CN107345148A - C4The method and apparatus that cut synthesizes high octane gasoline component with formaldehyde - Google Patents

C4The method and apparatus that cut synthesizes high octane gasoline component with formaldehyde Download PDF

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Publication number
CN107345148A
CN107345148A CN201710549080.XA CN201710549080A CN107345148A CN 107345148 A CN107345148 A CN 107345148A CN 201710549080 A CN201710549080 A CN 201710549080A CN 107345148 A CN107345148 A CN 107345148A
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China
Prior art keywords
cut
component
formaldehyde
high octane
reaction
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Inventor
唐清松
薛真真
张培杰
商红岩
崔春涛
姜翠玉
罗立文
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Ordos Easy To Petrochemical Technology Co Ltd
China University of Petroleum East China
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Ordos Easy To Petrochemical Technology Co Ltd
China University of Petroleum East China
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Priority to CN201710549080.XA priority Critical patent/CN107345148A/en
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    • 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
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • C10G3/48—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
    • C10G3/49—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support containing crystalline aluminosilicates, e.g. molecular sieves
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1088—Olefins
    • C10G2300/1092—C2-C4 olefins
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/30—Physical properties of feedstocks or products
    • C10G2300/305—Octane number, e.g. motor octane number [MON], research octane number [RON]
    • 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

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The present invention relates to gasoline synthesis method and apparatus, specially C4The method and apparatus that cut synthesizes high octane gasoline component with formaldehyde, solves existing C at present4The problem of utilization rate of alkene is low in cut, scheme：1）, by C4Cut in a device, nitrogen and solid acid catalyst condition, controls feed space velocity, reaction temperature, conversion zone pressure, reflux ratio, tower top temperature, bottom temperature reaction with formaldehyde；2）, tower top obtain unreacted light component, tower reactor obtains mixing hydrocarbon high octane gasoline component；3）, the recycling of tower top light component continued to react or produces；4）, tower reactor component output, obtain mix hydrocarbon antiknock component.Advantage：1st, C is rationally utilized4Alkene resource in cut, improve the oil-refining chemical performance of enterprises；2nd, raw material is provided for related industries development；3rd, can be with the C of positive structure4Alkene acts on, by C after ether4Reacted as raw material and participate in reaction, can be with deep exploitation C4Alkene resource.

Description

C4The method and apparatus that cut synthesizes high octane gasoline component with formaldehyde
Technical field
The present invention relates to gasoline synthesis method and apparatus, specially C4Cut synthesizes high octane gasoline component with formaldehyde Method and apparatus.
Background technology
In recent years, Domestic Automotive Industry development is at full speed, and the product oil of annual newly-increased automobile consumption is equivalent to newly-built one The oil plant of 2000 tons.Therefore, the refining capacity in China is being continuously increased, and refining capacity in 2015 is more than 700,000,000 tons, together When oil plant C4The yield of cut reaches 30,000,000 tons.C4Alkene in cut is important industrial chemicals, using just, isobutene A variety of chemical products can be produced.At present, C4Isobutene in cut it is most widely used be and methanol reaction generation methyl- tert fourth Base ether（MTBE）.Using isobutene as raw material, occur just with methanol under acidic catalyst (polystyrolsulfon acid resin) effect Carbon ion reaction generation MTBE.After etherification technology or resin hydrating process make full use of isobutene, C4Cut remaining ingredient Middle n-butene it is dense, be mostly used for oxidative dehydrogenation butadiene, cis-butenedioic anhydride, MEK.The main application of 2- butylene utilizes Indirect alkylation technology:（1）Gasoline alkylate is produced, this is the main application of 2- butylene, accounts for 90 % of 2- butylene dosages； (2) by 2- butylene and ethylene production propylene.
Current domestic C4The utilization of alkene resource is still in the starting stage in cut, and utilization rate only has 16%, wherein chemical industry profit With rate less than 3%.In recent years, in C4In cut in the utilization of alkene, in addition to butadiene, other components are generally as common combustion Material burn-up, cause the significant wastage of resource.Rationally utilize C4Alkene resource in cut, oil-refining chemical enterprise can not only be improved Industry benefit, moreover it is possible to provide the raw material of preciousness for the development of related industries.With the change of fossil resources general layout, C4Alkene in cut Resource is more and more valuable, improves C4The utilization rate of alkene is extremely urgent in cut.
The content of the invention
The present invention solves existing C at present4A kind of the problem of utilization rate of alkene is low in cut, there is provided C4Cut and formaldehyde The method and apparatus for synthesizing high octane gasoline component.
