hydrocarbon reaction, the present invention is by the catalyst bed of fixed bed methanol hydrocarbon reaction system
Be divided into two parts: combination fixed bed methanol hydrocarbon reaction is collectively formed in major catalyst bed and supplement catalysts bed
System.Wherein, major catalyst bed mainly completes Fast exothermic reaction, without because to consider to ensure that methanol conversion is brought
The problem of, bed can suitably be thinned, and be conducive to simplify temperature control device structure.Lower reaction temperature is controlled, to slow down
Coking.Supplement catalyst bed mainly ensures the conversion ratio of methanol, because thermal discharge is small, can not have to that additional temperature control is arranged
Device processed simplifies structure.
In some embodiments, above-mentioned heat-conducting piece 22 is located at 5 inside of major catalyst bed and entrance side.
The present invention is inside major catalyst bed and entrance side sets up solid heat storage heat-conducting piece, is partially inhaled by catalyst granules
The reaction heat of receipts passes through the thermal contact conductance and solid conductive heat of solid heat transfer part, by the solid of the heat guiding entrance of catalyst granules
Accumulation of heat heat-conducting piece；The thermal contact conductance that part passes through the solid heat transfer part into catalyst bed by the reaction heat that reaction product absorbs
And solid conductive heat, also by the solid heat storage heat-conducting piece of heat guiding entrance.Constantly flow through major catalyst bed inside and entrance side
The material benzenemethanol of solid heat storage heat-conducting piece, which is heated to after reaction temperature, starts exothermic heat of reaction into catalyst bed.It product and urges
Catalyst particles temperature increases, and conducts heat to heat transfer piece, and heat transfer piece conducts heat to material benzenemethanol again.
In some embodiments, heat exchanger 23 is provided between the feed pipe of the methanol feedstock and the first caching room 3.
Methanol feedstock from raw material pump 1 is by inlet valve 2, via 23 heat temperature raising of heat exchanger being built in the first caching room 3
High-speed flow is formed by the ejection of raw material nozzles 4, injection first caches the hot product gases in room 3, enters after mixed heat transfer
Major catalyst bed inlet side second caches room 20, becomes owner of catalyst bed, reaction using 22 heat temperature raising of heat-conducting piece is laggard
Heat release, catalyst granules and heat-conducting piece 22 of a part of reaction heat through major catalyst bed are for heating reactant.Another part
Reaction heat carries out major catalyst bed by product.Major catalyst bed outlets products, a part via major catalyst bed outside
Outer passage of heat 21 between side and the inner wall of reactor shell 17, into the first caching room 3.Another part is via medial compartment 19
Reactor shell 17 is discharged after into supplement catalyst bed reaction, through product valve 16, exchanges heat into rectifying column tower bottom reboiler
After cooling, into grease gas separating device 12, the water separated enters water treatment system 13, and C2 or less dry gas enters dry-gas recovery
Utilize system 11, C3+The above fraction enters rectifying column via liquid hydrocarbon pump 10, isolates product and enters products pot 6, liquefied gas enters
Liquid gas storage tank 7, tower top dry gas 9 enter dry-gas recovery and utilize system 9, and tower bottom heavy hydrocarbon enters heavy hydrocarbon tank 15.
In some embodiments, it is provided between 5 outside of major catalyst bed and the inner wall of reactor shell 17 outer
Passage of heat 21 (that is: gas passage).The present invention arranges major catalyst bed using radial flow, to shorten solid conductive heat way
Diameter reduces thermal resistance.Reaction raw materials enter catalyst bed, after reaction, the effluent outside catalyst bed on the inside of catalyst bed
Out.The reaction product of outflow is divided into two-way, all the way after supplement catalyst bed completes reaction, carries the discharge of part reaction heat
Reaction system, into separation system, remaining a small amount of reaction heat radiation loss.Another way through on the outside of major catalyst bed with react
Channel between device shell enters injector arrival end caching interior, is exchanged heat by injector heat exchanger and material benzenemethanol, into one
Step further passes through major catalyst bed with the material benzenemethanol mixed heat transfer from injector nozzle by injector injection
After entrance side solid heat storage heat-conducting piece is heated to reaction temperature, reacted into major catalyst bed.
In some embodiments, it is provided between the liquid hydrocarbon outlet and the feed inlet of rectifying column 8 of the oil water separator 12
Liquid hydrocarbon pump 10.
In some embodiments, 8 discharge port of rectifying column is connected with products pot 6.C3+The above fraction is via liquid hydrocarbon pump 10
It is pumped into rectifying column, isolates product (account for about total hydrocarbon products 80%) into products pot 6.
In some embodiments, the exhaust outlet of 8 tower top of rectifying column is connected with dry gas caching using 11 air inlet of system.
C2 or less dry gas (account for about total hydrocarbon products 1%) enters dry-gas recovery and utilizes system 11.
In some embodiments, the 8 tower bottom leakage fluid dram of rectifying column is connected with 15 inlet of heavy hydrocarbon tank.Tower bottom heavy hydrocarbon is (about
The 5% of the total hydrocarbon products of Zhan) enter heavy hydrocarbon tank 15.
In some embodiments, the material of the heat-conducting piece 22 includes but is not limited to porcelain ball filler, carbon steel, stainless steel, aluminium
Material.It is preferred that thermal coefficient is high, moderate aluminium.
