CN106365941B - A kind of conversion process of lower carbon number hydrocarbons - Google Patents

Abstract

The present invention relates to a kind of conversion process of lower carbon number hydrocarbons, with C4/C5/C6 alkane tops as main component, coking light naphthar, oil field light hydrocarbon, pentane oil etc. and mixture manufacturings butadiene, pentadiene and the method rich in high-octane rating ether compound gasoline component such as the catalytically cracked C four rich in alkene, cracking c_4.Using the logistics rich in four light dydrocarbon carbon of carbon, six alkane and rich in the logistics of alkene, by catalytic dehydrogenation and oxidative dehydrogenation, the hydrocarbon stream after butadiene and pentadiene will be isolated, into methyltertiarvbutyl ether reactor, produce high octane gasoline component, utilization rate and added value rich in four light dydrocarbon carbon of carbon, six alkane stream further are improved, while also providing one rich in olefin feedstock for mixing carbon four, catalytic light gasoline etc. and utilizing method.

Description

A kind of conversion process of lower carbon number hydrocarbons

Technical field

The present invention provides one kind to be mixed by lower carbon number hydrocarbons such as refinery's tops, pentane oil, catalytically cracked C four, cracking c_4s Produce the process of alkadienes and high octane gasoline component.

Background technique

Into 12, with 20,000,000 tons/year of China Petroleum Guangdong petrochemical industry oil refining, 10,000,000 tons/year of Kunming oil refining, four The projects such as 1,200,000 tons/year of river petrochemical industry Integrated Refinery And Petrochemical engineering, 800,000 tons/year of ethylene of Fushun petrochemical industry, Daqing petrochemical expansion of ethylene Propulsion, the refining capacity and ethylene production capacity of China Petroleum are also by further expansion, tops, pentane oil, the coke of refinery's by-product The yield of naphtha, catalytic cracking C4 and c4 cleavage resource is also being significantly increased.C4 resource is except part is for producing MTBE, alkane Outside base carburetion, polymerized monomer, burnt up mostly as domestic fuel.Pentane oil is changed by the technology of isomerization, high temperature aromatisation It is made as gasoline, dry gas production quantity is larger, and utilization rate is not high.And C4 hydrocarbon and tops are not only cheap, and transportation cost is high, fortune It is lost greatly during defeated, low-value product is belonged to for refinery.

With the rapid development of china's national economy, car ownership is continuously increased, demand to vehicle fuel gasoline It measures increasing.Meanwhile also with environmental requirement to the increasingly stringent of gasoline quality standard, motor petrol quality standard to Low sulfur content, low olefin-content, low-steam pressure and high-octane direction are developed.Market is to volume increase premium-type gasoline and to low Sulphur, low olefin-content, high octane value gasoline blending component have very big demand, and the technological development of this aspect has become the country and respectively grinds Study carefully the hot issue of unit and enterprises pay attention.

Butadiene is the primary raw material of synthetic rubber, accounts for the 71% of total raw material, butadiene demand is up to 350 within 2015 Ten thousand tons.Chinese butadiene source is relatively simple, mainly uses four extraction process of carbon, is produced by ethylene unit, by ethylene energy in 2015 21,000,000 tons of power calculating, butadiene total resources are 284~2,940,000 tons, and serious notch will occur in butadiene.Butadiene it is another Important sources are butylene oxidation-dehydrogenation technologies.Butylene oxidation-dehydrogenation is using positive structure butylene as raw material, domestic n-butene catalysis dehydrogenation Agent is at home under the joint efforts of relevant unit, experienced ternary molybdenum series catalyst, hexa-atomic molybdenum series catalyst, H-198 iron series and B-O2 Fe-series catalyst, reaction bed are also insulation fix bed by the two sections of axial directions of initial deflector apron fluidized bed development finally. However since the 1980s, with domestic large-scale ethylene plant constantly build up, the production technology of butadiene gradually by Replaced less expensive four extraction process of carbon of cost, numerous n-butene oxidative dehydrogenation devices gradually stops production, therefore domestic n-butene Oxidative dehydrogenation technology could not further be developed.But it in the long run, is influenced, is extracted by ethylene cracker raw material lighting The newly-increased butadiene production capacity of method will be increasingly difficult to meet the needs of following downstream synthetic rubber is to butadiene.

Pentadiene chemical property is active, be production polyisoprene rubber, specific rubber, Petropols, pesticide, medicine, The important industrial chemicals of a variety of petrochemicals such as fragrance, curing agent, fire retardant and fine chemical product.Pentadiene is mainly Separating-purifying obtains from the by-product of petroleum cracking ethylene, thus its production capacity and utilization rate are by region dispersion and technique shape The serious limitation of condition.

However, in four light dydrocarbon of carbon of tops, coking light naphthar, oil field light hydrocarbon, pentane oil and other devices recycling The restructuring of six hydro carbons of carbon etc. is mainly carried out by isomerization of paraffins, aromatisation, purpose product is main using in technology And improve the gasoline blend component of octane number and stability.It is the huge notch in alkadienes market on one side, another side is Further exploitation is needed rich in four light dydrocarbon carbon of carbon, six alkane oil product restructuring technology, the present invention is primarily directed to above situation, in benefit While producing butadiene, pentadiene, remaining part is used to produce high-octane rating with four light dydrocarbon carbon of carbon, six paraffinic feedstock Gasoline component.

Summary of the invention

The purpose of the present invention is to provide one kind with C4/C5/C6 alkane tops as main component, coking pumice brain Oil, oil field light hydrocarbon, pentane oil etc. with rich in mixture manufacturings butadiene, pentadiene such as the catalytically cracked C four of alkene, cracking c_4s And the method for the gasoline component rich in high-octane rating ether compound.

A kind of conversion process of lower carbon number hydrocarbons, it is characterised in that include at least following steps:

The first step will be enriched in the raw material of four light dydrocarbon carbon of carbon, six alkane and hydrogen is sent into catalytic dehydrogenation unit, and production is rich in alkene Logistics a；Logistics a is sent into separative unit I by second step, is separated into carbon six and the above hydrocarbon material flow b and light dydrocarbon and following hydro carbons Logistics c；Logistics c is sent into oxidation with raw material, the material containing oxidant and the water or water vapour for being rich in alkene and taken off by third step Hydrogen unit, production are rich in the logistics d of alkadienes；Logistics d is sent into separative unit II by the 4th step, obtains object after isolating alkadienes Flow e；Logistics e and logistics b are sent into etherificate unit by the 5th step, mixs with alcohols material, alcohol and are entered and are etherified unit hydrocarbon material In Tertiary olefin carry out etherification reaction；Etherification product is sent into separative unit III by the 6th step, isolates the carbon in etherification product Four hydrocarbon are simultaneously sent into the recycling of catalytic dehydrogenation unit, and other groups after removing on-condensible gas are divided into the gasoline rich in ether compound Component.

In the present invention rich in four light dydrocarbon carbon of carbon, six alkane raw material refer to refinery in process of production institute's by-product with carbon four Six alkane of light dydrocarbon carbon is the hydro carbons of main component, such as tops, coking light naphthar, oil field light hydrocarbon, pentane oil and other dresses Put back into four light dydrocarbon carbon of carbon, six hydro carbons etc. of receipts.