The present invention is realized by following operating procedure：C4Cut synthesizes the side of high octane gasoline component with formaldehyde Method, realized by following operating procedure：1）, by containing 1- butylene, 2- butylene, three kinds of active components of isobutene C4Cut With formaldehyde according to mol ratio 3:1~8:1, by being pumped into catalysis reaction rectifying device, keeps nitrogen atmosphere, in solid acid catalysis Under the conditions of agent, it is 0.1h to control raw material volume air speed-1~4h-1, reaction temperature is 70 DEG C ~ 150 DEG C, and conversion zone pressure is 0.1MPa ~ 2MPa, reflux ratio 1-10, tower top temperature are 30-60 DEG C, and bottom temperature is 100-170 DEG C and reacted；2）, tower top obtains Unreacted light component, tower reactor obtain mixing hydrocarbon high octane gasoline component；3）, by step 2）Obtained tower top is light Component, which is recycled in catalysis reaction rectifying device, to be continued reaction or directly produces to be C4Cut uses；4）, step 2）Obtain Tower reactor component is exported by pump, obtains mixing hydrocarbon antiknock component.The present invention replaces methanol and C using formaldehyde4Alkene Etherification reaction occurs for hydrocarbon., not only can be with the C of isomery because the activity of formaldehyde is very high4Alkene acts on, can also be with the C of positive structure4 Alkene acts on, and methanol and C4The etherification of alkene is only the same as the C of isomery4Alkene acts on, therefore technology road provided by the invention Line can also utilize methanol and C4Cut reaction generation methyl tertiary butyl ether(MTBE)（MTBE）C after the completion of reaction4Cut（That is C after ether4） Reacted as raw material and participate in reaction, can be with deep exploitation C4Alkene resource, utilize C after Reaction Separation recycling ether4In cut N-butene, to improving China C4The utilization rate of cut has great importance.
The formaldehyde is the formalin or metaformaldehyde of mass concentration 37% ~ 85%.The catalysis reaction rectifying device Theoretical cam curve is 10-60 blocks.The solid acid catalyst is macropore strong acid cation exchanger resin, molecular sieve catalysis The mixing of one or more arbitrary proportions in agent, solid super acid catalyst or solid-carrying heteropolyacid catalyst.The macropore is strong Acid cation exchange resin is polystyrene macropore strong acid cation exchanger resin;Described molecular sieve catalysts be with ZSM-5 molecular sieve, H-Y molecular sieves, H- beta-molecular sieves, SBA-15 molecular sieves, one kind in MCM-41 or MCM-22 molecular sieves or several Modification or unmodified catalyst of the kind for carrier；Described solid super acid catalyst is SO4 2-/Fe2O3、SO4 2-/ZrO2、 SO4 2-/TiO2In one or more；The supported quantity of heteropoly acid is 2~20wt% in described solid-carrying heteropolyacid catalyst（Often The how many 2-20g heteropoly acids of 100g supported on carriers）, described heteropoly acid is phosphotungstic acid, in silico-tungstic acid, phosphomolybdic acid, silicomolybdic acid One or more, described carrier be ZSM-5 molecular sieve, H-Y molecular sieves, H- beta-molecular sieves, SBA-15 molecular sieves, MCM-41 or One or more in MCM-22 molecular sieve catalysts.
C4Cut synthesizes the device of high octane gasoline component, including catalytic rectifying column body with formaldehyde, on toward Under be followed successively by rectifying section column plate, catalyst reaction section, stripping section and tower reactor；The catalyst reaction section loads solid acid catalyst；Institute State catalyst reaction section and be provided with material inlet, C is connected with material inlet4Component, formaldehyde mixed material input pipe, tower top are provided with out Gas port, the gas outlet are connected with extraction pipeline, and circulation branch road is provided between the extraction pipeline and raw material input pipe；Bottom of towe is set The product for having product delivery outlet to obtain tower reactor is discharged by output pipe.
The present invention has advantages below：1st, C is rationally utilized4Alkene resource in cut, improve the oil-refining chemical performance of enterprises； 2nd, raw material is provided for related industries development；3rd, can be with the C of positive structure4Alkene acts on, by C after ether4Reacted as raw material and participate in reaction, Can be with deep exploitation C4Alkene resource.
Brief description of the drawings
Fig. 1 is C4Cut synthesizes the apparatus structure schematic diagram of high octane gasoline component with formaldehyde；
In figure：1- catalyst reaction sections, 2- tower reactors, 3- raw material input pipes, 4- extraction pipelines, 5- circulation branch roads.
Embodiment
The embodiment of technical solution of the present invention is described in detail below in conjunction with accompanying drawing.Following examples are only used for More clear explanation technical scheme, therefore be only used as example, without being limited the scope of the invention with this. Raw material formaldehyde and C4The reaction product structure of alkene is as shown in table 1：
The raw material formaldehyde of table 1 and C4The reaction product list of olefin component in cut
Embodiment one：
C4The method that cut synthesizes high octane gasoline component with formaldehyde, realized by following operating procedure：1）, will contain 1- butylene, 2- butylene, the C of three kinds of active components of isobutene4The formalin that cut and mass concentration are 37% is according to mol ratio 4: 1 by being pumped into the catalysis reaction rectifying device that theoretical cam curve is 12 pieces, and holding nitrogen atmosphere is strong in polystyrene macropore Under the conditions of acid cation exchange resin, it is 1h to control raw material volume air speed-1, reaction temperature is 140 DEG C, and conversion zone pressure is 1.5MPa, reflux ratio 6, tower top temperature are 45 DEG C, and bottom temperature is 170 DEG C and reacted；2）, tower top obtain it is unreacted light Component, tower reactor obtain mixing hydrocarbon high octane gasoline component；3）, by step 2）Obtained tower top light component recycling Continue reaction into catalysis reaction rectifying device or C is in directly extraction4Cut uses；4）, step 2）Obtained tower reactor component by Pump exports, and obtains mixing hydrocarbon antiknock component.The conversion ratio and gained hydrocarbon of C4 alkene and formaldehyde Octane number be shown in Table 2.