The present invention also provides any above-mentioned composite heat-exchange combination fixed bed methanol hydrocarbon reaction systems in methanol hydrocarbon
In application.
The beneficial effects of the present invention are:
(1) the advantage of the invention is that power consumption is small, equipment investment is low.
(2) present invention eliminates the larger gas compressors of power consumption of existing methanol hydrocarbon device, using injector pair
Recyclegas pressurization, methanol solution mutually pressurize, and power consumption is greatly reduced.
(3) present invention eliminates the outer loop hydrocarbon system of existing methanol hydrocarbon device and its heat-exchange system, separation system,
Refining system, the circulatory system, equipment investment are greatly lowered.
(4) for the present invention using a set of built-in injector system, reaction system is stable and reliable in work, is easy to debug.
(5) injector of the invention is built in inside reactor, compared with being mounted on outside reactor, external pressure in injector
Difference is small, low to intensity and toughness sealing requirements, convenient for manufacture, is easily installed, and is not required to setting insulating layer.Gas flow resistance is small,
It is evenly distributed.
(6) the required recyclegas of the present invention is flowed in inside reactor leading portion major catalyst bed inner-outer circulation, back segment
The flow of catalyst bed is much smaller than existing reaction system, and catalyst use efficiency is high.
(7) the required recyclegas of the present invention is flowed in inside reactor leading portion catalyst bed inner-outer circulation, and existing
Reaction process is compared, the oil-water separation system outside reactor, and distillation system recycles the flow of the hydrocarbon vaporate superheating system significantly
It reduces, equipment investment is greatly lowered, and energy source and power consumption is greatly reduced.
(8) present invention is by being placed in one for high temperature services such as high-temperature heat-exchanging, two-stage catalytic agent bed, injector systems
In reactor enclosure body, solves prior art and sealing caused by heavy-caliber high-temperature high pressure valve, high temperature and pressure flange is needed to want
Ask high, the big problem of maintenance workload improves the safety of device.
(9) system structure of the application is simple, operating cost is low, has universality, is easy to large-scale production.
Detailed description of the invention
The accompanying drawings constituting a part of this application is used to provide further understanding of the present application, and the application's shows
Meaning property embodiment and its explanation are not constituted an undue limitation on the present application for explaining the application.
Fig. 1 is that the composite heat-exchange of embodiment 1 combines fixed bed methanol hydrocarbon reaction system.
Wherein, raw material pump 1, inlet valve 2, the first caching room 3, heat exchanger 23, raw material nozzles 4, catalyst bed 5, product
Tank 6, liquefied gas storage 7, rectifying column 8, the top of the distillation column dry gas 9, liquid hydrocarbon pump 10, dry gas caching utilize system 11, oil-water-gas point
From device 12, water treatment system 13, heat exchanger 14, heavy hydrocarbon 15, product valve 16, reactor shell 17 supplements catalyst bed 18,
Medial compartment 19, catalyst bed entrance side second cache room 20, outer passage of heat 21, heat-conducting piece 22, interior passage of heat 45.
Specific embodiment
It is noted that following detailed description is all illustrative, it is intended to provide further instruction to the application.Unless another
It indicates, all technical and scientific terms used in this application have logical with the application person of an ordinary skill in the technical field
The identical meanings understood.
It should be noted that term used herein above is merely to describe specific embodiment, and be not intended to restricted root
According to the illustrative embodiments of the application.As used herein, unless the context clearly indicates otherwise, otherwise singular
Also it is intended to include plural form, additionally, it should be understood that, when in the present specification using term "comprising" and/or " packet
Include " when, indicate existing characteristics, step, operation, device, component and/or their combination.
As background technique is introduced, for the methanol hydrocarbon reaction such as current fluidized bed, fixed bed system there is
The problems such as power consumption is big, and equipment investment is big.Therefore, the present invention proposes a kind of composite heat-exchange combination fixed bed methanol hydrocarbon reaction
System.
The study found that in the reaction process of existing fixed bed methanol hydrocarbon, methanol in catalyst bed, first into
Row etherificate and the process for generating low-carbon alkene, on HZSM-5 catalyst, this process can be higher when temperature is more than 200 DEG C
Air speed carry out, and release most of reaction heat, this process is in the relatively thin catalyst bed of the arrival end of catalyst bed
It can be completed.The second half section of catalyst bed, processes, the thermal discharges such as mainly the reaction was continued to ensure unreacted methanol are smaller.
In the case where needing the conditions such as aromatic hydrocarbon product or temperature and catalyst to permit, aromatization process is completed.
Using this feature of methanol hydrocarbon reaction, the present invention is by the catalyst bed of fixed bed methanol hydrocarbon reaction system
Be divided into two parts: combination fixed bed methanol hydrocarbon reaction is collectively formed in major catalyst bed and supplement catalysts bed
System.Wherein, major catalyst bed mainly completes Fast exothermic reaction, without because to consider to ensure that methanol conversion is brought
The problem of, bed can suitably be thinned, and be conducive to simplify temperature control device structure.Lower reaction temperature is controlled, to slow down
Coking.Supplement catalyst bed mainly ensures the conversion ratio of methanol, because thermal discharge is small, can not have to that additional temperature control is arranged
Device processed simplifies structure.