The content of the general alkane of ingredient requirement in the present invention rich in four light dydrocarbon carbon of carbon, six alkane is best 90% or more It is 95%.The boiling range of raw material 95% at 75 DEG C hereinafter, preferably at 70 DEG C hereinafter, the content of n-alkane be not less than 20%, can To be same raw material, it is also possible to different material mixing.The not specified percentage of the present invention is quality %.This be because High for naphthene content in raw material, catalytic dehydrogenation product middle ring olefin(e) centent increases, and can block the duct of catalytic dehydrogenation catalyst, Accelerate inactivation.Boiling range temperature is higher in raw material, and hydro carbons carbon number is more, and the reaction of catalytic dehydrogenation and oxidative dehydrogenation will become suitable Complexity, and then increase the burden of separative unit.Many starting isomeric Determination of Alkane Content are excessively high, normal olefine content after catalytic dehydrogenation It is considerably less, the yield of alkadienes can be made very low.

Dehydrogenation is not particularly limited in catalytic dehydrogenation unit of the present invention, it is desirable that catalytic dehydrogenation product is (in logistics a) Olefin(e) centent is not less than 35%, is preferably such that olefin(e) centent 45% or more.The reaction condition of catalytic dehydrogenating reaction in the present invention It is best are as follows: 480~700 DEG C, 0.01~3MPa of pressure, volume space velocity is 0.1~10h when liquid^-1.The reaction condition of special recommendation Are as follows: 560~650 DEG C, 0.4~1.2MPa of pressure, volume space velocity is 2~7h when liquid^-1.Hydrogen in catalytic dehydrogenating reaction device in the present invention Gas and all hydrocarbons molar ratios for entering catalytic dehydrogenation unit are 0.01~1:1, preferably 0.1~0.5:1.

In the present invention in separative unit I, it is desirable that in logistics c, hydro carbons of the carbon number greater than 6 is not higher than 1%, and the present invention is to separation Method is not required, but compares recommendation rectifying.

Refer to the C_4 hydrocarbon generated in oil refining and chemical process rich in the raw material of alkene in the present invention, such as carbon four after ether is urged Change cracking carbon four, cracking c_4, the original met the requirements that the separation component or other devices for being also possible to light petrol are separated Material.Wherein the boiling range of raw material 95% is at 75 DEG C hereinafter, preferably at 70 DEG C hereinafter, the mass content of normal olefine and isomeric olefine The sum of be not less than 35%, preferably not below 45%, can be the raw material in same source, be also possible to the mixed of separate sources raw material It closes.

In the present invention, the raw material rich in four light dydrocarbon carbon of carbon, six alkane and the material quality ratio rich in alkene can be 0.001 ~100:1, preferably 0.3~50:1.

The catalyst of oxidative dehydrogenation unit does not specially require in the present invention, is generally able to satisfy n-butene and n-pentene converts Rate is not less than 70% respectively, is preferably not less than 75% requirement respectively.Oxydehydrogenation catalyst can be using some resistance to The framework material of high temperature loads the main active component of specific ratios and helps active component to complete.Wherein, skeleton resistant to high temperature Structure can be wire mesh, more empty materials all in one piece or aluminium oxide of different shapes, silica, zirconium oxide, cordierite, oxidation Titanium, mullite, stable aluminium oxide, stable zirconium oxide etc. are also possible to two kinds or two kinds of the above heat-resisting material Above mixture.The mode of loading of active component can be micro- wet impregnated with method, chemical vapour deposition technique, coprecipitation etc..It is main Active component can be 3%~8% lanthanide element perhaps oxide of lanthanide element or for above several objects Matter is mutually mixed, and specifically can be combination one or several kinds of in samarium, cerium, praseodymium, terbium and its oxide；It is also possible to 0.2%~1% platinum group and their combination specifically can be one of ruthenium, rhodium, palladium, osmium, iridium or platinum or several. In catalyst preferably also comprising the metal of 0.01%~0.07% group VIII, group VIII metal oxide or they Combination, specially iron, iron oxide, nickel, nickel oxide, palladium, palladium oxide, platinum, platinum oxide, sail, vanadium oxide, chromium, chromium oxide, manganese, oxygen Change one of manganese etc. or several combinations.0.1% alkaline-earth metal and rare earth element conduct below can also be added and help work Property component.Ferrous acid with spinelle or hexahedron structure while Oxydehydrogenation catalyst is preferably coprecipitation method preparation The catalyst of salt and alpha-ferric oxide structure.Metal ion in ferrite can be zinc, barium, magnesium, calcium, strontium, nickel, one in copper Kind is several.A kind of spinelle-alpha-ferric oxide structure the oxidative dehydrogenation using coprecipitation method preparation for comparing recommendation is urged In agent, wherein spinelle content 45-60%, the content 2.8%~4.4% of zinc ferrite and is not higher than other ferrous acid salt contents 3%.

The reaction condition of oxidative dehydrogenation unit is slightly different according to different catalyst in the present invention, but best are as follows: 280 DEG C~470 DEG C of temperature, preferably 310 DEG C~395 DEG C, 0~100KPa of pressure, preferably 0~40KPa, volume space velocity 10~ 500h^-1, preferably 60~400h^-1.Volume space velocity when the not specified air speed of the present invention is liquid.

The logistics containing oxidant of oxidative dehydrogenation unit can be oxygen, oxygen rich air, air etc. containing aerobic in the present invention Molecule or containing oxidizing strong oxygen atom material stream, preferably air, oxygen rich air and oxygen in the present invention.It is particularly preferably oxygen-enriched Gas.Oxygen rich air of the special recommendation oxygen content between 32%~45%.Wherein, in the logistics containing oxidant with oxymeter, Oxygen and the olefin molar ratio for entering all hydrocarbon materials in oxidative dehydrogenation unit are 0.1~1.0:1, preferably 0.3~0.85:1. In the fill process of this unit, the water or vapor of certain ratio can be added, to prevent coking and the catalyst bed of catalyst Temperature is caused to rise too fast problem due to coking.The matter of water or vapor and all hydrocarbon materials into the reaction member Measuring ratio can be 0.5~30 ︰ 1, preferably 5~20 ︰ 1.

The reactor of oxidative dehydrogenation unit can be anti-for fixed bed reactors, fluidized-bed reactor, moving bed in the present invention Answer device, trickle bed reactor, or catalystic rectifying reactor, fixed bed reaction tube bank can also be the above reactor Series connection or and parallel connection.Preferred reactor is the parallel way of two or more fixed bed reactors or fluidized-bed reactor, convenient The regeneration of catalyst and technical process it is continuous.

Separation method can be extraction, rectifying in separative unit II in the present invention, or extracting rectifying, azeotropic essence It evaporates, UF membrane, chemical absorbing etc..The isolation technics of Technical comparing maturation can be used, to obtain qualified butadiene, pentadiene Product and logistics e.Due to the raw material that logistics e is aromatisation unit, it requires that the mass content of alkadienes in logistics e is not high In 0.3%, it is preferably not higher than 0.1%.The raw material of qualified diene hydrocarbon product and aromatisation unit in order to obtain, this separative unit In separation method and separator can be respectively diversified forms combination.

