CN106367108B - A kind of method of lower carbon number hydrocarbons production high octane gasoline component - Google Patents

Abstract

The present invention relates to a kind of methods of lower carbon number hydrocarbons production high octane gasoline component, the logistics rich in four light dydrocarbon carbon of carbon, six alkane and the logistics rich in alkene are utilized simultaneously, hydrocarbon stream after catalytic dehydrogenation and oxidative dehydrogenation production butadiene and pentadiene, into low temperature aromatization reactor, produce good gasoline component, the utilization rate and added value of the logistics rich in four light dydrocarbon carbon of carbon, six alkane are further improved, while also being provided for mixing carbon four, catalytic light gasoline etc. rich in olefin feedstock and a kind of utilizing method.

Description

A kind of method of lower carbon number hydrocarbons production high octane gasoline component

Technical field

Catalytic dehydrogenation technology, oxidative dehydrogenation technology are combined with low temperature aromatization technology the present invention provides a kind of, by Lower carbon number hydrocarbons mixture manufacturing high octane gasoline component and the diene such as refinery's tops, pentane oil, catalytically cracked C four, cracking c_4 The method of hydrocarbon.

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, generation dry gas amount 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, belongs to low-value product for the 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 also becomes domestic 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. It is continuous newly-built with domestic large-scale ethylene plant however since the 1980s, 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 It is to be obtained from the separating-purifying of petroleum cracking Crude products.deep process, thus compare its production capacity and utilization rate by region dispersion and work The serious limitation of skill situation.

In four light dydrocarbon carbon of carbon, six hydrocarbon of tops, coking light naphthar, oil field light hydrocarbon, pentane oil and other devices recycling The restructuring of class etc. is mainly carried out by isomerization of paraffins, high temperature aromatisation, purpose product is mainly using in technology It is the gasoline blend component for improving octane number and stability.Isomerization due in its production process to the unfriendly of environment, Through slowly having exited market.And high temperature aromatisation, under the action of high mild catalyst, dry gas production rate is higher than 20% easily, The economic benefit of technical process will receive no small loss, for intersection, produce high-knock rating gasoline with the raw material rich in alkene The low temperature aromatization technology of component, due to its reaction temperature is low, dry gas production quantity lower than 2%, it is environmentally friendly the advantages that, in richness Carbon containing four light dydrocarbons carbon, six alkane oil product is restructured in the exploitation of technology, undoubtedly an extraordinary technology.It needs further to open Hair and excavation.It is the huge notch in alkadienes market on one side, another side is to restructure skill rich in four light dydrocarbon carbon of carbon, six alkane oil product Art needs further exploitation, and the present invention is utilizing four light dydrocarbon carbon of carbon, six paraffinic feedstock dehydrogenation aromatization primarily directed to above situation During change, consider to produce a part of alkadienes, to improve the economic benefit of this technique, while eliminating catalytic dehydrogenation generation Influence of a small amount of alkadienes to aromatization catalyst activity.

The purpose of the present invention is developing a kind of technology, high octane gasoline component technology is being produced for low temperature aromatization While being rich in monoene hydrocarbon raw material technology of qualification is provided, the alkadienes that a certain amount of atomicity is more than or equal to 4, Lai Jinyi are produced Step improves the economic performance of low temperature aromatization technology.

Summary of the invention

Invention be designed to provide it is a kind of will be with C4/C5/C6 alkane tops as main component, coking pumice brain Oil, oil field light hydrocarbon, pentane oil etc. and the vapour that aromatic hydrocarbons is rich in rich in mixture manufacturings such as olefin feedstock catalytically cracked C four, cracking c_4s Oil ingredient and the method for producing alkadienes.

A kind of method of lower carbon number hydrocarbons production high octane gasoline component, include at least following steps: the first step is rich in carbon four The raw material and hydrogen of six alkane of light dydrocarbon carbon enter the catalytic dehydrogenation unit equipped with catalytic dehydrogenation catalyst, obtain logistics a, second step Logistics a enters separative unit I, is divided into carbon six and the above hydrocarbon material flow b and light dydrocarbon and following hydrocarbon material flow c；Third step is by logistics c The oxidative dehydrogenation that Oxydehydrogenation catalyst is housed is sent into raw material, the logistics containing oxidant and the water or vapor for being rich in alkene Unit, production are rich in diene material d；4th step logistics d enters separative unit II, and logistics e is obtained after alkadienes is separated；The Logistics e and logistics b, hydrogen are sent into the low temperature aromatization unit that aromatized catalyst is housed, it is anti-to carry out low temperature aromatization by five steps It answers；6th step aromatization products enter separative unit III, and six or less hydro carbons of separation of carbon is simultaneously sent into catalytic dehydrogenation unit circulation and is made With other groups after removing on-condensible gas are divided into the gasoline component rich in aromatic compound.