Embodiment two：
C4The method that cut synthesizes high octane gasoline component with formaldehyde, realized by following operating procedure：1）, will contain 1- butylene, 2- butylene, the C of three kinds of active components of isobutene4The formalin that cut and mass concentration are 45% is according to mol ratio 6: 1, by being pumped into the catalysis reaction rectifying device that theoretical cam curve is 53 pieces, keeps nitrogen atmosphere, with ZSM-5 molecular sieve Under the conditions of the modified catalyst of carrier, it is 0.1h to control raw material volume air speed-1, reaction temperature is 100 DEG C, and conversion zone pressure is 2MPa, reflux ratio 1, tower top temperature are 35 DEG C, and bottom temperature is 160 DEG C and reacted；2）, tower top obtain unreacted light group Point, tower reactor obtains mixing hydrocarbon high octane gasoline component；3）, by step 2）Obtained tower top light component is recycled to Continue reaction in catalysis reaction rectifying device or C is in directly extraction4Cut uses；4）, step 2）Obtained tower reactor component is by pump Output, obtain mixing hydrocarbon antiknock component.The conversion ratio and gained hydrocarbon of C4 alkene and formaldehyde Octane number is shown in Table 2.
Embodiment three：
C4The method that cut synthesizes high octane gasoline component with formaldehyde, realized by following operating procedure：1）, will contain 1- butylene, 2- butylene, the C of three kinds of active components of isobutene4The formalin that cut and mass concentration are 50% is according to mol ratio 5: 1 by being pumped into theoretical cam curve is in 23 pieces of catalysis reaction rectifying device, keeps nitrogen atmosphere, using H-Y molecular sieves as Under the catalysts conditions of the modification of carrier, it is 4h to control raw material volume air speed-1, reaction temperature is 85 DEG C, and conversion zone pressure is 0.8MPa, reflux ratio 3, tower top temperature are 55 DEG C, and bottom temperature is 115 DEG C and reacted；2）, tower top obtain it is unreacted light Component, tower reactor obtain mixing hydrocarbon high octane gasoline component；3）, by step 2）Obtained tower top light component recycling Continue reaction into catalysis reaction rectifying device or C is in directly extraction4Cut uses；4）, step 2）Obtained tower reactor component by Pump exports, and obtains mixing hydrocarbon antiknock component.The conversion ratio and gained hydrocarbon of C4 alkene and formaldehyde Octane number be shown in Table 2.
Example IV：
C4The method that cut synthesizes high octane gasoline component with formaldehyde, realized by following operating procedure：1）, will contain 1- butylene, 2- butylene, the C of three kinds of active components of isobutene4The formalin that cut and mass concentration are 85% is according to mol ratio 7: 1 by being pumped into theoretical cam curve is in 41 pieces of catalysis reaction rectifying device, keeps nitrogen atmosphere, using H- beta-molecular sieves as Under the unmodified catalysts conditions of carrier, it is 2.8h to control raw material volume air speed-1, reaction temperature is 150 DEG C, conversion zone pressure For 0.1MPa, reflux ratio 8, tower top temperature is 60 DEG C, and bottom temperature is 105 DEG C and reacted；2）, tower top obtain it is unreacted Light component, tower reactor obtain mixing hydrocarbon high octane gasoline component；3）, by step 2）Obtained tower top light component is followed again Ring continues reaction into catalysis reaction rectifying device or C is in directly extraction4Cut uses；4）, step 2）Obtained tower reactor component Exported by pump, obtain mixing hydrocarbon antiknock component.The conversion ratio and gained oxidation of coal of C4 alkene and formaldehyde close The octane number of thing is shown in Table 2.