It is etherified in unit in the present invention and is not particularly limited catalyst for etherification and its technique, it is desirable that the conversion ratio of Tertiary olefin Not less than 92%.

The alcohols being etherified in unit in the present invention refers to the low-carbon alcohols that carbon atom number is not more than 4, special recommendation methanol, second Alcohol, preferably methanol.

When entering etherification reaction unit in the present invention, alcohols and the tertiary carbon alkene for entering all hydrocarbon materials in methyltertiarvbutyl ether reactor Hydrocarbon molar ratio is 0.8~1.5:1, preferably 0.95~1.3:1.

In the present invention be etherified unit reaction condition are as follows: 45~90 DEG C, preferably 55~75 DEG C, pressure be 0.4~ 3.0MPa, preferably 0.5~2MPa, volume space velocity are 0.1~5h^-1, preferably 1~2h^-1。

Methyltertiarvbutyl ether reactor is not particularly limited in the present invention, can be fixed bed, moving bed suspension bed, catalytic distillation reaction One of device etc. or several combinations.But preferably catalytic distillation technology can be such that Tertiary olefin converts more complete. Methyltertiarvbutyl ether reactor entrance can be recycled in the alcohols of etherificate unit recycling to be recycled.

The present invention is not required the separation method of separative unit III, compares recommendation rectifying.After isolating ether compound Material is recycled in catalytic dehydrogenation unit in four logistics of carbon, and light dydrocarbon and the above hydro carbons mass content be not preferably high not higher than 5% In 2%.

In addition, containing the separator of on-condensible gas in separative unit of the invention, as flash tank, absorption/Analytic Tower, Cooling device and pressurizing device etc..

The more specific embodiment of the present invention are as follows: the content of alkane 90% or more, 95% boiling range at 75 DEG C or less Four light dydrocarbon carbon of carbon, six alkane, at 480~700 DEG C of temperature, 0.01~3MPa of pressure, volume space velocity is 0.1~10h^-1, hydrogen with After molar ratio into all hydrocarbons of catalytic dehydrogenation unit carries out catalytic dehydrogenation under conditions of being 0.01~1:1, separation For carbon six and the above hydro carbons and light dydrocarbon and following hydro carbons two streams.Light dydrocarbon and following hydro carbons and the raw material rich in alkene with Enter oxidative dehydrogenation unit after the mass ratio mixing of 0.001~100:1, is 280 DEG C~410 DEG C in temperature, pressure 0~ 100KPa, 10~500h of volume space velocity^-1, oxygen and the olefin molar ratio of all hydrocarbon materials for entering oxidative dehydrogenation unit are The work that 0.1~1.0:1, water or vapor and the mass ratio for entering all hydrocarbon materials of oxidative dehydrogenation unit are 0.5~30:1 Oxidative dehydrogenation is carried out under the conditions of skill, isolates the carbon separated in logistics and separative unit I in reaction product after alkadienes Six and the above hydro carbons together, be 45~90 DEG C in temperature, pressure is 0.4~3.0MPa, volume space velocity into etherification reaction unit For 0.1~5h^-1, alcohols and the Tertiary olefin molar ratio for entering all hydrocarbon materials of etherification reaction unit are 0.8~1.5:1's Under the conditions of, carry out etherification reaction.Product after etherificate isolates C_4 hydrocarbon class and is recycled to catalytic dehydrogenation unit.

The advantage of the invention is that utilizing the logistics rich in four light dydrocarbon carbon of carbon, six alkane and the logistics rich in alkene, warp simultaneously Catalytic dehydrogenation and oxidative dehydrogenation are crossed, the hydrocarbon stream after isolating butadiene and pentadiene produces Gaoxin into methyltertiarvbutyl ether reactor Alkane value gasoline component further improves utilization rate and added value rich in four light dydrocarbon carbon of carbon, six alkane stream, while One, which is provided, rich in olefin feedstock for mixing carbon four, catalytic light gasoline etc. utilizes method.It is produced using alkane catalytic dehydrogenation During alkene, the conversion ratio calibration structure alkane transformations that isoparaffin is converted into isomeric olefine are the conversion ratio of normal olefine It is high.And during utilizing oxydehydro process production alkadienes, normal olefine does main contributions, and isomeric olefine utilization rate is lower. 90% or more, normal olefine hardly converts the conversion ratio of Tertiary olefin in etherification technology.In summary three kinds of technology spies Three kinds of technologies are used in combination point, it will during restructuring and using rich in four light dydrocarbon six paraffinic feedstock of carbon of carbon, more finely Such value-added content of product of the raising of change.Present inventor provides the raw material rich in alkene by catalytic dehydrogenation, for etherificate unit It finds simultaneously, during C4~C6 alkane catalytic dehydrogenation, the pentadiene and butadiene of certain content can be generated, hexadiene Trace is then unobvious.The appearance of alkadienes will affect in etherificate unit the conversion ratio of isomeric olefine, high-knock rating gasoline yield with And in gasoline ether compound content, seriously affect the technique to C4~C6 alkane restructuring after influence.By separation or Add the means of hydrogen to handle the process of alkadienes, only will increase the cost and process complexity of this technique.On the other hand, alkadienes The huge notch in market, the market price are constantly high.Oxygen is added between two reaction members of catalytic dehydrogenation and etherificate in inventor Fluidized dehydrogenation produces diene units and alkadienes separative unit, and during producing high-knock rating gasoline, by-product is a certain amount of The alkadienes of high value undoubtedly improves the economic benefit and market competitiveness of this technique, also more to refine using low Carbon alkane class provides another technique.In addition, due to the generation of side reaction, can be generated a small amount of in oxidative dehydrogenation process Ketone and aldehyde.The amount that aldehyde and ketone generate is too high, while directly affecting diene hydrocarbon-selective, what processing washing aldehyde and ketone generated Waste water process also will increase process costs.In the present invention, controlled by oxygen content in control oxygen-enriched stream into reactant It is material total amount, to control the contact of oxygen atom in reaction system, alkene with catalyst, controls reaction from still further aspect and stop Time.This method not only can guarantee that monoolefine is fully converted into alkadienes in the complex reaction of this variety of olefin oxidation, And the generation of alcohols and aldehydes is effectively controlled, improve the yield and selectivity of alkadienes.

Detailed description of the invention

Fig. 1 is using a kind of process flow diagram of the invention.

In figure: R1- catalytic dehydrogenating reaction device, R2- oxidative dehydrogenation reactor, R3- methyltertiarvbutyl ether reactor, T1, T2, T3 are separation System I, II, III.