The study found that the reaction heat of methanol hydrocarbon is about 1.7-1.8MJ/kg, methanol is superheated to by 25 DEG C of heating evaporations
300 DEG C of methanol gas, institute calorific requirement about 1.7MJ/kg.Methanol gas starts on HZSM-5 catalyst at 200 DEG C or less
Exothermic heat of reaction, at 300 DEG C or more, reaction rate is higher.480 DEG C of general control catalyst bed hot(test)-spot temperature or less.It is existing
The insulation fix bed typical data of methanol hydrocarbon: 340 DEG C of catalyst bed inlet temperature, recycle ratio 10,400 DEG C of outlet temperature.
Methanol hydrocarbon reaction heat can also make Liquid Phase Methanol evaporation be superheated to reaction temperature or more.
Therefore, methanol can be evaporated using methanol hydrocarbon reaction heat and is superheated to reaction temperature；Alternatively, methanol was evaporated
Heat needed for heat to reaction temperature can be realized by absorbing methanol hydrocarbon reaction heat.
During methanol hydrocarbon, material benzenemethanol is before entering reaction system, and absorption is provided by heating device first
Heat up hot Q1, and by room temperature (such as 25 DEG C), heat absorption evaporation is superheated to reaction temperature (such as 300 DEG C), enters catalyst bed afterwards,
Start exothermic heat of reaction in catalyst bed, temperature increases, and after completing reaction, reaction product leaves reaction system with higher temperature
System.Under stationary conditions, reaction bed temperature will remain substantially stable, and reaction heat Q2 and the hot Q1 that heats up are both needed to removal system,
To maintain the stable operation of system.
The hot Q2 of methanol hydrocarbon reaction is larger, simulation calculation shows that, adiabatic temperature rise is more than 600K, existing methanol hydrocarbon catalysis
In agent, temperature is excessively high, the side reactions such as methanol decomposition reaction will occur, general control temperature is at 480 DEG C hereinafter, needing to mix circulation
Hydrocarbon is to control temperature rise.It is exported in present reactor, recycle hydrocarbons and newly-increased reaction product jointly again take Q1 and Q2 out of.
In existing methanol process for producing hydrocarbons device, for reaction system, material benzenemethanol was evaporated by room temperature liquid phase
Heat needed for heat to reaction temperature is first to be added by dividing wall type heat exchanger, then have product and recycle hydrocarbons to take out of.Q2 is reaction
Heat, it is necessary to take reaction system out of to maintain the stabilization of reaction system temperature, generally also by being passed through by product and recycle hydrocarbons
Dividing wall type heat exchanger trans-utilization.
The heat exchange mode of existing methanol process for producing hydrocarbons mainly uses liquid phase gaseous fluid medium dividing wall type heat exchanger to exchange heat,
A large amount of fluid circulations are repeatedly completed the processes such as boosting, decompression, heating, cooling, evaporation, overheat, condensation, mixing, separation, purification,
So power consumption is big, power-equipment, heat exchange equipment investment are big.
The present invention uses composite heat-exchange mode, and the mode including increasing solid dielectric thermal contact conductance share solves existing main
Big, the big problem of equipment investment by power consumption brought by fluid media (medium) heat transfer.
Signified solid-phase media of the invention includes but is not limited to catalyst, filler porcelain ball, internals, reactor shell, heat transfer
The component of the solid phases such as component.Between solid phase components interior and the solid phase component to contact with each other, direction of heat flow is always from high temperature dot
It is directed toward low-temperature region.In methanol hydrocarbon reactor, including conducting heat from the high temperature dot of catalyst granules itself to low-temperature region；From
High temperature catalyst particle is to the low temperature catalyst particle heat transfer directly contacted；Heat transfer from from catalyst granules to filler porcelain ball, from
Heat transfer of the porcelain ball to internals, the heat transfer to reactor shell.Total heat-transfer effect includes urging from catalyst bed against airflow direction
The heat transfer of agent bed inlet end further to arrival end filler, sieve, pressing plate heat transfer, and is conducted heat to the methanol feedstock gas flowed through.
This phenomenon is existing in existing methanol hydrocarbon reactor, but heat flow rate per unit area is weak, is not realized utilization.The present invention passes through
The mode of enhancing solid dielectric transmission of heat by contact intensity is taken, the share of solid dielectric back reaction fluid flow direction heat transfer is increased,
The temperature control mode of the gas-solids such as ejection circulation combination heat exchange, achievees the purpose that control reaction temperature inside binding reactor.
The mode of solid-phase media thermal contact conductance hardly needs power, solves bulk gas inside and outside present reactor and recycles
The problem that power consumption is big, equipment investment is big brought by hydrocarbon heat transfer.
Solid-phase media and Liquid Phase Methanol, gas-phase methanol, reaction product is immiscible to be changed in a manner of direct thermal contact conductance
Hot coefficient is big, solves the problems, such as that equipment investment brought by existing recycle hydrocarbons temperature control method is big.