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 and catalytic dehydrogenation process condition, usual feelings are not particularly limited in catalytic dehydrogenation unit of the present invention Shape requires catalytic dehydrogenation product, and (olefin(e) centent is generally not less than 35% in logistics a), is preferably such that olefin(e) centent 45% or more. Catalytic dehydrogenation process condition can be different and different with the selection of catalyst in the present invention, and the reaction condition of catalytic dehydrogenating reaction 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.Enter (the catalysis of catalytic dehydrogenating reaction device in the present invention Dehydrogenation unit) in hydrogen with rich in four light dydrocarbon carbon of carbon, six alkane stream mole ratio be 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 is recommended to use 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 rich in alkene that the separation component or other devices for being also possible to light petrol are separated Material.The boiling range of best raw material 95% is at 75 DEG C hereinafter, preferably at 70 DEG C hereinafter, normal olefine and different in raw material rich in alkene The sum of mass content of structure alkene is not less than 35%, preferably not below 45%, can be the raw material in same source, is also possible to The mixing of separate sources raw material.

In the present invention, the raw material rich in four light dydrocarbon carbon of carbon, six alkane is with the material quality rich in alkene than preferably 0.001 ~100:1, most 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 mechanism.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, content 45~60%, the content 2.8%~4.4% of zinc ferrite, other ferrous acid salt contents and be not higher than 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~410 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 present invention specially devises the single-stage low-temperature oxidation deoxy technology of step completion, is applied to catalytic dehydrogenation and aromatisation Between, specific advantage and principle are as follows:

1) be directed to carbon four, light dydrocarbon and the above alkane of light dydrocarbon, the temperature of oxidative dehydrogenation technology need it is relatively lower (be directed to The oxidative dehydrogenation of ethane, oxidative dehydrogenation of propane is compared).If temperature is too high, on the one hand it is particularly easy to cause to crack, purpose can be made The yield of product is at a fairly low.Another reverse side, in experimentation, carbon four, light dydrocarbon and the above alkanes oxidative dehydrogenation reaction of light dydrocarbon, in height Temperature is lower to be carried out, and catalyst is particularly easy to coking, shortening single reaction time, and catalyst regeneration time length compared with process also compared with second Complicated after alkane, oxidative dehydrogenation of propane, the conversion capability of regenerative agent is also greatly reduced compared to fresh dose.Therefore, oxygen of the invention Change deoxy technology preferably using lower than 395 DEG C reactions, avoids the counter productive of high temperature.

2) oxidation deoxy technology of the invention uses single-stage, that is, a step is completed.The use of this technical characteristic is also specially Design.If multi-stage oxidizing De-hydrogen Technology in the prior art is used in the present invention, it is added in catalytic dehydrogenation and aromatisation In step, experimental result is shown, normal olefine will be contained after catalytic dehydrogenation and reaction raw materials are added several times and contain for isomeric olefine Carrier of oxygen is by reaction, and as the concentration of alkadienes gradually increases, oxygen concentration also can be increased gradually, and oxidation reaction can be further Deepen.The drawbacks of oxidation deoxy technology of the invention uses single-stage, that is, avoids reaction of high order.

In oxidative dehydrogenation process of the invention, oxygen content in specified in more detail temperature, pressure and oxygen flow, in addition to It can guarantee the conversion ratio of oxidative dehydrogenation, inhibit excessive oxidation to generate alcohol, outside ether, water or vapor are additionally added, to prevent The coking of catalyst and catalyst bed cause temperature to rise too fast problem due to coking, very effective can reach carbon The purpose of four or more hydrocarbon oxidation dehydrogenations production alkadienes.

It finds during the experiment, the low-temperature oxidative dehydrogenation technology of four or more alkane of carbon whether directly through the invention is also It is existing multistage high-temperature oxydation technology, the yield of alkadienes is all well below first reoxidizing dehydrogenation after material catalytic dehydrogenation Technical process, and the material after catalytic dehydrogenation carries out oxidative dehydrogenation again, can provide sufficient amount for aromatization process Monoolefine also improve the economic benefit of this technique to greatly improve the utilization rate of raw material, added value.