Specific embodiment

The present invention is described in detail below by embodiment.1~table of table 4 is used the property of raw material by embodiment, and wherein raw material A is Circulating water plant of Dushanzi Refinery is hydrocracked lighter hydrocarbons, and raw material B is circulating water plant of Dushanzi Refinery pentane oil, and raw material C is that Lanzhou Petrochemical Company is catalyzed vehicle Between mix carbon four, raw material D be 75 DEG C of Liaohe River Effect of Catalysis In Petrochemistry cracking gasoline with front-end volatiles.Methanol is had using commercially available Cangzhou Zheng Yuan chemical industry The methanol of limit company production, wherein the mass content of methanol is 99.5%.Ethyl alcohol uses the limited public affairs of commercially available Yixing City autumn cloud chemical industry The dehydrated alcohol of production is taken charge of, wherein the mass content of ethyl alcohol is 99.5%.

Embodiment is all made of technique as shown in Figure 1, and catalytic dehydrogenating reaction device is the pressurization static bed reaction of 200ml in embodiment Two reactor cycles of device use, and oxidative dehydrogenation unit uses the suspended-bed reactor of 100ml, and etherification reaction system is using catalysis Distillation reaction device, pre- methyltertiarvbutyl ether reactor are 200ml fixed bed, and loaded catalyst is 150ml in reactive distillation column.Analyze sample Product are the instantaneous sample after reacting 3 hours.Use in separative unit I (T1) theoretical cam curve for 18 rectifying column.Separative unit II (T2) after being dehydrated in using cyclone separator, flash distillation removes on-condensible gas, and extraction isolates alkadienes.Separative unit III (T3) use number of theoretical plate for 10 rectifying column.

It is prepared in raw material used by catalyst in embodiment, sesbania powder is technical grade, and other is the commercially available pure examination of chemistry Agent.

Water is deionized-distilled water.

Oxygen-enriched stream is to mix with air configuration by technical grade pure oxygen.

In embodiment, the calculation method of the content of alkene, the yield of alkadienes, the yield of aromatization products, arene content It is as follows:

Own in quality/catalytic dehydrogenation product of generated butylene, amylene in the content of alkene=catalytic dehydrogenation product The quality * 100 of hydro carbons

Alcohols quality caused by the mass yield of alcohols=oxidative dehydrogenation unit and/enter oxidative dehydrogenation unit in The quality * 100 of hydrocarbon material

Ketone quality caused by the mass yield of ketone=oxidative dehydrogenation unit and/enter oxidative dehydrogenation unit in The quality * 100 of hydrocarbon material

Alkadienes quality caused by the mass yield of alkadienes=oxidative dehydrogenation unit/enter hydrocarbon in oxidative dehydrogenation unit The quality * 100 of class material

Quality after all product removal on-condensible gases of yield=etherificate of etherification product/enter etherification reaction unit hydro carbons The quality * 100 of material

The content of ether compound=generated all ether materials quality/generated etherification product quality * 100

1 raw material A of table forms (W%)

Component	Cycloalkane	Branched paraffin	Linear paraffin	Aromatic hydrocarbons
					C4		5.81	8.82
C5	0.92	50.87	14.47
					C6	1.75	15.47	1.38	0.11
C7	0.12	0.22		0.01
					C8				0.05
It is total	2.79	72.37	24.67	0.17

2 raw material B of table forms (W%)

Component	Cycloalkane	Branched paraffin	Linear paraffin	Alkene
					C4		0.23	11.60	0.07
C5	0.32	50.15	31.36	0.86
					C6		3.02	2.13
It is total	0.32	53.40	45.09	0.93

3 raw material C of table forms (W%)

Component

ω %

Component

ω %

Propane	0.04	Isobutene	17.11
				Propylene	0.01	Cis-butene-2	12.51
Iso-butane	24.50	Isopentane	0.66
				Normal butane	14.16	1,3- butadiene	0.09
Trans-butene-2	17.51	2- methyl-2-butene	0.01
				1- butylene	13.39	1- amylene	0.01

4 raw material D of table forms (W%)

Carbon number	Alkane	Cycloalkanes	Alkene	Cyclenes	Aromatic hydrocarbons
						C4	0.69		3.13
C5	24.62	0.33	25.09	0.81
						C6	19.69	2.64	16.29	1.90	0.67
C7	1.95	0.45	1.32	0.24	0.08
						C8			0.03	0.04
It is other				0.02
						It is total	46.95	3.41	45.86	3.02	0.75

Embodiment 1

Catalytic dehydrogenation catalyst uses Haitai company HTPB-DH dehydrogenation, wherein with Al₂O₃For carrier, with Pt and Cl For active component, wherein the mass content of Pt is 1%, and chlorine mass content is 2%, specific surface area 200m²/ g, Kong Rong 0.5ml/ G, diameter 1.59mm, heap density 0.6g/cm³.Olefin oxidation dehydrogenation is using embodiment 2 in patent CN102671714A Preparation method preparation, it is specific the preparation method is as follows: 17 grams of magnesium nitrate hexahydrates are dissolved in 20ml distilled water, will be resulting Solution and 20 grams of zirconium oxides are mixed with dipping, and zirconium oxide 12 hours at 80 DEG C after dry MgO-Supported are put into Muffle furnace, Resulting solid sample is heated in air atmosphere at 550 DEG C 3 hours, then use metavanadic acid ammonia spirit impregnated sample.Inclined vanadium Sour ammonia spirit is by preparing 5 grams of metavanadic acid ammonia and 10.6 grams of dissolving oxalic acids in a small amount of distilled water.By metavanadic acid ammonia The sample of solution dipping is 12 hours dry at 80 DEG C, then in Muffle furnace, heats in the air atmosphere at 550 DEG C resulting Solid sample 3 hours, final sizing was that 40~80 mesh are stand-by.Catalyst for etherification is that the big synthesis Chemical Co., Ltd. in south is produced Novel ether catalysts, granularity are 16-50 mesh, and bulk density 0.55-0.65g/ml, specific surface area is greater than 20m²/g, Aperture is greater than 10nm, and sky, which holds, is greater than 0.2cc/g.Using raw material A and raw material C, wherein raw material A and the mass ratio of raw material C are 0.001:1.It is 1:1 in hydrogen and hydrocarbon material (raw material A) molar ratio in dehydrogenation reactor, 570 DEG C of reaction temperature, volume Air speed 3.0h^-1, alkane catalytic dehydrogenating reaction is carried out under conditions of reaction pressure 1.7MPa, obtaining olefin(e) centent in product is 57.5%.Catalytic dehydrogenation product after separative unit I separation, light dydrocarbon and following hydro carbons with rich in olefin feedstock C, empty gas and water Enter oxidative dehydrogenation reactor by preheating, at 380 DEG C, 50KPa, hydrocarbon material (light dydrocarbon isolated in separative unit I and with Lower hydro carbons and raw material C) volume space velocity 60h^-1, alkene: oxygen=1:1 (molar ratio), hydrocarbon material: the item of water=1:5 (mass ratio) Olefin oxidation dehydrogenation reaction is carried out under part.The mass yield of alkadienes is 30.2% in reaction product.The mass yield of alcohols is 0.89%, the mass yield of ketone is 0.47%.Production of the oxidative dehydrogenation product after separative unit II isolates alkadienes The carbon six and the above logistics isolated in object and separative unit I are mixed into etherification reaction unit, and the reaction condition of etherificate is: instead Answer temperature 45 C, volume space velocity 2h^-1, reaction pressure 1.5MPa, wherein the molar ratio of methanol and Tertiary olefin in hydrocarbon material be 0.8:1.After reaction product removes on-condensible gas, yield 106.4%, wherein the content of ether compound is 38.5%.