The study found that in the reaction system of methanol hydrocarbon, the solid phases such as catalyst, filler porcelain ball, internals, reactor shell
Component volume specific heat be hundreds times to thousand times of the methanol gas of gas phase and its volume specific heat of product water and hydrocarbon mixture with
On.This shows that gas-phase product once passes through catalyst bed, and catalyst bed can't be made to have obvious temperature rise, meanwhile, because of gas
The mutual heat exchange of the solid-phase constructions such as phase product and catalyst, the temperature rise of gas-phase product also will receive inhibition.Product, which once passes through, urges
The temperature of agent bed, product and catalyst slightly increases, and temperature rise is little.When being mixed with inert circulating air in product, reaction
Heat round-trip transmitting mutually between product, circulating air, catalyst bed different location, is redistributed.It is exported in catalyst bed,
The mixed gas of product and circulating air leaves catalyst bed with the state for being higher than inlet temperature, and recycle ratio is smaller, and temperature rise is higher.
In cold start, catalyst bed outlet temperature is gradually risen, and under stationary conditions, compares entrance, catalyst bed outlet
Also there is temperature rise, outlet temperature keeps stablizing.
The present invention is inside major catalyst bed and entrance side sets up solid heat storage heat-conducting piece, is partially inhaled by catalyst granules
The reaction heat of receipts passes through the thermal contact conductance and solid conductive heat of solid heat transfer part, by the solid of the heat guiding entrance of catalyst granules
Accumulation of heat heat-conducting piece；The reaction heat that part is absorbed by reaction product by the thermal contact conductance of the solid heat transfer part in catalyst bed and
Solid conductive heat, also by the solid heat storage heat-conducting piece of heat guiding entrance.It constantly flows through inside major catalyst bed and entrance side is solid
The material benzenemethanol of body accumulation of heat heat-conducting piece, which is heated to after reaction temperature, starts exothermic heat of reaction into catalyst bed.Product and catalysis
Agent particle temperature increases, and conducts heat to heat transfer piece, and heat transfer piece conducts heat to material benzenemethanol again.
The material of solid heat storage heat-conducting piece includes but is not limited to porcelain ball filler, carbon steel, stainless steel, aluminium etc., preferably thermally conductive
Coefficient is high, moderate aluminium.
The present invention arranges major catalyst bed using radial flow, to shorten solid conductive heat approach, reduces thermal resistance.Reaction is former
Material enters catalyst bed on the inside of catalyst bed, after reaction, flows out from catalyst bed outside.The reaction product of outflow point
It carries part reaction heat all the way after supplement catalyst bed completes reaction for two-way and reaction system is discharged, into segregative line
System, remaining a small amount of reaction heat radiation loss.Another way through the channel on the outside of major catalyst bed between reactor shell into
It is indoor to enter injector arrival end caching, is exchanged heat by injector heat exchanger and material benzenemethanol, further by injector injection, and comes
From in the material benzenemethanol mixed heat transfer of injector nozzle, further pass through major catalyst bed entrance side solid heat storage heat-conducting piece
After being heated to reaction temperature, reacted into major catalyst bed.
The present invention ensures exchange capability of heat using injector complex solid heat-conducting mode built in reactor.Injector is to utilize to penetrate
Turbulent diffusion is flowed, fluid machinery and mix reaction equipment that mass transfer passes energy are carried out.High pressure draught is sprayed from nozzle at high speeds, is drawn
The low-pressure gas around nozzle is penetrated, two strands of air-flows are mixed in mixing chamber and diffuser, are pressurized, and are consuming certain high-pressure work
Under conditions of gas, the low-pressure gas pressure for entering injector from suction inlet is improved, this equipment is known as jet pump.Workflow
Body is come out with very high speed from nozzle, into the receiving chamber of injector, and the lower medium belt of pressure before injector
It walks.The fluid being pulled away is driving fluid, improves the pressure of driving fluid without directly consuming mechanical energy, this is that injector is most main
The performance wanted.Due to this property, in many cases, using injector than using mechanical supercharging equipment (compressor,
Pump, air blower and air-introduced machine etc.) it is more simple, more reliable.Other than this body structure is extremely simple, injector is set with various
The method of standby connection is also very simple, and manufacture is also uncomplicated, is widely applied in engineering.
Methanol feedstock from raw material pump 1 is by inlet valve 2, via the heat exchanger 23 being built in the first caching room 3
High-speed flow is formed through the ejection of raw material nozzles 4 after heat temperature raising, injection first caches the hot product gases in room 3, and mixing is changed
Heat it is laggard becomes owner of catalyst bed inlet side second cache room 20, using after 22 heat temperature raising of heat-conducting piece enter major catalyst bed
Layer, exothermic heat of reaction, catalyst granules and heat-conducting piece 22 of a part of reaction heat through major catalyst bed are for heating reactant.Separately
A part of reaction heat carries out major catalyst bed by product.Major catalyst bed outlets products, a part is via major catalyst
Outer passage of heat 21 on the outside of bed between the inner wall of reactor shell 17, into the first caching room 3.Another part is in
Discharge reactor shell 17 is boiled through product valve 16 into rectifying tower bottom again after compartment 19 enters supplement catalyst bed reaction
After device heat exchange is cooling, into grease gas separating device 12, the water separated enters water treatment system 13, and C2 or less dry gas enters dry
Gas recycling system 11, C3+The above fraction enters rectifying column via liquid hydrocarbon pump 10, isolates product and enters products pot 6, liquefies
Gas enters liquid gas storage tank 7, and tower top dry gas 9 enters dry-gas recovery and utilizes system 9, and tower bottom heavy hydrocarbon enters heavy hydrocarbon tank 15.