The logistics containing oxidant of oxidative dehydrogenation unit can be oxygen, oxygen rich air, air etc. containing aerobic in the present invention Molecule or stream containing oxidizing strong oxygen atom, 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 mole content between 32%~45%.Wherein, with oxygen in the logistics containing oxidant Meter, oxygen and enter oxidative dehydrogenation unit in all hydrocarbon materials olefin molar ratio be 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 the coking and catalysis of catalyst Agent bed causes temperature to rise too fast problem due to coking.All hydro carbons in water or vapor and entrance oxidative dehydrogenation unit The mass ratio of material 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 and parallel connection.Preferred reactor is the parallel way of two or more fixed bed reactors or fluidized-bed reactor, is conveniently urged The regeneration of agent 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.

The present invention does not specially require low temperature aromatization catalyst, generally requires the aromatisation conversion ratio of alkene preferably not Lower than 92%.Catalyst preferably contains molecular sieve and one or more active components.

In the present invention, hydrogen and all hydrocarbon material (such as objects in entrance aromatization unit in aromatization unit Flow e, logistics b mixing hydrocarbon material) molar ratio be 0.01~1:1, preferably 0.1~0.5:1.

The reaction condition that low temperature aromatization reacts in the present invention is different according to the difference of the catalyst used, best are as follows: 260 ~600 DEG C, more preferably 300~520 DEG C, special recommendation press 320~400 DEG C, pressure be 0.5~5.0MPa, preferably 1.4~ 3.0MPa volume space velocity is 0.1~10h^-1, preferably 1~4h^-1.Aromatization temperature is high, though arene content is high, and can turn Change a part of alkane, but since dry gas amount is very big, and cause hydrocarbon loss too big, therefore the present invention is recommended to use low temperature aromatization Change.

In the present invention in catalytic dehydrogenation and low temperature aromatization unit, the source of used hydrogen can be the pure hydrogen of outer confession Gas is also possible to the dry gas separated after catalytic dehydrogenation unit and aromatisation unit process.

The aromatization reactor and catalytic dehydrogenating reaction device being related in the present invention are fixed bed reactors, can be one Reactor is used alone, and is realized by two process intervals of reaction-catalyst regeneration, can also be in parallel with two or more reactors Using circulate operation is carried out, multiple reactors can also be divided to be used in combination in parallel and serial.When in one or several reactors Catalyst is due to carbon distribution serious inactivation, and by switching material import and export, decaying catalyst is recycled after regenerating, realization reaction, The continuous operation of regenerative system.

The present invention is not required the separation method of separative unit III, compares recommendation rectifying.It is urged it is required that being recycled to after separation In fluidized dehydrogenation unit in six or less logistics of carbon, carbon six and the above hydro carbons mass content are not higher than 2%, are preferably not higher than 0.5%.

In separative unit of the invention can also have be added on-condensible gas separator, as flash tank, absorption/Analytic Tower, Cooling device and compression set 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 Molar ratio into all hydrocarbons of catalytic dehydrogenation unit obtains after carrying out catalytic dehydrogenation under conditions of being 0.1~0.5:1 Logistics a.Logistics a is separated into carbon six and the above hydro carbons (logistics b) and light dydrocarbon and following hydro carbons (logistics c) two streams.Logistics c with Raw material rich in alkene is 280 DEG C~410 in temperature to enter oxidative dehydrogenation unit after the mass ratio mixing of 0.001~100:1 DEG C, 0~100KPa of pressure, 10~500h of volume space velocity^-1, containing, with oxymeter, oxygen is reacted with into this in oxidant stream In all hydrocarbon materials (including logistics c, the mixed material of the raw material rich in alkene) of unit the molar ratio of alkene be 0.1~ It is carried out under the process conditions that the mass ratio of 1.0 ︰ 1, vapor and all hydrocarbon materials for entering this reaction member is 0.5~30:1 Oxidative dehydrogenation, the carbon six and the above hydro carbons one separated in other logistics after alkadienes and raw material are isolated in logistics after reaction It rises, is 0.1~0.5:1, temperature 260 in hydrogen and the hydrocarbon material molar ratio for entering aromatisation unit into aromatisation unit ~600 DEG C, 0.5~5.0MPa of pressure, volume space velocity is 0.1~10h^-1Under conditions of low temperature aromatization.After low temperature aromatization It after product removal on-condensible gas, isolates six or less hydro carbons of carbon and is recycled to catalytic dehydrogenation unit, remaining logistics is rich in virtue The gasoline component of hydrocarbon.