Embodiment 2

Dehydrogenation is prepared using the method for embodiment 4 in CN101940922A.The specific steps are that: first weigh 117.5 grams of chromium oxide, is dissolved in deionized water and being sufficiently stirred, and being configured to weight concentration is 47% oxidation chromium solution.It is reconfigured The potassium nitrate aqueous solution that weight concentration is 3.86%.Then by 55.0 grams of boehmites, 2.2 grams of bentonites, match with 7.59 grams The oxidation chromium solution made is sufficiently mixed, and is mediated, is extruded into bead.Then 3 hours dry at 120 DEG C, then in 500 DEG C of constant temperature 3 hours, 620 DEG C constant temperature 2 hours, finally under 20% water and 80% air 760 DEG C roast 4 hours.Prepared oxygen is taken again Change 11.39 grams of chromium solution, roasting sample is impregnated 20 minutes, it is 3 hours dry at 120 DEG C, it is small in 550 DEG C of constant temperature calcinings 5 When.Take prepared potassium nitrate aqueous solution to impregnate again, it is 3 hours dry at 120 DEG C, then 620 DEG C constant temperature calcining 6 hours it is spare.Alkene Preparation method of the hydrocarbon Oxydehydrogenation catalyst using catalyst in embodiment 1 in patent CN99106660.X, specific preparation side Method is as follows: the manganese dioxide powder of 43.5g and 1000ml water agitating and heating in same container after ten minutes, are added 1.09 Gram antimony trioxide powder, stirs 2 hours after system is heated to 80 DEG C, temperature is then heated to 90 DEG C and is stirred for 4 hours, when System forming paste, it is 14 hours dry at 120 DEG C, powder is made, forms, final sizing is that 40~80 mesh are stand-by.Etherificate Catalyst uses the D005-II resin catalyst of Dandong Mingzhu Special Type Resin Co., Ltd.'s production.Its particle size range 0.315~ 1.25mm 1180~1200g/l of wet true density, total exchange capacity >=5.2mmol/g [H⁺], mechanical strength >=95% (H-type).It adopts With raw material B and raw material C, wherein the mass ratio of raw material B and raw material C is 100:1.Raw material B is in dehydrogenation reactor, in hydrogen and hydrocarbon Class material (raw material B) molar ratio be 0.3:1,600 DEG C of reaction temperature, volume space velocity 5.0h^-1, reaction pressure 1.1MPa progress alkane Catalytic dehydrogenating reaction, it is 67.3% that reaction, which obtains olefin(e) centent in dehydrogenation product,.Catalytic dehydrogenation product passes through separative unit I, point From for light dydrocarbon and following with carbon six and the above two streams.Wherein light dydrocarbon and it is following with rich in olefin feedstock C, oxygenous 45% Oxygen-enriched stream, water are mixed into oxidative dehydrogenation reactor at 410 DEG C, 250KPa, volume space velocity 500h^-1, alkene: oxygen=1: 0.8 (molar ratio), hydrocarbon material (light dydrocarbon isolated in separative unit I and following hydro carbons and raw material C): water=1:16 (quality Than) under conditions of carry out olefin oxidation dehydrogenation reaction, the mass yield of alkadienes is 49.6% in reaction product.The quality of alcohols Yield is 0.88%, and the mass yield of ketone is 0.48%.In oxidative dehydrogenation product and separative unit I after isolating alkadienes The carbon six and the above logistics isolated are mixed into etherification reaction unit, and the condition of etherification reaction is: 80 DEG C of reaction temperature, volume Air speed 3.0h^-1, reaction pressure 1.0MPa, wherein the molar ratio of methanol and the Tertiary olefin in hydrocarbon material is 1.1:1.Reaction produces After object removes on-condensible gas, yield 106.4%, wherein the content of ether compound is 38.5%.Reaction product removes not After solidifying gas, yield 78.6%, wherein the content of ether compound is 31.2%.

Embodiment 3

Catalytic dehydrogenation catalyst is prepared using the method for embodiment 1 in patent CN 101618319.By 2.24 grams of calcium oxide Be dissolved in 120ml deionized water with 3.1 grams of polyethylene glycol, 240 DEG C hydro-thermal process 24 hours, 600 DEG C after calcination 5 hours, by it It being uniformly mixed with appropriate dehydrated alcohol with 7.2 grams of chromic nitrates, 6 grams of aluminum oxides, grinding is uniform after drying 12 hours, It is spare after calcination 3 hours at 550 DEG C.Olefin oxidation dehydrogenation uses the side of preparation example 2 in patent 200780013916.9 Method is made, and stirs the specific steps of which are as follows: 69 grams of ammonium molybdate is dissolved in 500ml distilled water, then by 108.1 grams of nitre Sour bismuth is added in 5.3% nitric acid solution and stirs to after being completely dissolved, and is added drop-wise in ammonium molybdate solution.Then ammonium hydroxide, which is added dropwise, to be made The pH to 1.5 of above-mentioned solution, after stirring 1 hour, decompression, which filters, obtains solid sample, then to solid sample drying at 100 DEG C It after 26 hours, in Muffle furnace at 475 DEG C, calcines 24 hours, last crushing and screening is that 20~80 mesh are stand-by.Catalyst for etherification The D005-II resin catalyst produced using Dandong Mingzhu Special Type Resin Co., Ltd..0.315~1.25mm of its particle size range, 1180~1200g/l of wet true density, total exchange capacity >=5.2mmol/g [H⁺], mechanical strength >=95% (H-type).Using raw material A With raw material D, wherein the mass ratio of raw material A and raw material D are 1:1.Hydrogen and hydrocarbon material (raw material A) mole in dehydrogenation reactor Than for 0.15:1, at 650 DEG C of reaction temperature, volume space velocity 8.0h^-1, it is de- that alkane catalysis is carried out under conditions of reaction pressure 2.4MPa Hydrogen reacts, and olefin(e) centent is 43.8% in product.Catalytic dehydrogenation product passes through separative unit I, is separated into light dydrocarbon and following and carbon Six and the above two streams.Wherein light dydrocarbon and following it is mixed into rich in olefin feedstock D, oxygenous 35% oxygen-enriched stream, water Enter in oxidative dehydrogenation reactor at 280 DEG C, 10KPa, volume space velocity 10h^-1, alkene: oxygen=1:0.55 (molar ratio), hydrocarbon material (light dydrocarbon isolated in separative unit I and following hydro carbons and raw material C): alkene oxygen is carried out under conditions of water=1:30 (mass ratio) Fluidized dehydrogenation reaction.Diene content is 27.9% in reaction product, and the mass yield of alcohols is 0.53%, the mass yield of ketone It is 0.26%.After separative unit II separation, the carbon six isolated in logistics after isolating alkadienes and separative unit I and The above logistics is mixed into etherification reaction unit, and the condition of etherification reaction is: 65 DEG C of reaction temperature, volume space velocity 4h^-1, reaction pressure Power 0.4MPa, wherein the molar ratio of methanol and the Tertiary olefin in hydrocarbon material is 1.3:1.Reaction product remove on-condensible gas with Afterwards, yield 116.3%, wherein the content of ether compound is 48.7%.