Heat-conducting piece 22 can preferentially use metal material, including use sieve using filler porcelain ball, metal material etc.,
Plate, the forms such as pipe are carried out in conjunction with the manufacture and installation of internals.Laminated construction, catalyst bed are formed between heat-conducting piece and catalyst
Inert filler porcelain ball, wire, the structure types such as sheet metal are loaded in mixture in layer.
It is illustrated below by way of technical solution of the specific embodiment to the application.
Embodiment 1, preparing gasoline by methanol component, liquefied gas and heavy gasoline components.
About solid conductive heat system, the embodiment of heat-conducting piece 22: facade and interior side elevation are used on the outside of major catalyst bed
Metallic sieve to shield and sustain catalyst bed, and reduces gas flow resistance.Top and bottom are closed with metal plate, and have reinforcement
Structure is connect with reactor shell.Using annular carbon steel plate or aluminium disks as main heat-conducting piece, catalyst bed and annular
Aluminium disks alternative stacked, by adjusting catalyst bed thickness and along the distribution of radial direction, aluminium dish thickness and radius etc. because
Element, it is available to meet the thermo parameters method needed.
Selection about injection heat-exchange system designs, and heat is passed through heat exchanger 23 by the high-temperature gas in the first caching room 3
The working fluid material benzenemethanol in injector system is delivered heat to, material benzenemethanol is made to heat up, also increases the ability to work of injector,
And itself cools down and cools down and be also beneficial to improve the mass ratio of induced-to-inducing air of injector.It, can be with by increasing the exchange capability of heat of heat exchanger 23
The injection ratio of injector is improved, but the cost of heat exchanger 23 can increase.Optimize heat-conducting piece structure, increases solid conductive heat institute
Share is accounted for, the requirement of 23 exchange capability of heat of heat exchanging device can be reduced, reduces cost.
Methanol feedstock after heat temperature raising forms high-speed flow through the ejection of raw material nozzles 4, and high-speed flow enters broadening formation
After the pressurization of channel reduction of speed, enter catalyst bed 5 from the interior passage of heat 45 of the entrance side of catalyst bed, meanwhile, catalyst
After the heat-conducting piece 22 absorbing reaction heat of 5 entrance side of bed, which is passed to the air-flow of entrance side, then, air-flow warp
The main part that interior passage of heat 45 passes through catalyst bed 5 is reacted, and finally, is excluded by 5 outlet side of catalyst bed.
The heat-conducting piece 22 passes through closed processes, after making gas that can only pass through 5 main body of catalyst bed, by catalyst bed
The discharge of 5 outlet sides.
The center of the catalyst bed 5 is the channel (diameter gradually changes from small to big) of broadening formation, and the broadening formation is logical
The side wall in road is the entrance side of catalyst bed 5, and the outermost (close to the side of fixed bed shell) of the catalyst bed is
The outlet side of catalyst bed 5.
Injector refers in the application: the structure that the channel of nozzle 4 and broadening formation forms.
The solid conductive heat of the application is not limited in the heat-conducting piece 22 of catalyst bed, constitutes the interior thermally conductive of catalyst bed
Each component of the solid-states connections such as channel, partition, floor, and corresponding fixed bed shell, caching room all can serve as heat-conducting piece
22 extension promotes the export of reaction heat.
Wherein, interior 45 hollow type of passage of heat design can effectively guarantee that the heat between heat of reaction and heat-conducting piece 22 is handed over
Efficiency is changed, control reaction temperature, the purpose of slow down coking are reached.
By the way of solid conductive heat and injector system composite heat-conducting, methanol hydrocarbon device catalyst bed can satisfy
Temperature controlled needs.Solid conductive heat and the heat exchange share of injector mixed heat transfer can also appropriate adjustments.Increase solid conductive heat
Share can reduce the heat exchange area of heat exchanger 23, it might even be possible to save heat exchanger 23.
From the methanol feedstock of raw material pump 1, pressure 1.3-1.5Mpa, temperature is 25 DEG C -- 30 DEG C, pass through inlet valve
2, through raw material nozzles 4 with 1.2- after being heated to 150 DEG C -160 DEG C via the heat exchanger 23 being built in the first caching room 3
The pressure of 1.4Mpa sprays, and forms high-speed flow, it is 0.9-1.0Mpa, temperature 300 that injection first, which caches the pressure in room 3,
DEG C -- 310 DEG C of hot product gases, it is 1.1-1.3Mpa that pressure is formed after mixed heat transfer, and temperature is 200 DEG C -- 250 DEG C mixed
It closes gas and enters the caching of major catalyst bed inlet side second room 20, be heated to 300 DEG C -320 DEG C using heat-conducting piece 22
It is laggard to become owner of catalyst bed 5, exothermic heat of reaction, a part of catalyst particles of the reaction heat (10%-15%) through major catalyst bed 5
Grain and heat-conducting piece 22 are for heating reactant.Another part reaction heat (80%-90%) carries out major catalyst bed by product.