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 Hydrocarbon stream after crossing catalytic dehydrogenation and oxidative dehydrogenation production butadiene and pentadiene is produced into low temperature aromatization reactor Good gasoline component further improves the utilization rate and added value of the logistics rich in four light dydrocarbon carbon of carbon, six alkane, is Mixing carbon four, catalytic light gasoline etc. provide a kind of new utilization method rich in olefin feedstock.

In four light dydrocarbon carbon of carbon, six hydrocarbon of tops, coking light naphthar, oil field light hydrocarbon, pentane oil and other devices recycling The restructuring of class etc. is mainly carried out by isomerization of paraffins, high temperature aromatisation, purpose product is mainly using in technology It is the gasoline blend component for improving octane number and stability.Isomerization due in its production process to the unfriendly of environment, Through slowly having exited market.And high temperature aromatisation, under the action of high mild catalyst, dry gas production rate is higher than 20% easily, The economic benefit of technical process will receive no small loss, in contrast, produce high-knock rating gasoline with the raw material rich in alkene The low temperature aromatization technology of component, due to its reaction temperature is low, dry gas production quantity lower than 2%, it is environmentally friendly the advantages that, in richness Carbon containing four light dydrocarbons carbon, six alkane oil product is restructured in the exploitation of technology, undoubtedly a technology for being especially worth continuing deeper into research. During using alkane catalytic dehydrogenation production alkene, the conversion ratio that isoparaffin is converted into isomeric olefine turns compared with n-alkane Turn to the high conversion rate of normal olefine.In low temperature aromatization technology 90% or more low-carbon alkene can be converted into non-benzene aromatic hydrocarbons or The alkene that enter reaction system can almost be converted modification by long chain alkane completely.But present inventor is de- by catalysis Hydrogen, discovery while providing the raw material rich in alkene for low temperature aromatization can produce during C4~C6 alkane catalytic dehydrogenation The pentadiene and butadiene of raw certain content, the trace of hexadiene are then unobvious.The appearance of alkadienes can seriously affect low temperature virtue During structure, the content of the conversion ratio of monoolefine, high-knock rating gasoline yield and Aromatic Hydrocarbon in Gasoline.By separating or adding The means of hydrogen handle the process of alkadienes, only will increase the cost and process complexity of this technique.Another side is alkadienes city The huge notch of field, the market price are constantly high.Inventor adds between two reaction members of catalytic dehydrogenation and low temperature aromatization Enter oxidative dehydrogenation production diene units and alkadienes separative unit, during producing high-knock rating gasoline, by-product is certain The alkadienes of the high value of amount undoubtedly improves the economic benefit and market competitiveness of this technique, also the benefit more to refine Another technique is provided with lower alkanes hydro carbons.In addition, due to the generation of side reaction, can be generated in oxidative dehydrogenation process A small amount of ketone and aldehyde.The amount that aldehyde and ketone generate is too high, and while directly affecting diene hydrocarbon-selective, processing washing aldehyde and ketone are produced Raw waste water, process also will increase process costs.In the present invention, controlled by oxygen content in control oxygen-enriched stream into anti- System material total amount is answered, to control the contact of oxygen atom in reaction system, alkene with catalyst, controls and reacts from still further aspect Residence time.This method not only can guarantee that monoolefine is fully converted into two in the complex reaction of this variety of olefin oxidation Alkene simultaneously, and effectively controls the generation of alcohols and aldehydes, improves the yield and selectivity of alkadienes.

Below in conjunction with the drawings and specific embodiments, the present invention will be described in detail, but not as a limitation of the invention.

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- low temperature aromatization reactor, T1, T2, T3 For separation system I, II, III.

Specific embodiment

The present invention is described in detail below by embodiment.1~table of table 3 is the property for the raw material that embodiment uses, 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, 75 DEG C of Effect of Catalysis In Petrochemistry cracking gasoline of the Liaohe River raw material D is with front-end volatiles.