Embodiment 4

Dehydrogenation is prepared using the method for embodiment 4 in CN101940922A.The specific steps are that: first weigh 117.5 grams of chromium oxide, is dissolved in deionized water and being sufficiently stirred, and being configured to weight concentration is 47% oxidation chromium solution.It prepares again The potassium nitrate aqueous solution that weight concentration is 3.86%.Then by 55.0 grams of boehmites, 2.2 grams of bentonites, match with 7.59 grams The oxidation chromium solution made is sufficiently mixed, and is mediated, is extruded into bead.Then 3 hours dry at 120 DEG C again, then in 500 DEG C of constant temperature 3 hours, 620 DEG C constant temperature 2 hours, finally under 20% water and 80% air 760 DEG C roast 4 hours.Prepared oxygen is taken again Change 11.39 grams of chromium solution, roasting sample is impregnated 20 minutes, it is 3 hours dry at 120 DEG C, it is small in 550 DEG C of constant temperature calcinings 5 When.Take prepared potassium nitrate aqueous solution to impregnate again, it is 3 hours dry at 120 DEG C, 620 DEG C constant temperature calcining 6 hours it is spare.Alkene Hydrocarbon Oxydehydrogenation catalyst is made using the method for preparing embodiment 2 in patent 200880014941.3, the specific steps of which are as follows: 14.2 grams of zinc chloride and 56.1 grams of ferric chloride hexahydrates are dissolved in 800ml distilled water, are stirred well to after being completely dissolved, are dripped The pH value for adding the sodium hydrate aqueous solution of 3M to adjust above-mentioned solution is to 8, and decompression is filtered and obtained after being then stirred at room temperature 12 hours Obtain solid sample.Solid sample is 16 hours dry at 175 DEG C, it is calcined 12 hours at 650 DEG C, last crushing and screening is 20 ~65 mesh are stand-by.Catalyst for etherification is urged using Jiangsu AudioCodes petrochemistry Technology Co., Ltd. macropore strong acid resin produced Agent, granularity 0.315-1.25mm, bulk density 0.77-0.85g/ml, specific surface area are greater than 20-70m²/ g, aperture are big In 20-50nm, sky, which holds, is greater than 0.3-0.5cc/g.Using raw material B and raw material D, wherein the mass ratio of raw material B and raw material D is 50: 1.Raw material B is entered in dehydrogenation reactor, is 0.5:1, reaction temperature 550 in the molar ratio of hydrogen and hydrocarbon material (raw material B) DEG C, volume space velocity 10.0h^-1, reacted under conditions of reaction pressure 3.0MPa, obtaining olefin(e) centent in dehydrogenation product is 50.4%.Catalytic dehydrogenation product passes through separative unit I, is separated into light dydrocarbon and following and carbon six and the above two streams.Wherein carbon It five and is mixed into oxidative dehydrogenation reactor with rich in olefin feedstock D, oxygenous 40% oxygen-enriched stream, water below 400 DEG C, atmospheric pressure, volume space velocity 250h^-1, alkene: oxygen=1:0.1 (molar ratio), hydrocarbon material (are isolated in separative unit I Light dydrocarbon and following hydro carbons with raw material D): reacted under conditions of water=1:0.3 (mass ratio), obtain the content of alkadienes in product It is 31.4%, the mass yield of alcohols is 0.70%, and the mass yield of ketone is 0.35%.Oxidative dehydrogenation product is single by separation The carbon six and the above logistics isolated in first II, logistics after isolating alkadienes and separative unit I are mixed into etherification reaction The condition of unit, etherification reaction is: 75 DEG C of reaction temperature, volume space velocity 5h^-1, reaction pressure 3MPa, wherein methanol and tertiary carbon alkene The molar ratio of hydrocarbon is 1.5:1.Reaction product remove on-condensible gas after, yield 102.1%, wherein the content of ether compound be 32.5%.

Embodiment 5

Catalytic dehydrogenation catalyst is prepared using the method for embodiment 9 in patent CN96121452.X.Weigh 17 grams of Cr (NO₃)₃·9H₂O, 1.1 grams of Cu (NO₃)₂·3H₂O, 80.8 grams of Al (NO₃)₃·9H₂O prepares catalyst with coprecipitation, precipitating 10% KOH (or NaOH) solution is selected in agent, and nitrate is dissolved in distilled water, and precipitating reagent is added while stirring, makes it completely Gel being formed, and pH value is 8.5~9, aging 3 hours, filtering was 20 hours dry at 110 DEG C, it is roasted 7 hours at 650 DEG C, It is spare after after crushing and screening.Olefin oxidation dehydrogenation is made using method in embodiment 4 in CN96113127, specific steps It is as follows: by 177 grams of Fe (NO₃)₃·9H₂O, 43.3 grams of Zn (NO₃)₂·6H₂O, 43 grams of Ca (NO₃)₂·4H₂O, 1.5 grams of Co (NO₃)₂·6H₂O is dissolved in the distilled water of 500ml, quickly the ammonia precipitation process of the lower instillation 20% of stirring, is added 1 gram in precipitation process Sesbania powder.When pH value in solution is to 8.5, terminates ammonium hydroxide and instill.Sediment 80 DEG C heat ageing 1 hour, in 55 DEG C of agings 30 minutes, filtering used 1000ml water washing, altogether twice every time.Filter cake is 12 hours dry at 110 DEG C, small in 650 DEG C of calcinings 14 When, final sizing is that 40~80 mesh are stand-by.Catalyst for etherification uses the etherified resin catalyst of Kai Rui Chemical Co., Ltd. production, Its particle size range 0.335~1.25mm, 0.75~0.85g/ml of wet true density, total exchange capacity >=5.2mmol/g, mechanical strength >=95%.Using raw material A, raw material B and raw material C, wherein raw material A, raw material B, raw material C mass ratio be 0.4:1:1.Raw material A and B It is 0.75:1 in hydrogen and hydrocarbon material (raw material A and raw material B) molar ratio after mixing, 480 DEG C of reaction temperature, volume space velocity 0.1h^-1, catalytic dehydrogenation under conditions of reaction pressure 0.01MPa, it is 42.7% that reaction, which obtains olefin(e) centent in dehydrogenation product,.Catalysis By separative unit I be separated into light dydrocarbon after dehydrogenation and following with carbon six and the above two streams, light dydrocarbon and following logistics be rich in Olefin feedstock C enters oxidative dehydrogenation reactor, with oxygenous 32% oxygen-enriched stream, water by preheating enter oxidative dehydrogenation In device, at 340 DEG C, 70KPa, volume space velocity 400h^-1, alkene: oxygen=1:0.68 (molar ratio), hydrocarbon material is (in separative unit I The light dydrocarbon isolated and following hydro carbons and raw material C): oxidative dehydrogenation is carried out under conditions of water=1:12 (mass ratio).By Separative unit II isolates alkadienes, yield 28.6%, and the mass yield of alcohols is 0.71%, the mass yield of ketone It is 0.38%.The carbon six and the above logistics isolated in other hydro carbons and separative unit I are mixed into etherification reaction unit, ether The condition for changing reaction is: 55 DEG C of reaction temperature, volume space velocity 0.1h^-1, reaction pressure 2.0MPa, wherein ethyl alcohol and Tertiary olefin Molar ratio is 1.2:1.After isolating fixed gas, the yield of etherification product is 106.1%, and wherein the content of ether compound is 34.8%.