Embodiment five：
C4The method that cut synthesizes high octane gasoline component with formaldehyde, realized by following operating procedure：1）, will contain 1- butylene, 2- butylene, the C of three kinds of active components of isobutene4The formalin that cut and mass concentration are 75% is according to mol ratio 8: 1, by being pumped into the catalysis reaction rectifying device that theoretical cam curve is 35 pieces, keeps nitrogen atmosphere, with SBA-15 molecular sieves Under catalysts conditions for the modification of carrier, it is 3h to control raw material volume air speed-1, reaction temperature is 70 DEG C, and conversion zone pressure is 0.3MPa, reflux ratio 10, tower top temperature are 32 DEG C, and bottom temperature is 100 DEG C and reacted；2）, tower top obtain it is unreacted Light component, tower reactor obtain mixing hydrocarbon high octane gasoline component；3）, by step 2）Obtained tower top light component is followed again Ring continues reaction into catalysis reaction rectifying device or C is in directly extraction4Cut uses；4）, step 2）Obtained tower reactor component Exported by pump, obtain mixing hydrocarbon antiknock component.The conversion ratio and gained oxidation of coal of C4 alkene and formaldehyde close The octane number of thing is shown in Table 2.
Embodiment six：
C4The method that cut synthesizes high octane gasoline component with formaldehyde, realized by following operating procedure：1）, will contain 1- butylene, 2- butylene, the C of three kinds of active components of isobutene4The formalin that cut and mass concentration are 55% is according to mol ratio 3: 1, by being pumped into the catalysis reaction rectifying device that theoretical cam curve is 60 pieces, keeps nitrogen atmosphere, with MCM-41 molecular sieves It is 1.5h under the unmodified catalysts conditions of carrier, to control raw material volume air speed-1, reaction temperature is 75 DEG C, conversion zone pressure Power is 1MPa, and reflux ratio 2, tower top temperature is 38 DEG C, and bottom temperature is 130 DEG C and reacted；2）, tower top obtain it is unreacted Light component, tower reactor obtain mixing hydrocarbon high octane gasoline component；3）, by step 2）Obtained tower top light component is followed again Ring continues reaction into catalysis reaction rectifying device or C is in directly extraction4Cut uses；4）, step 2）Obtained tower reactor component Exported by pump, obtain mixing hydrocarbon antiknock component.The conversion ratio and gained oxidation of coal of C4 alkene and formaldehyde close The octane number of thing is shown in Table 2.
Embodiment seven：
C4The method that cut synthesizes high octane gasoline component with formaldehyde, realized by following operating procedure：1）, will contain 1- butylene, 2- butylene, the C of three kinds of active components of isobutene4The formalin that cut and mass concentration are 60% is according to mol ratio 3.5:1, by being pumped into the catalysis reaction rectifying device that theoretical cam curve is 47 pieces, keeps nitrogen atmosphere, with MCM-22 points Under catalysts conditions of the son sieve for the modification of carrier, it is 2h to control raw material volume air speed-1, reaction temperature is 80 DEG C, conversion zone pressure Power is 1.2MPa, and reflux ratio 4, tower top temperature is 40 DEG C, and bottom temperature is 110 DEG C and reacted；2）, tower top obtain unreacted Light component, tower reactor obtain mix hydrocarbon high octane gasoline component；3）, by step 2）Obtained tower top light component is again It is recycled in catalysis reaction rectifying device and continues reaction or directly produce to be C4Cut uses；4）, step 2）Obtained tower reactor group Divide and exported by pump, obtain mixing hydrocarbon antiknock component.The conversion ratio and gained oxidation of coal of C4 alkene and formaldehyde The octane number of compound is shown in Table 2.
Embodiment eight：
C4The method that cut synthesizes high octane gasoline component with formaldehyde, realized by following operating procedure：1）, will contain 1- butylene, 2- butylene, the C of three kinds of active components of isobutene4The formalin that cut and mass concentration are 40% is according to mol ratio 4.5:1, by being pumped into the catalysis reaction rectifying device that theoretical cam curve is 18 pieces, keeps nitrogen atmosphere, in SO4 2-/Fe2O3 Under the conditions of solid super acid catalyst, it is 1.7h to control raw material volume air speed-1, reaction temperature is 130 DEG C, and conversion zone pressure is 1.8MPa, reflux ratio 9, tower top temperature are 57 DEG C, and bottom temperature is 163 DEG C and reacted；2）, tower top obtain it is unreacted light Component, tower reactor obtain mixing hydrocarbon high octane gasoline component；3）, by step 2）Obtained tower top light component recycling Continue reaction into catalysis reaction rectifying device or C is in directly extraction4Cut uses；4）, step 2）Obtained tower reactor component by Pump exports, and obtains mixing hydrocarbon antiknock component.The conversion ratio and gained hydrocarbon of C4 alkene and formaldehyde Octane number be shown in Table 2.
Embodiment nine：
C4The method that cut synthesizes high octane gasoline component with formaldehyde, realized by following operating procedure：1）, will contain 1- butylene, 2- butylene, the C of three kinds of active components of isobutene4The formalin that cut and mass concentration are 70% is according to mol ratio 6.5:1, by being pumped into the catalysis reaction rectifying device that theoretical cam curve is 29 pieces, keeps nitrogen atmosphere, in SO4 2-/ZrO2 Under the conditions of solid super acid catalyst, it is 3.5h to control raw material volume air speed-1, reaction temperature is 115 DEG C, and conversion zone pressure is 0.6MPa, reflux ratio 5, tower top temperature are 50 DEG C, and bottom temperature is 120 DEG C and reacted；2）, tower top obtain it is unreacted light Component, tower reactor obtain mixing hydrocarbon high octane gasoline component；3）, by step 2）Obtained tower top light component recycling Continue reaction into catalysis reaction rectifying device or C is in directly extraction4Cut uses；4）, step 2）Obtained tower reactor component by Pump exports, and obtains mixing hydrocarbon antiknock component.The conversion ratio and gained hydrocarbon of C4 alkene and formaldehyde Octane number be shown in Table 2.