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	Cycloalkane	Alkene	Cycloolefin	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 is all made of technique as shown in Figure 1, and Examples 1 to 3 is that catalytic dehydrogenating reaction device and aromatization reactor are equal For the single intermittently operated of 200ml fixed bed reactor, oxidative dehydrogenation unit uses the suspended-bed reactor of 100ml.Implement In example 4~6, catalytic dehydrogenating reaction device and aromatization reactor are two reactor cycles of 200ml fixed bed reactor It uses, oxidative dehydrogenation unit uses the suspended-bed reactor of 100ml.Analysis sample is the instantaneous sample after reacting 2 hours.Separation is single Use in first I (T1) theoretical cam curve for 12 rectifying column, 57 DEG C of tower top temperature, reflux ratio 1.5,110 DEG C of bottom temperature.Separation After being dehydrated in unit II (T2) using cyclone separator, flash distillation removes the gas other than C_4 hydrocarbon, and extraction isolates butadiene After obtain other four components of carbon.Use in separative unit III (T3) theoretical cam curve for 17 rectifying column, 64 DEG C of tower top temperature, Reflux ratio 1.3,125 DEG C of bottom temperature.

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 rich air 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=aromatisation of aromatization products/enter aromatization list The quality * 100 of first hydrocarbon material

Arene content=generated aromatic hydrocarbons quality/generated aromatization products quality * 100

Embodiment 1

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 configuring 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 500 DEG C of constant temperature again 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, will be impregnated 20 minutes with burned sample, 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 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, by impregnating by resulting solution and 20 grams of zirconium oxides, at 80 DEG C After zirconium oxide 12 hours of lower dry MgO-Supported, in Muffle furnace, heated in the air atmosphere at 550 DEG C resulting solid Body sample 3 hours, then use metavanadic acid ammonia spirit impregnated sample.Metavanadic acid ammonia spirit be by by 5 grams of metavanadic acid ammonia with 10.6 grams of dissolving oxalic acids are prepared in a small amount of distilled water.By the sample of metavanadic acid ammonia solution dipping dry 12 small at 80 DEG C When, then resulting solid sample in Muffle furnace, is being heated in the air atmosphere at 550 DEG C 3 hours, final sizing be 40~ 80 mesh are stand-by.Aromatized catalyst uses the method for CN 1586721A Catalyst Preparation Example 3 and active component Pr is added, Specific preparation process is as follows for it: going out ZSM-11 zeolite powder, 3 hours dry, 550 DEG C of dryings 24 at 110 DEG C using hydrothermal synthesis Hour.Then according to 70g zeolite 30g aluminium oxide butt and 7g drying Pr (NO₃)₂Powder hand mix is uniform, then with 10% Dust technology kneading, then with after double screw extruder extruded moulding at 110 DEG C it is 3 hours dry, after it is small in 550 DEG C of constant temperature 3 When.Then consolidating volume ratio with 1mol/L, exchange liquid is 5, each swap time 2 hours, is exchanged 3 times, liquid is changed in centre.Exchange is completed After be washed with deionized, it is cooling to use at 550 DEG C after constant temperature 5 hours and dry 3 hours at 110 DEG C.Using raw material A With raw material D, the mass ratio of raw material A and raw material D are 100 ︰ 1.In dehydrogenation reactor, rub in hydrogen and hydrocarbons (raw material A) You than 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, instead Should obtain olefin(e) centent in dehydrogenation product is 66.7%.Catalytic dehydrogenation product passes through separative unit I, is separated into light dydrocarbon and following hydrocarbon Class and carbon six and the above hydro carbons two streams.Wherein light dydrocarbon and it is following with rich in alkene raw material D, oxygenous 45% it is oxygen-enriched Gas and water is mixed into oxidative dehydrogenation reactor at 410 DEG C, atmospheric pressure, the hydrocarbon material (light dydrocarbon isolated in separative unit I And following hydro carbons and raw material D) liquid hourly space velocity (LHSV) 500h^-1, alkene: oxygen=1:1 (molar ratio), hydrocarbon material (separate in separative unit I Light dydrocarbon out and following hydro carbons and raw material D): water=1:16 (mass ratio), the mass yield of alkadienes is in reaction product 25.8%, the mass yield of alcohols is 0.89%, and the mass yield of ketone is 0.47%.Oxidative dehydrogenation after isolating alkadienes The carbon six and the above hydro carbons isolated in product and separative unit I are mixed into aromatization reactor, in hydrogen and hydro carbons Molar ratio is 0.3:1,260 DEG C of reaction temperature, volume space velocity 10h^-1, react under the conditions of reaction pressure 4.1MPa.Reaction product is de- After on-condensible gas, the yield of product is 70.1%, and wherein arene content is 52.4%.