Embodiment 6

Dehydrogenation uses in patent CN 101623633A and prepares catalyst the step of catalyst preparation in embodiment 1. ZSM-5 molecular sieve original powder is placed in the SnCl of 0.16M first₂·2H₂10hr is impregnated at 80 DEG C in O solution, so that Sn in catalyst Load capacity reach 4wt%, the then dry 6hr at 120 DEG C.Sample after drying roasts 4hr under 550 DEG C of air atmospheres. The H of powder after roasting in 0.03M₂PtCl₆·6H₂4hr is impregnated at 80 DEG C in O solution, it is urging for 20wt% that Pt content, which is made, Agent, then the dry 6hr at 120 DEG C, roasts 4hr at 550 DEG C.It is finally spare in 550 DEG C of hydrogen reducing 12hr.Alkene oxygen Fluidized dehydrogenation catalyst is prepared using the preparation method of embodiment 1 in patent CN103055890, the specific steps are as follows: first by 280 Gram iron powder and 80.3 grams of zinc powder be added in the nitric acid solution of 1000 milliliters of 1M, it is to be dissolved completely after, add 97.1 grams Manganese nitrate and 3.3 grams of magnesium nitrates after being completely dissolved, under conditions of 60 DEG C of solution temperature, are added dropwise 20% ammonium hydroxide and sufficiently stir It mixes, until pH value, after 7.5, solution temperature continues to be kept for 60 DEG C, continues stirring aging 60 minutes, filters slurries and wash to pH value 7.0~9.0, then by after filter cake extrusion, 200 DEG C drying 12 hours, it is 500 DEG C after calcining 48 hours, strip catalyst is short Broken is 2~3 millimeters stand-by.Catalyst for etherification buys the RZE-3 zeolite catalyst for etherification of petrochemical industry academy of sciences research and development, and shape is Diameter 8mm is spherical, bulk density 0.71g/cm³, specific surface area 487m²/ g, Kong Rong 0.464mL/g, average pore size 175nm, intensity >20N.Using raw material B, raw material C, raw material D, wherein raw material B, raw material C, raw material D mass ratio be 15:1:15, raw material B is in hydrogen With hydrocarbon material (raw material B) molar ratio be 0.1:1,700 DEG C of reaction temperature, volume space velocity 1.0h^-1, reaction pressure 0.15Mpa item Catalytic dehydrogenation is carried out under part, it is 58.3% that reaction, which obtains olefin(e) centent in dehydrogenation product,.Catalytic dehydrogenation product passes through separative unit I After separation, light dydrocarbon and following hydro carbons are mixed with raw material C, D rich in alkene, de- into oxidation by preheating with pure oxygen gas and water In hydrogen reactor, at 350 DEG C, pressure 100KPa, volume space velocity 350h^-1, alkene: oxygen=1:0.3 (molar ratio), hydrocarbon material (light dydrocarbon isolated in separative unit I and following hydro carbons and raw material C, raw material D): alkene is carried out under conditions of water=20 (mass ratio) Hydrocarbon oxidative dehydrogenation.Oxidative dehydrogenation product passes through separative unit II, isolates alkadienes, and the yield of alkadienes is 34.1%, The mass yield of alcohols is 1.27%, and the mass yield of ketone is 0.86%.The carbon isolated in other hydro carbons and separative unit I Six and the above logistics be mixed into etherification reaction unit, etherification reaction condition is: 90 DEG C of reaction temperature, volume space velocity 1.4h^-1, instead Pressure 1.7MPa is answered, wherein the molar ratio of methanol and Tertiary olefin is 0.95.After isolating fixed gas, the yield of etherification product It is 124.3%, wherein ether compound content is 58.7%.

Comparative example

Catalytic dehydrogenation catalyst uses Haitai company HTPB-DH dehydrogenation, wherein with Al₂O₃For carrier, with Pt and Cl For active component, wherein the mass content of Pt is 1%, and chlorine mass content is 2%, specific surface area 200m²/ g, Kong Rong 0.5ml/ G, diameter 1.59mm, heap density 0.6g/cm³.Catalyst for etherification is the big synthesis Chemical Co., Ltd.'s novel ether produced in south Change catalysts, granularity is 16-50 mesh, and bulk density 0.55-0.65g/ml, specific surface area is greater than 20m²/ g, aperture are big It is greater than 0.2cc/g in 10nm, Kong Rong.Using raw material A and raw material C, wherein the mass ratio of raw material A and raw material C are 0.001:1.? It is 0.5:1 in the molar ratio of hydrogen and hydrocarbon material (raw material A) in dehydrogenation reactor, 570 DEG C of reaction temperature, volume space velocity 3.0h^-1, alkane catalytic dehydrogenating reaction is carried out under conditions of reaction pressure 1.7MPa, obtaining olefin(e) centent in product is 57.5%. Catalytic dehydrogenation product enters etherification reaction unit, and the reaction condition of etherificate is: 45 DEG C of reaction temperature, volume space velocity 2h^-1, reaction pressure Power 1.5MPa, wherein the molar ratio of methanol and Tertiary olefin is 1.2:1.After reaction product removes on-condensible gas, yield is 101.4%, wherein the content of ether compound is 18.5%.

Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe Various corresponding changes and modifications, but these corresponding changes and modifications can be made according to the present invention by knowing those skilled in the art It all should belong to the protection scope of the claims in the present invention.

Claims (34)

1. a kind of conversion process of lower carbon number hydrocarbons, it is characterised in that include at least following steps:

The first step will be enriched in the raw material of four light dydrocarbon carbon of carbon, six alkane and hydrogen is sent into catalytic dehydrogenation unit, and production is rich in the object of alkene Flow a；Logistics a is sent into separative unit I by second step, is separated into carbon six and the above hydrocarbon material flow b and light dydrocarbon and following hydrocarbon material flow c；Logistics c is sent into oxidative dehydrogenation unit with raw material, the logistics containing oxidant and the water or vapor for being rich in alkene by third step, Production is rich in the logistics d of alkadienes；Logistics d is sent into separative unit II by the 4th step, obtains logistics e after isolating alkadienes；The Logistics e and logistics b are sent into etherificate unit by five steps, mixs with alcohols material, alcohol with into hydrocarbon material in methyltertiarvbutyl ether reactor Tertiary olefin carry out etherification reaction；Etherification product is sent into separative unit III by the 6th step, is isolated C_4 hydrocarbon and is sent into catalysis Dehydrogenation unit is recycled, and other groups after removing on-condensible gas are divided into the gasoline component rich in ether compound；

Wherein, the raw material rich in four light dydrocarbon carbon of carbon, six alkane refers to using four light dydrocarbon carbon of carbon, six alkane as the hydro carbons of main component；Or The content of person's alkane is 90% or more；Or the boiling range of raw material 95% at 75 DEG C hereinafter, the content of n-alkane is not less than 20%.