Embodiment ten：
C4The method that cut synthesizes high octane gasoline component with formaldehyde, realized by following operating procedure：1）, will contain 1- butylene, 2- butylene, the C of three kinds of active components of isobutene4The formalin that cut and mass concentration are 65% is according to mol ratio 5.5:1, by being pumped into the catalysis reaction rectifying device that theoretical cam curve is 38 pieces, keeps nitrogen atmosphere, in SO4 2-/TiO2 Under the conditions of solid super acid catalyst, it is 0.4h to control raw material volume air speed-1, reaction temperature is 90 DEG C, and conversion zone pressure is 0.7MPa, reflux ratio 7, tower top temperature are 53 DEG C, and bottom temperature is 140 DEG C and reacted；2）, tower top obtain it is unreacted light Component, tower reactor obtain mixing hydrocarbon high octane gasoline component；3）, by step 2）Obtained tower top light component recycling Continue reaction into catalysis reaction rectifying device or C is in directly extraction4Cut uses；4）, step 2）Obtained tower reactor component by Pump exports, and obtains mixing hydrocarbon antiknock component.The conversion ratio and gained hydrocarbon of C4 alkene and formaldehyde Octane number be shown in Table 2.
Embodiment 11：
C4The method that cut synthesizes high octane gasoline component with formaldehyde, realized by following operating procedure：1）, will contain 1- butylene, 2- butylene, the C of three kinds of active components of isobutene4The formalin that cut and mass concentration are 80% is according to mol ratio 7.5:1, by being pumped into the catalysis reaction rectifying device that theoretical cam curve is 56 pieces, keeps nitrogen atmosphere, in immobilized phosphotungstic acid Under the conditions of, the supported quantity of the phosphotungstic acid is 2wt%, and it is 0.7h to control raw material volume air speed-1, reaction temperature is 125 DEG C, reaction Section pressure is 1.9MPa, and reflux ratio 3, tower top temperature is 30 DEG C, and bottom temperature is 150 DEG C and reacted；2）, tower top obtains not The light component of reaction, tower reactor obtain mixing hydrocarbon high octane gasoline component；3）, by step 2）Light group of obtained tower top Divide to be recycled in catalysis reaction rectifying device and continue reaction or directly produce to be C4Cut uses；4）, step 2）Obtained tower Kettle component is exported by pump, obtains mixing hydrocarbon antiknock component.The conversion ratio and gained carbon of C4 alkene and formaldehyde The octane number of oxygen compound is shown in Table 2.
Embodiment 12：
C4The method that cut synthesizes high octane gasoline component with formaldehyde, realized by following operating procedure：1）, will contain 1- butylene, 2- butylene, the C of three kinds of active components of isobutene4The formalin that cut and mass concentration are 58% is according to mol ratio 4.5:1, by being pumped into the catalysis reaction rectifying device that theoretical cam curve is 10 pieces, keeps nitrogen atmosphere, in immobilized silico-tungstic acid Under the conditions of, the supported quantity of the silico-tungstic acid is 20wt%, and it is 2.4h to control raw material volume air speed-1, reaction temperature is 135 DEG C, reaction Section pressure is 1.7MPa, and reflux ratio 6, tower top temperature is 48 DEG C, and bottom temperature is 125 DEG C and reacted；2）, tower top obtains not The light component of reaction, tower reactor obtain mixing hydrocarbon high octane gasoline component；3）, by step 2）Light group of obtained tower top Divide to be recycled in catalysis reaction rectifying device and continue reaction or directly produce to be C4Cut uses；4）, step 2）Obtained tower Kettle component is exported by pump, obtains mixing hydrocarbon antiknock component.The conversion ratio and gained carbon of C4 alkene and formaldehyde The octane number of oxygen compound is shown in Table 2.