Embodiment 2

Dehydrogenation 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, and precipitating reagent is selected 10% KOH (or NaOH) solution, nitrate are dissolved in distilled water, and precipitating reagent is added while stirring, form it completely solidifying Glue, and pH value is 8.5~9, aging 3 hours, filtering was 20 hours dry at 110 DEG C, roasted 7 hours at 650 DEG C, through broken It is spare after screening.Olefin oxidation dehydrogenation uses the preparation method of catalyst in embodiment 1 in patent CN99106660.X, It is specific the preparation method is as follows: by the manganese dioxide powder of 43.5g and 1000ml water agitating and heating 10 minutes in same container Afterwards, 1.09 grams of antimony trioxide powder are added, is stirred 2 hours after system is heated to 80 DEG C, temperature is then heated to 90 DEG C It is stirred for 4 hours, it is 14 hours dry at 120 DEG C when System forming paste, powder is made, forms, final sizing is 40~ 80 mesh are stand-by.Aromatized catalyst uses the preparation method of catalyst C1 in embodiment 1 in patent CN101898150A.Specific step It is rapid as follows: to take 100 grams of SiO₂/Al₂O₃Molecule molar ratio is the HZSM-5 molecular sieve of 65 ︰ 1, is first 6.32 millis with 100 milliliters of concentration Grams per milliliter phosphoric acid solution impregnates 8 hours, and 110 DEG C after drying 4 hours, then with 100 milliliters of concentration be 3.04 mg/mls LaCl₃·6H₂O solution impregnates 8 hours, so that the content of La in the catalyst is 8wt%, then 110 DEG C drying 4 hours, 550 DEG C roasting 4 hours it is spare.Using raw material B and raw material C, wherein the mass ratio of raw material B and raw material C is 0.001:1.Raw material B is de- Hydrogen and hydrocarbon material (raw material B) molar ratio are 1:1 in hydrogen reactor, at 650 DEG C of reaction temperature, volume space velocity 8.0h^-1, reaction Alkane catalytic dehydrogenating reaction is carried out under conditions of pressure 2.4MPa, olefin(e) centent is 40.3% in product.Production after catalytic dehydrogenation Object passes through separative unit I, is separated into light dydrocarbon and following hydro carbons and carbon six and the above hydro carbons two streams.Wherein light dydrocarbon and it is following with Raw material C rich in alkene, oxygenous 35% oxygen-enriched stream, water are mixed into oxidative dehydrogenation reactor at 280 DEG C, 10KPa, Hydrocarbon material (light dydrocarbon isolated in separative unit I and following hydro carbons and raw material C) liquid hourly space velocity (LHSV) 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): water=1:10 (quality Than), olefin oxidation dehydrogenation reaction is carried out under this condition.Diene content is 47.8% in reaction product, and the quality of alcohols is received Rate is 0.51%, and the mass yield of ketone is 0.25%.After separative unit II separation, isolates the logistics of alkadienes and divide It is mixed into aromatization reactor from the carbon six and the above hydrocarbon isolated in unit I, is in the molar ratio of hydrogen and hydro carbons 0.15 ︰ 1,400 DEG C of reaction temperature, volume space velocity 1.5h^-1, react under conditions of reaction pressure 5.0MPa.Reaction product removes not After solidifying gas, yield 51.3%, wherein arene content is 27.7%.