It is 0.9-1.0Mpa that major catalyst bed outlets products, which are pressure, and temperature is 350 DEG C -- 450 DEG C of hot product gases, one
Divide (80%-90%) via the outer passage of heat 21 on the outside of major catalyst bed between the inner wall of reactor shell 17, enters
First caching room 3.Another part (10%-20%) enters after supplement catalyst bed 18 reacts to be discharged via medial compartment 19 to react
Device shell 17, heat of reaction part pass to reactor shell 17, and reaction product pressure is 0.9-1.0Mpa, temperature 380
DEG C -- 460 DEG C of hot product gases exchange heat into rectifying column tower bottom reboiler (i.e. heat exchanger 14) and cool down through product valve 16
Afterwards, into grease gas separating device 12, the water separated enters water treatment system 13, and C2 or less dry gas (accounts for about total hydrocarbon products
1%) enter dry-gas recovery and utilize system 11, C3+The above fraction is pumped into rectifying column via liquid hydrocarbon pump 10, isolates product and (accounts for about
The 80% of total hydrocarbon products) enter products pot 6, liquefied gas (account for about total hydrocarbon products 13%) enters liquid gas storage tank 7, tower top dry gas 9
(account for about total hydrocarbon products 1%) enter dry-gas recovery and utilize system 9, tower bottom heavy hydrocarbon (account for about total hydrocarbon products 5%) enters heavy hydrocarbon
Tank 15.
Compared with existing fixed bed preparing gasoline by methanol process unit, powerful circulating air compressor, power are eliminated
Consumption is greatly lowered.Heat exchanger number and total heat exchange area are greatly lowered, and equipment investment is greatly lowered.
Embodiment 2
Methanol BTX aromatics.Referring to attached drawing 1, methanol is reacted with light aromatic hydrocarbons, can produce more alkylaromatic hydrocarbons, e.g., front three
Base benzene, durol etc..As industrial chemicals, added value is higher than gasoline.Increase dividing in major catalyst bed for heat-conducting piece 22
Cloth density increases the share of solid conductive heat, can simplify heat exchanger 23.
From the methanol feedstock of raw material pump 1, pressure 2.5-2.6Mpa, temperature is 25 DEG C -- 30 DEG C, pass through inlet valve
2, it is sprayed via through raw material nozzles 4 with the pressure of 2.5-2.6Mpa, forms high speed methanol aerosol stream, injection first caches in room 3
Pressure be 1.0-1.2Mpa, temperature is 380 DEG C -- 450 DEG C of hot product gases, it is 1.2- that pressure is formed after mixed heat transfer
1.4Mpa, temperature are 150 DEG C -- 200 DEG C of mixed gas enters major catalyst bed inlet side second and caches room 20, using
Heat-conducting piece 20 is heated to 310 DEG C -350 DEG C and laggard becomes owner of catalyst bed, exothermic heat of reaction, a part of reaction heat (10%-
15%) catalyst granules and heat-conducting piece 22 through major catalyst bed are for heating reactant.Another part reaction heat (80%-
90%) major catalyst bed is carried out by product.It is 1.1-1.3Mpa that major catalyst bed outlets products, which are pressure, and temperature is
360 DEG C -- 460 DEG C of hot product gases, a part of (80%-90%) is via major catalyst bed outside and reactor shell
Outer passage of heat 21 between 17 inner wall, into the first caching room 3.Another part (10%-20%) via medial compartment 19 into
Reactor shell 17 is discharged after entering to supplement catalyst bed reaction, heat of reaction part passes to reactor shell 17, and reaction produces
Object pressure is 1.0-1.1Mpa, and temperature is 380 DEG C -- 480 DEG C of hot product gases, through product valve 16, into rectifying tower bottom
After reboiler (i.e. heat exchanger 14) heat exchange is cooling, into grease gas separating device 12, the water separated enters water treatment system 13,
C2 or less dry gas (account for about total hydrocarbon products 1%) enters dry-gas recovery and utilizes system 11, C3+The above fraction is via 10 pump of liquid hydrocarbon pump
Enter rectifying column, isolates mixing light aromatic hydrocarbons product (account for about total hydrocarbon products 60%) and enter products pot 6, mixed light-hydrocarbon (accounts for about total
The 12% of hydrocarbon products) enter liquid gas storage tank 7, tower top dry gas 9 (account for about total hydrocarbon products 2%) enters dry-gas recovery and utilizes system 9,
Tower bottom mixes heavy aromatics (account for about total hydrocarbon products 25%) and enters heavy hydrocarbon tank 15.
Compared with existing fixed bed methanol aromatics process device, powerful circulating air compressor, power are eliminated
Consumption is greatly lowered.Heat exchanger number and total heat exchange area are greatly lowered, and equipment investment is greatly lowered.
Embodiment 3
A kind of composite heat-exchange combination fixed bed methanol hydrocarbon reaction system, comprising: fixed bed, rectifying column 8, the fixed bed
The first caching room 3 is followed successively by shell 17 from top to bottom, catalyst bed 5, second caches room 20, medial compartment 19, supplement catalysis
Agent bed 18；The catalyst bed 5 is symmetrical arranged relative to the nozzle 4 that the first caching room 3 exports, the catalyst bed 5
Import and the second caching room 20 between be additionally provided with heat-conducting piece 22, the material outlet and 8 tower of rectifying column of the fixed bed bottom
Bottom reboiler 14, oil water separator 12 are sequentially connected, and the oil water separator 12 utilizes system 11 and water with dry gas caching respectively
Processing system 13 is connected.