Embodiment 13：
C4The method that cut synthesizes high octane gasoline component with formaldehyde, realized by following operating procedure：1）, will contain 1- butylene, 2- butylene, the C of three kinds of active components of isobutene4The formalin that cut and mass concentration are 43% is according to mol ratio 6.3:1, by being pumped into the catalysis reaction rectifying device that theoretical cam curve is 20 pieces, keeps nitrogen atmosphere, in immobilized phosphomolybdic acid Under the conditions of, the supported quantity of the phosphomolybdic acid is 10wt%, and it is 3.8h to control raw material volume air speed-1, reaction temperature is 145 DEG C, reaction Section pressure is 1.6MPa, and reflux ratio 8, tower top temperature is 43 DEG C, and bottom temperature is 135 DEG C and reacted；2）, tower top obtains not The light component of reaction, tower reactor obtain mixing hydrocarbon high octane gasoline component；3）, by step 2）Light group of obtained tower top Divide to be recycled in catalysis reaction rectifying device and continue reaction or directly produce to be C4Cut uses；4）, step 2）Obtained tower Kettle component is exported by pump, obtains mixing hydrocarbon antiknock component.The conversion ratio and gained carbon of C4 alkene and formaldehyde The octane number of oxygen compound is shown in Table 2.
Embodiment 14：
C4The method that cut synthesizes high octane gasoline component with formaldehyde, realized by following operating procedure：1）, will contain 1- butylene, 2- butylene, the C of three kinds of active components of isobutene4The formalin that cut and mass concentration are 48% is according to mol ratio 7.3:1, by being pumped into the catalysis reaction rectifying device that theoretical cam curve is 15 pieces, keeps nitrogen atmosphere, in immobilized silicomolybdic acid Under the conditions of, the supported quantity of the silicomolybdic acid is 6wt%, and it is 1.3h to control raw material volume air speed-1, reaction temperature is 95 DEG C, conversion zone Pressure is 1.4MPa, and reflux ratio 10, tower top temperature is 34 DEG C, and bottom temperature is 145 DEG C and reacted；2）, tower top obtains not The light component of reaction, tower reactor obtain mixing hydrocarbon high octane gasoline component；3）, by step 2）Light group of obtained tower top Divide to be recycled in catalysis reaction rectifying device and continue reaction or directly produce to be C4Cut uses；4）, step 2）Obtained tower Kettle component is exported by pump, obtains mixing hydrocarbon antiknock component.The conversion ratio and gained carbon of C4 alkene and formaldehyde The octane number of oxygen compound is shown in Table 2.
Embodiment 15：
C4The method that cut synthesizes high octane gasoline component with formaldehyde, realized by following operating procedure：1）, will contain 1- butylene, 2- butylene, the C of three kinds of active components of isobutene4The formalin that cut and mass concentration are 38% is according to mol ratio 8: 1, by being pumped into the catalysis reaction rectifying device that theoretical cam curve is 32 pieces, keeps nitrogen atmosphere, with ZSM-5 molecular sieve Under catalysts conditions of the SBA-15 molecular sieves for the modification of carrier, it is 1h to control raw material volume air speed-1, reaction temperature 130 DEG C, conversion zone pressure is 1.6MPa, and reflux ratio 4, tower top temperature is 38 DEG C, and bottom temperature is 110 DEG C and reacted；2）, tower Top obtains unreacted light component, and tower reactor obtains mixing hydrocarbon high octane gasoline component；3）, by step 2）Obtain Tower top light component, which is recycled in catalysis reaction rectifying device, to be continued reaction or directly produces to be C4Cut uses；4）, step 2） Obtained tower reactor component is exported by pump, obtains mixing hydrocarbon antiknock component.The conversion ratio of C4 alkene and formaldehyde with And the octane number of gained hydrocarbon is shown in Table 2.
Embodiment 16：
C4The method that cut synthesizes high octane gasoline component with formaldehyde, realized by following operating procedure：1）, will contain 1- butylene, 2- butylene, the C of three kinds of active components of isobutene4The formalin that cut and mass concentration are 60% is according to mol ratio 5.3:1, by being pumped into the catalysis reaction rectifying device that theoretical cam curve is 26 pieces, keeps nitrogen atmosphere, with H-Y molecules Sieve and MCM-41 molecular sieves is under the unmodified catalysts conditions of carrier, it are 3h to control raw material volume air speed-1, reaction temperature is 150 DEG C, conversion zone pressure is 0.4MPa, and reflux ratio 7, tower top temperature is 51 DEG C, and bottom temperature is 165 DEG C and reacted；2）、 Tower top obtains unreacted light component, and tower reactor obtains mixing hydrocarbon high octane gasoline component；3）, by step 2）Obtain Tower top light component be recycled in catalysis reaction rectifying device continue reaction or directly extraction be C4Cut uses；4）, step 2）Obtained tower reactor component is exported by pump, obtains mixing hydrocarbon antiknock component.The conversion ratio of C4 alkene and formaldehyde And the octane number of gained hydrocarbon is shown in Table 2.