2. conversion process according to claim 1, it is characterised in that the raw material rich in four light dydrocarbon carbon of carbon, six alkane, which refers to, to be pulled out Hair oil, coking light naphthar, oil field light hydrocarbon, pentane oil and or other devices recycling four light dydrocarbon carbon of carbon, six hydro carbons；Or alkane The content of hydrocarbon is 95%；Or the boiling range of raw material 95% at 70 DEG C hereinafter, the content of n-alkane be not less than 20%.

3. conversion process according to claim 1, it is characterised in that olefin(e) centent is not less than 35% in catalytic dehydrogenation product.

4. conversion process according to claim 3, it is characterised in that olefin(e) centent is 45% or more in catalytic dehydrogenation product.

5. conversion process according to claim 1, it is characterised in that the reaction condition of catalytic dehydrogenation unit are as follows: 480~700 DEG C, 0.01~3MPa of pressure, volume space velocity is 0.1~10h when liquid^-1。

6. conversion process according to claim 5, it is characterised in that the reaction condition of catalytic dehydrogenation unit are as follows: 560~650 DEG C, 0.4~1.2MPa of pressure, volume space velocity is 2~7h when liquid^-1。

7. conversion process according to claim 1, it is characterised in that in catalytic dehydrogenation unit, hydrogen with enter catalytic dehydrogenation The molar ratio of all hydrocarbon materials is 0.01~1 in unit.

8. conversion process according to claim 7, it is characterised in that in catalytic dehydrogenation unit, hydrogen with enter catalytic dehydrogenation The molar ratio of all hydrocarbon materials is 0.1~0.5 in unit.

9. conversion process according to claim 1, it is characterised in that the raw material rich in alkene refers to oil refining and chemical process The C_4 hydrocarbon of middle generation, the separation component of light petrol.

10. conversion process according to claim 9, it is characterised in that the raw material rich in alkene splits for carbon four, catalysis after ether The boiling range of change carbon four, cracking c_4 or raw material 95% is at 75 DEG C hereinafter, the raw material rich in alkene is to meet normal olefine It is not less than 35% with the sum of the mass content of isomeric olefine.

11. conversion process according to claim 9, it is characterised in that the raw material rich in alkene is that the boiling range of raw material 95% exists 70 DEG C hereinafter, the raw material rich in alkene is the sum of mass content for meeting normal olefine and isomeric olefine not less than 45%.

12. conversion process according to claim 1, it is characterised in that raw material rich in four light dydrocarbon carbon of carbon, six alkane be rich in The material quality ratio of alkene is 0.001~100.

13. conversion process according to claim 12, it is characterised in that raw material and richness rich in four light dydrocarbon carbon of carbon, six alkane The material quality ratio of olefin-containing is 0.3~50:1.

14. conversion process according to claim 1, it is characterised in that the reaction condition of oxidative dehydrogenation unit are as follows: temperature 280 DEG C~470 DEG C, 0~100KPa of pressure, 10~500h of volume space velocity^-1。

15. conversion process according to claim 14, it is characterised in that the reaction condition of oxidative dehydrogenation unit are as follows: temperature 310 DEG C~395 DEG C, 0~40KPa of pressure, 60~400h of volume space velocity^-1。

16. conversion process according to claim 1, it is characterised in that the oxidant of oxidative dehydrogenation unit is to contain oxygen molecule Or containing oxidizing strong oxygen atom material stream.

17. conversion process according to claim 16, it is characterised in that the oxidant of oxidative dehydrogenation unit is air, oxygen-enriched Gas or oxygen.

18. conversion process according to claim 1, it is characterised in that in oxidative dehydrogenation unit, oxygen takes off with oxidation is entered The olefin molar ratio of all hydrocarbon materials in hydrogen unit is 0.1~1.0:1.

19. conversion process according to claim 18, it is characterised in that in oxidative dehydrogenation unit, oxygen takes off with oxidation is entered The olefin molar ratio of all hydrocarbon materials in hydrogen unit is 0.3~0.85:1.

20. conversion process according to claim 1, it is characterised in that n-butene and n-pentene convert in oxidative dehydrogenation unit Rate is not less than 70% respectively.

21. conversion process according to claim 20, it is characterised in that n-butene and n-pentene turn in oxidative dehydrogenation unit Rate is not less than 75% respectively.

22. conversion process according to claim 1, it is characterised in that the reactor of oxidative dehydrogenation unit is fixed bed reaction Device, fluidized-bed reactor, moving-burden bed reactor, trickle bed reactor, catalystic rectifying reactor or fixed bed reaction tube bank, can be with Be separate unit or more reactors series connection or and parallel connection.

23. conversion process according to claim 22, it is characterised in that the reactor of oxidative dehydrogenation unit is more fixations The parallel connection of bed reactor or fluidized-bed reactor.

24. conversion process according to claim 1, it is characterised in that the logistics after isolating alkadienes in separative unit II The mass content of middle alkadienes is not higher than 0.3%.

25. conversion process according to claim 1, it is characterised in that in etherificate unit, the conversion ratio of Tertiary olefin is not low In 92%.

26. conversion process according to claim 1, it is characterised in that the alcohols material in etherificate unit refers to carbon atom Number is not more than 4 low-carbon alcohols.

27. conversion process according to claim 26, it is characterised in that the alcohols material in etherificate unit is methanol, second Alcohol.

28. conversion process according to claim 26, it is characterised in that the alcohols material in etherificate unit is methanol.

29. conversion process according to claim 1, it is characterised in that in etherification reaction unit, alcohols material with enter ether The Tertiary olefin molar ratio for changing all hydrocarbon materials in reactor is 0.8~1.5.

30. conversion process according to claim 29, it is characterised in that in etherification reaction unit, alcohols material with enter ether The Tertiary olefin molar ratio for changing all hydrocarbon materials in reactor is 0.95~1.3.

31. conversion process according to claim 1, it is characterised in that be etherified the reaction condition of unit are as follows: reaction temperature 45 ~90 DEG C, pressure is 0.4~3.0MPa, and volume space velocity is 0.1~5h^-1。

32. conversion process according to claim 31, it is characterised in that be etherified the reaction condition of unit are as follows: reaction temperature is 55~75 DEG C, pressure is 0.5~2MPa, and volume space velocity is 1~2h^-1。

33. conversion process according to claim 1, it is characterised in that the Matter Transfer for isolating ether compound is extremely catalyzed In four logistics of carbon in dehydrogenation unit, light dydrocarbon and the above hydro carbons mass content are not higher than 5%.

34. conversion process according to claim 33, it is characterised in that isolate the Matter Transfer of ether compound to urging In four logistics of carbon in fluidized dehydrogenation unit, light dydrocarbon and the above hydro carbons mass content are not higher than 2%.