Embodiment 4
A kind of composite heat-exchange combination fixed bed methanol hydrocarbon reaction system, comprising: fixed bed, rectifying column 8, the fixed bed
The first caching room 3 is followed successively by shell 17 from top to bottom, catalyst bed 5, second caches room 20, medial compartment 19, supplement catalysis
Agent bed 18；The catalyst bed 5 is symmetrical arranged relative to the nozzle 4 that the first caching room 3 exports, the catalyst bed 5
Import and the second caching room 20 between be additionally provided with heat-conducting piece 22, the material outlet and 8 tower of rectifying column of the fixed bed bottom
Bottom reboiler 14, oil water separator 12 are sequentially connected, and the oil water separator 12 utilizes system 11 and water with dry gas caching respectively
Processing system 13 is connected.
The heat-conducting piece 22 is located at 5 inside of major catalyst bed and entrance side.
Embodiment 5
A kind of composite heat-exchange combination fixed bed methanol hydrocarbon reaction system, comprising: fixed bed, rectifying column 8, the fixed bed
The first caching room 3 is followed successively by shell 17 from top to bottom, catalyst bed 5, second caches room 20, medial compartment 19, supplement catalysis
Agent bed 18；The catalyst bed 5 is symmetrical arranged relative to the nozzle 4 that the first caching room 3 exports, the catalyst bed 5
Import and the second caching room 20 between be additionally provided with heat-conducting piece 22, the material outlet and 8 tower of rectifying column of the fixed bed bottom
Bottom reboiler 14, oil water separator 12 are sequentially connected, and the oil water separator 12 utilizes system 11 and water with dry gas caching respectively
Processing system 13 is connected.
Heat exchanger 23 is provided between the feed pipe of the methanol feedstock and the first caching room 3.
Embodiment 6
A kind of composite heat-exchange combination fixed bed methanol hydrocarbon reaction system, comprising: fixed bed, rectifying column 8, the fixed bed
The first caching room 3 is followed successively by shell 17 from top to bottom, catalyst bed 5, second caches room 20, medial compartment 19, supplement catalysis
Agent bed 18；The catalyst bed 5 is symmetrical arranged relative to the nozzle 4 that the first caching room 3 exports, the catalyst bed 5
Import and the second caching room 20 between be additionally provided with heat-conducting piece 22, the material outlet and 8 tower of rectifying column of the fixed bed bottom
Bottom reboiler 14, oil water separator 12 are sequentially connected, and the oil water separator 12 utilizes system 11 and water with dry gas caching respectively
Processing system 13 is connected.
Outer passage of heat 21 is provided between 5 outside of major catalyst bed and the inner wall of reactor shell 17.
Embodiment 7
A kind of composite heat-exchange combination fixed bed methanol hydrocarbon reaction system, comprising: fixed bed, rectifying column 8, the fixed bed
The first caching room 3 is followed successively by shell 17 from top to bottom, catalyst bed 5, second caches room 20, medial compartment 19, supplement catalysis
Agent bed 18；The catalyst bed 5 is symmetrical arranged relative to the nozzle 4 that the first caching room 3 exports, the catalyst bed 5
Import and the second caching room 20 between be additionally provided with heat-conducting piece 22, the material outlet and 8 tower of rectifying column of the fixed bed bottom
Bottom reboiler 14, oil water separator 12 are sequentially connected, and the oil water separator 12 utilizes system 11 and water with dry gas caching respectively
Processing system 13 is connected.
The liquid hydrocarbon of the oil water separator 12 is exported is provided with liquid hydrocarbon pump 10 between the feed inlet of rectifying column 8.
Embodiment 8
A kind of composite heat-exchange combination fixed bed methanol hydrocarbon reaction system, comprising: fixed bed, rectifying column 8, the fixed bed
The first caching room 3 is followed successively by shell 17 from top to bottom, catalyst bed 5, second caches room 20, medial compartment 19, supplement catalysis
Agent bed 18；The catalyst bed 5 is symmetrical arranged relative to the nozzle 4 that the first caching room 3 exports, the catalyst bed 5
Import and the second caching room 20 between be additionally provided with heat-conducting piece 22, the material outlet and 8 tower of rectifying column of the fixed bed bottom
Bottom reboiler 14, oil water separator 12 are sequentially connected, and the oil water separator 12 utilizes system 11 and water with dry gas caching respectively
Processing system 13 is connected.
8 discharge port of rectifying column is connected with products pot 6.
Embodiment 9
A kind of composite heat-exchange combination fixed bed methanol hydrocarbon reaction system, comprising: fixed bed, rectifying column 8, the fixed bed
The first caching room 3 is followed successively by shell 17 from top to bottom, catalyst bed 5, second caches room 20, medial compartment 19, supplement catalysis
Agent bed 18；The catalyst bed 5 is symmetrical arranged relative to the nozzle 4 that the first caching room 3 exports, the catalyst bed 5
Import and the second caching room 20 between be additionally provided with heat-conducting piece 22, the material outlet and 8 tower of rectifying column of the fixed bed bottom
Bottom reboiler 14, oil water separator 12 are sequentially connected, and the oil water separator 12 utilizes system 11 and water with dry gas caching respectively
Processing system 13 is connected.
The exhaust outlet of 8 tower top of rectifying column is connected with dry gas caching using 11 air inlet of system.C2 or less dry gas (accounts for about
The 1% of total hydrocarbon products) enter dry-gas recovery and utilizes system 11.