Embodiment 17：
C4The method that cut synthesizes high octane gasoline component with formaldehyde, realized by following operating procedure：1）, will contain 1- butylene, 2- butylene, the C of three kinds of active components of isobutene4The formalin that cut and mass concentration are 75% is according to mol ratio 4: 1, by being pumped into the catalysis reaction rectifying device that theoretical cam curve is 44 pieces, keeps nitrogen atmosphere, in SO4 2-/TiO2With SO4 2-/ZrO2Under the conditions of solid super acid catalyst, it is 2h to control raw material volume air speed-1, reaction temperature is 115 DEG C, conversion zone Pressure is 0.2MPa, and reflux ratio 3.5, tower top temperature is 30 DEG C, and bottom temperature is 110 DEG C and reacted；2）, tower top obtains not The light component of reaction, tower reactor obtain mixing hydrocarbon high octane gasoline component；3）, by step 2）Light group of obtained tower top Divide to be recycled in catalysis reaction rectifying device and continue reaction or directly produce to be C4Cut uses；4）, step 2）Obtained tower Kettle component is exported by pump, obtains mixing hydrocarbon antiknock component.The conversion ratio and gained carbon of C4 alkene and formaldehyde The octane number of oxygen compound is shown in Table 2.
Embodiment 18：
C4The method that cut synthesizes high octane gasoline component with formaldehyde, realized by following operating procedure：1）, will contain 1- butylene, 2- butylene, the C of three kinds of active components of isobutene4The formalin that cut and mass concentration are 85% is according to mol ratio 7: 1, by being pumped into the catalysis reaction rectifying device that theoretical cam curve is 50 pieces, keeps nitrogen atmosphere, in immobilized silico-tungstic acid and admittedly Under the conditions of carrying silicomolybdic acid, the supported quantity of the silico-tungstic acid is 12wt%, and the supported quantity of the silicomolybdic acid is 16wt%, controls raw material body Product air speed is 3.3h-1, reaction temperature is 80 DEG C, and conversion zone pressure is 1.25MPa, and reflux ratio 5, tower top temperature is 55 DEG C, tower Kettle temperature degree is 155 DEG C and reacted；2）, tower top obtain unreacted light component, tower reactor obtains mixing hydrocarbon higher octane It is worth gasoline component；3）, by step 2）Obtained tower top light component, which is recycled in catalysis reaction rectifying device, continues reaction or straight Connect extraction and be C4Cut uses；4）, step 2）Obtained tower reactor component is exported by pump, obtains mixing hydrocarbon high-octane rating Component.The octane number of the conversion ratio and gained hydrocarbon of C4 alkene and formaldehyde is shown in Table 2.
Comparative example：
C 4 fraction and methanol in molar ratio 1:1 is pumped into the catalytic rectifying column equipped with cationic ion-exchange resin, controls conversion zone Temperature is 80 DEG C, operating pressure 1.0MPa, reflux ratio 4, and tower top temperature is 45 DEG C, and bottom temperature is 120 DEG C, and tower top obtains not The alkene and methanol of reaction, tower reactor mainly obtain MTBE.The conversion ratio of C4 alkene and gained MTBE octane number are shown in Table 2.The C4 of table 2 The octane number of the conversion ratio and gained hydrocarbon of alkene and formaldehyde
The conversion ratio of formaldehyde（%） C4The conversion per pass of cut（%） Hydrocarbon octane number
Embodiment one 96.28 34.11 96.5
Embodiment two 91.86 41.55 96.3
Embodiment three 95.13 36.37 97.8
Example IV 97.46 32.58 96.5
Embodiment five 93.25 37.16 97.4
Embodiment six 92.67 39.83 98.0
Embodiment seven 93.12 38.65 97.2
Embodiment eight 95.61 32.86 97.5
Embodiment nine 97.08 33.34 96.5
Embodiment ten 92.49 36.17 97.2
Embodiment 11 94.66 40.05 97.2
Embodiment 12 93.85 41.13 96.5
Embodiment 13 93.82 39.73 97.7
Embodiment 14 96.80 34.61 96.4
Embodiment 15 95.77 33.23 96.9
Embodiment 16 94.35 37.93 97.1
Embodiment 17 95.42 38.34 97.3
Embodiment 18 96.28 34.58 97.2
Comparative example — 14.35 118
Although pass through C it can be seen from the data comparison of upper table 24The pungent of the high octane gasoline component prepared is reacted with formaldehyde Alkane value is slightly less than MTBE octane number, and still, this octane number scope has fully met China's gasoline component to octane number requirement, Meanwhile C4The conversion ratio of alkene is but largely increased, C4Normal olefine in alkene equally has non-in the reaction with formaldehyde Often high reactivity.
Obviously, above-described embodiment is only intended to clearly illustrate example, and is not the restriction to embodiment.It is right For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of change or Change.There is no necessity and possibility to exhaust all the enbodiments.And the obvious change thus extended out or Among changing still in the protection domain of the invention.