Embodiment 3

Dehydrogenation uses in patent CN 101623633A and prepares catalyst the step of catalyst preparation in embodiment 1. First ZSM-5 molecular sieve original powder carrier 0.16M SnCl₂·2H₂In 80 DEG C of dipping 10hr in O solution, so that in catalyst The load capacity of Sn reach 4wt%, then dry 6hr at 120 DEG C again.Sample after drying roasts under 550 DEG C of air atmospheres 4hr.The H of powder after roasting in 0.03M₂PtCl₆·6H₂4hr is impregnated at 80 DEG C in O solution, makes that Pt content finally is made The catalyst of 20wt%, then the dry 6hr at 120 DEG C, roasts 4hr at 550 DEG C.It is standby in 550 DEG C of hydrogen reducing 12hr afterwards With.Olefin oxidation dehydrogenation is made using the method for preparation example 2 in patent 200780013916.9, and specific steps are such as Under: 69 grams of ammonium molybdate is dissolved in 500ml distilled water and is stirred, then 108.1 grams of bismuth nitrate is added to 5.3% nitre It stirs to after being completely dissolved, is added drop-wise in ammonium molybdate solution in acid solution.Then ammonium hydroxide, which is added dropwise, makes the PH of above-mentioned solution to 1.5, After stirring 1 hour, decompression, which filters, obtains solid sample, then after 100 DEG C small dry 26 hours to solid sample, in Muffle furnace In at 475 DEG C, calcine 24 hours, last crushing and screening is that 20~80 mesh are stand-by.Aromatized catalyst uses patent The method preparation that in embodiment 1 prepared by aromatized catalyst in CN98101358.9.Specific preparation step are as follows: by 10gHZSM-5 With Al₂O₃Than pouring into the Zn (NH that concentration is 54 mg/mls in the carrier for 65:35₃)₄(NO₃)₂12 milliliters of aqueous solution, dipping 2 Hour.Then twice with deionized water flushing, 120 DEG C drying 6 hours.Then with 8 milliliters of chloride containing mischmetals (industrial goods, The production of Inner Mongol packet header industrial group, wherein lanthana 31%, oxygen cerium oxide 51%, praseodymium oxide 14%, neodymia 4%) water Solution impregnates two hours at room temperature, 110 DEG C drying 16 hours, 540 DEG C after roasting 6 hours, 540 DEG C steam treatment 2 hours. Rare earth oxide content 0.34wt% in catalyst, Zn content 2.1wt% is made.Using raw material B and raw material D, wherein raw material B and former The mass ratio for expecting D is 3 ︰ 1.Raw material B enters in dehydrogenation reactor, is 0.5 ︰ 1 in hydrogen and hydrocarbon material (raw material B) molar ratio, 550 DEG C of reaction temperature, volume space velocity 10.0h^-1, reacted under conditions of reaction pressure 3.0MPa, obtain alkene in dehydrogenation product Hydrocarbon content is 49.3%.Catalytic dehydrogenation product passes through separative unit I, is separated into light dydrocarbon and following hydro carbons and carbon six and the above hydro carbons Two streams.Wherein light dydrocarbon and following hydro carbons and raw material D, oxygenous 40% oxygen-enriched stream, water are through being mixed into oxidative dehydrogenation In reactor at 300 DEG C, 30KPa, hydrocarbon material (light dydrocarbon isolated in separative unit I and following hydro carbons and raw material D) liquid Air speed 250h^-1, alkene: oxygen=1:0.1 (molar ratio), hydrocarbon material (light dydrocarbon isolated in separative unit I and following hydro carbons with Raw material D): water=1:0.5 (mass ratio) reacts under this condition, and the content for obtaining alkadienes in product is 28.1%, alcohols Mass yield is 0.77%, and the mass yield of ketone is 0.38%.Oxidative dehydrogenation product passes through separative unit II, isolates diene Logistics after hydrocarbon enters in aromatization reactor, is 0.5 ︰ 1 in the molar ratio of hydrogen and hydro carbons, 560 DEG C of reaction temperature, volume is empty Fast 3.5h^-1, reacted under conditions of reaction pressure 0.5MPa.After reaction product removes on-condensible gas, yield is 68.65%, wherein arene content is 30.8%.