Embodiment 10
A kind of composite heat-exchange combination fixed bed methanol hydrocarbon reaction system, comprising: fixed bed, rectifying column 8, the fixed bed
The first caching room 3 is followed successively by shell 17 from top to bottom, catalyst bed 5, second caches room 20, medial compartment 19, supplement catalysis
Agent bed 18；The catalyst bed 5 is symmetrical arranged relative to the nozzle 4 that the first caching room 3 exports, the catalyst bed 5
Import and the second caching room 20 between be additionally provided with heat-conducting piece 22, the material outlet and 8 tower of rectifying column of the fixed bed bottom
Bottom reboiler 14, oil water separator 12 are sequentially connected, and the oil water separator 12 utilizes system 11 and water with dry gas caching respectively
Processing system 13 is connected.
The 8 tower bottom leakage fluid dram of rectifying column is connected with 15 inlet of heavy hydrocarbon tank.Tower bottom heavy hydrocarbon (account for about total hydrocarbon products 5%)
Into heavy hydrocarbon tank 15.
Embodiment 11
A kind of composite heat-exchange combination fixed bed methanol hydrocarbon reaction system, comprising: fixed bed, rectifying column 8, the fixed bed
The first caching room 3 is followed successively by shell 17 from top to bottom, catalyst bed 5, second caches room 20, medial compartment 19, supplement catalysis
Agent bed 18；The catalyst bed 5 is symmetrical arranged relative to the nozzle 4 that the first caching room 3 exports, the catalyst bed 5
Import and the second caching room 20 between be additionally provided with heat-conducting piece 22, the material outlet and 8 tower of rectifying column of the fixed bed bottom
Bottom reboiler 14, oil water separator 12 are sequentially connected, and the oil water separator 12 utilizes system 11 and water with dry gas caching respectively
Processing system 13 is connected.
The material of the heat-conducting piece 22 includes but is not limited to porcelain ball filler, carbon steel, stainless steel, aluminium.It is preferred that thermal coefficient
Height, moderate aluminium.
Finally it should be noted that the foregoing is only a preferred embodiment of the present invention, it is not limited to this hair
It is bright, although the present invention is described in detail referring to the foregoing embodiments, for those skilled in the art, still
It can modify to technical solution documented by previous embodiment, or part is equivalently replaced.It is all in this hair
Within bright spirit and principle, any modification, equivalent replacement, improvement and so on should be included in protection scope of the present invention
Within.Above-mentioned, although specific embodiments of the present invention have been described, and it is not intended to limit the protection scope of the present invention, institute
Category field technical staff should be understood that based on the technical solutions of the present invention those skilled in the art do not need to pay wound
The various modifications or changes that the property made labour can be made are still within protection scope of the present invention.
Claims (10)
1. a kind of composite heat-exchange combines fixed bed methanol hydrocarbon reaction system characterized by comprising fixed bed, rectifying column, institute
It states and is followed successively by the first caching room, catalyst bed, the second caching room, medial compartment, supplement catalysis in fixed bed shell from top to bottom
Agent bed；The catalyst bed is symmetrical arranged relative to the nozzle of the first caching room outlet, the import of the catalyst bed
Heat-conducting piece, the material outlet and rectifying column tower bottom reboiler, oil of the fixed bed bottom are additionally provided between the second caching room
Separator is sequentially connected, and the oil water separator is connected with dry gas caching using system and water treatment system respectively.
2. composite heat-exchange as described in claim 1 combines fixed bed methanol hydrocarbon reaction system, which is characterized in that above-mentioned thermally conductive
Part is located inside major catalyst bed and entrance side.
3. composite heat-exchange as described in claim 1 combines fixed bed methanol hydrocarbon reaction system, which is characterized in that the methanol
Heat exchanger is provided between the feed pipe of raw material and the first caching room.
4. composite heat-exchange as described in claim 1 combines fixed bed methanol hydrocarbon reaction system, which is characterized in that the main reminder
Outer passage of heat is provided between the inner wall of reactor shell on the outside of agent bed.
5. composite heat-exchange as described in claim 1 combines fixed bed methanol hydrocarbon reaction system, which is characterized in that the grease
The liquid hydrocarbon of separator is exported is provided with liquid hydrocarbon pump between the feed inlet of rectifying column.
6. composite heat-exchange as described in claim 1 combines fixed bed methanol hydrocarbon reaction system, which is characterized in that the rectifying
Tower discharge port is connected with products pot.
7. composite heat-exchange as described in claim 1 combines fixed bed methanol hydrocarbon reaction system, which is characterized in that the rectifying
The exhaust outlet of column overhead is connected with dry gas caching using system air inlet.
8. composite heat-exchange as described in claim 1 combines fixed bed methanol hydrocarbon reaction system, which is characterized in that the rectifying
Tower tower bottom leakage fluid dram is connected with heavy hydrocarbon tank inlet.
9. composite heat-exchange as described in claim 1 combines fixed bed methanol hydrocarbon reaction system, which is characterized in that described thermally conductive
The material of part includes but is not limited to porcelain ball filler, carbon steel, stainless steel, aluminium.
10. the described in any item composite heat-exchange combination fixed bed methanol hydrocarbon reaction systems of claim 1-9 are in methanol hydrocarbon
Application.
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