Claims (6)

  1. A kind of 1. C4The method that cut synthesizes high octane gasoline component with formaldehyde, it is characterised in that be by following operating procedure Realize：1）, by containing 1- butylene, 2- butylene, three kinds of active components of isobutene C4Cut is with formaldehyde according to mol ratio 3:1~ 8:1, by being pumped into catalysis reaction rectifying device, keeps nitrogen atmosphere, under the conditions of solid acid catalyst, controls raw material body Product air speed is 0.1h-1~4h-1, reaction temperature is 70 DEG C ~ 150 DEG C, and conversion zone pressure is 0.1MPa ~ 2MPa, reflux ratio 1-10, Tower top temperature is 30-60 DEG C, and bottom temperature is 100-170 DEG C and reacted；2）, tower top obtain unreacted light component, tower reactor Obtain mixing hydrocarbon high octane gasoline component；3）, by step 2）It is anti-that obtained tower top light component is recycled to catalysis Answer and continue reaction in rectifier unit or directly produce to be C4Cut uses；4）, step 2）Obtained tower reactor component is exported by pump, is obtained To mixing hydrocarbon antiknock component.
  2. 2. C according to claim 14The method that cut synthesizes high octane gasoline component with formaldehyde, it is characterised in that：Institute State the formalin or metaformaldehyde that formaldehyde is mass concentration 37% ~ 85%.
  3. 3. C according to claim 1 or 24The method that cut synthesizes high octane gasoline component with formaldehyde, it is characterised in that： The theoretical cam curve of the catalysis reaction rectifying device is 10-60 blocks.
  4. 4. C according to claim 34The method that cut synthesizes high octane gasoline component with formaldehyde, it is characterised in that：Institute Solid acid catalyst is stated as macropore strong acid cation exchanger resin, molecular sieve catalysts, solid super acid catalyst or solid The mixing of one or more arbitrary proportions in carrying heteropolyacid catalyst.
  5. 5. C according to claim 44The method that cut synthesizes high octane gasoline component with formaldehyde, it is characterised in that：Institute It is polystyrene macropore strong acid cation exchanger resin to state macropore strong acid cation exchanger resin;Described molecular sieve is urged Agent is with ZSM-5 molecular sieve, H-Y molecular sieves, H- beta-molecular sieves, SBA-15 molecular sieves, MCM-41 or MCM-22 molecular sieves Modification or unmodified catalyst of the one or more for carrier；Described solid super acid catalyst is SO4 2-/Fe2O3、 SO4 2-/ZrO2、SO4 2-/TiO2In one or more；In described solid-carrying heteropolyacid catalyst the supported quantity of heteropoly acid be 2~ 20wt%, described heteropoly acid are the one or more in phosphotungstic acid, silico-tungstic acid, phosphomolybdic acid, silicomolybdic acid, and described carrier is One in ZSM-5 molecular sieve, H-Y molecular sieves, H- beta-molecular sieves, SBA-15 molecular sieves, MCM-41 or MCM-22 molecular sieve catalysts Kind is several.
  6. A kind of 6. C4Cut synthesizes the device of high octane gasoline component, including catalytic rectifying column body, its feature with formaldehyde It is：Rectifying section column plate, catalyst reaction section are followed successively by from top to bottom（1）, stripping section and tower reactor（2）；The catalyst reaction section（1） Load solid acid catalyst；The catalyst reaction section（1）Provided with material inlet, C is connected with material inlet4Component, formaldehyde mix Close raw material input pipe（3）, tower top is provided with gas outlet, the gas outlet and extraction pipeline（4）Connection, the extraction pipeline（4）With Raw material input pipe（3）Between be provided with circulation branch road（5）；Bottom of towe is provided with the product that product delivery outlet obtains tower reactor and passes through efferent duct Discharge on road.
CN201710549080.XA 2017-07-07 2017-07-07 C4The method and apparatus that cut synthesizes high octane gasoline component with formaldehyde Pending CN107345148A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1060228A (en) * 1991-10-15 1992-04-15 齐鲁石化公司研究院 Catalytic rectifying tower and uses thereof
CN1208663A (en) * 1997-08-20 1999-02-24 中国石化齐鲁石油化工公司 Catalysis-distillation equipment by mixing erecting catalyst with fraction elements
CN106520180A (en) * 2017-01-06 2017-03-22 中国石油大学(华东) Method for reducing olefin content of catalytically cracked gasoline
CN106753506A (en) * 2017-01-06 2017-05-31 中国石油大学(华东) The method that formaldehyde and liquefied gas synthesize antiknock component

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1060228A (en) * 1991-10-15 1992-04-15 齐鲁石化公司研究院 Catalytic rectifying tower and uses thereof
CN1208663A (en) * 1997-08-20 1999-02-24 中国石化齐鲁石油化工公司 Catalysis-distillation equipment by mixing erecting catalyst with fraction elements
CN106520180A (en) * 2017-01-06 2017-03-22 中国石油大学(华东) Method for reducing olefin content of catalytically cracked gasoline
CN106753506A (en) * 2017-01-06 2017-05-31 中国石油大学(华东) The method that formaldehyde and liquefied gas synthesize antiknock component

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
乔庆东: "《碳五烯烃的精细化工利用》", 31 January 2015, 辽宁科学技术出版社 *
侯祥麟: "《中国炼油技术》", 31 July 2001, 中国石化出版社 *

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Application publication date: 20171114