Embodiment 4

Catalytic dehydrogenation dehydrogenation uses Haitai company HTPB-DH dehydrogenation, wherein with Al₂O₃It is carrier with Pt It is active component with Cl, 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 uses patent 200880014941.3 The method of middle preparation embodiment 2 is made, the specific steps of which are as follows: by 14.2 grams of zinc chloride and 56.1 grams of ferric chloride hexahydrate dissolutions It in 800ml distilled water, is stirred well to after being completely dissolved, the sodium hydrate aqueous solution that 3M is added dropwise adjusts the pH value of above-mentioned solution To 8, after being then stirred at room temperature 12 hours, decompression, which is filtered, obtains solid sample.By solid sample, drying 16 is small at 175 DEG C When, it is calcined 12 hours at 650 DEG C, last crushing and screening is that 20~65 mesh are stand-by.Aromatized catalyst uses CN 1586721A Simultaneously active component Ni is added in the method for Catalyst Preparation Example 3, and specific preparation process is as follows: going out crystal grain using hydrothermal synthesis Degree is less than the silica-rich zeolite original powder of 500nm, 3 hours dry at 110 DEG C, 550 DEG C drying 24 hours.Then according to 80g zeolite 20g Ni (the NO of the drying of aluminium oxide butt and 3.66g₃)₂Powder hand mix is uniform, then with 10% dust technology kneading, then uses After double screw extruder extruded moulding dry 3 hours at 110 DEG C, after 550 DEG C constant temperature 3 hours.Then with 0.6mol/L, friendship Changing liquid to consolidate volume ratio is 10 ︰ 1, each swap time 1 hour, is exchanged 5 times, liquid is changed in centre.It is washed with deionized water after the completion of exchange It washs, and 3 hours dry at 110 DEG C, it is cooling to use at 550 DEG C after constant temperature 5 hours.Using raw material A and raw material C, Central Plains The mass ratio for expecting A and raw material C is 0.1 ︰ 1.Raw material A is 0.25:1, reaction temperature in the molar ratio of hydrogen and hydrocarbon material (raw material A) 480 DEG C of degree, volume space velocity 0.1h^-1, catalytic dehydrogenation under conditions of reaction pressure 0.01MPa, reaction obtains alkene in dehydrogenation product Content is 40.9%.Light dydrocarbon and following hydro carbons and six or more carbon are separated into after separative unit I separation after catalytic dehydrogenation Two streams, light dydrocarbon and following hydrocarbon material flow enter oxidative dehydrogenation reactor, with raw material C, oxygenous 32% oxygen-enriched stream, water Enter in oxidative dehydrogenation reactor by preheating at 340 DEG C, 70KPa, hydrocarbon material (light dydrocarbon isolated in separative unit I and Following hydro carbons and raw material C) volume space velocity 400h^-1, alkene: oxygen=1:0.68 (molar ratio), hydrocarbon material (divide in separative unit I The light dydrocarbon separated out and following hydro carbons and raw material C): water=1:30 (mass ratio) carries out oxidative dehydrogenation under this condition.By Separative unit II isolates alkadienes, yield 43.9%, and the mass yield of alcohols is 0.72%, the mass yield of ketone It is 0.40%.The carbon six isolated in the hydro carbons after alkadienes and separative unit I will be isolated and the above hydro carbons is mixed into virtue In structure reactor, the molar ratio of hydrogen and hydro carbons be 0.25 ︰ 1,340 DEG C of reaction temperature, volume space velocity 0.8h^-1, reaction pressure Aromatisation is carried out under the conditions of power 1.8MPa.After isolating fixed gas, the yield of aromatization products is 55.4%, and wherein aromatic hydrocarbons contains Amount is 28.1%.

Embodiment 5

Catalytic dehydrogenation catalyst uses Haitai company HTPB-DH dehydrogenation, wherein with Al₂O₃It is 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 method in embodiment 4 in CN96113127 It is made, the specific steps are 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, in precipitation process 1 gram of sesbania powder is added.When pH value is to 8.5 in solution, terminates ammonium hydroxide and instill.Sediment 80 DEG C heat ageing 1 hour, 55 DEG C aging 30 minutes, filtering used 1000ml water washing, altogether twice every time.Filter cake is 12 hours dry at 110 DEG C, it is forged at 650 DEG C It burns 14 hours, final sizing is that 40~80 mesh are stand-by.The boiling of ZSM-5 containing chromium that aromatized catalyst is provided using Dalian University of Technology Stone molecular sieve catalyst, carrier Al₃O₂, wherein chromium content is 4%, and ZSM-5 zeolite molecular sieve content 25%, shape is straight The cylindrical bars of diameter 1.5mm long 3mm, heap density 0.65g/ml, specific surface area 340m²/ g, Kong Rongwei 0.25ml/g.Using raw material A, Raw material B, raw material C, wherein raw material A, raw material B, raw material C mass ratio be 40:10:1.Raw material A and raw material B, in hydrogen and hydro carbons Material (raw material A and raw material B) molar ratio is 0.1:1,700 DEG C of reaction temperature, volume space velocity 1.0h^-1, reaction pressure 0.15MPa into Row catalytic dehydrogenation, it is 61.4% that reaction, which obtains olefin(e) centent in dehydrogenation product,.Catalytic dehydrogenation product by separative unit I separate with Afterwards, light dydrocarbon and following hydro carbons enter oxidative dehydrogenation reactor, enter oxidative dehydrogenation by preheating with raw material C, pure oxygen gas and water In device at 350 DEG C, pressure 100KPa, hydrocarbon material (light dydrocarbon isolated in separative unit I and following hydro carbons and raw material C) liquid Air speed 350h^-1, alkene: oxygen=1:0.3 (molar ratio), hydrocarbon material (light dydrocarbon isolated in separative unit I and following hydro carbons with Raw material C): water=1:20 (mass ratio) carries out olefin oxidation dehydrogenation reaction under this condition.Oxidative dehydrogenation product is single by separation First II isolates alkadienes, and the yield of alkadienes is 53.0%, and the mass yield of alcohols is 1.20%, the mass yield of ketone It is 0.82%.The carbon six and the above hydro carbons isolated in hydro carbons and separative unit I after isolating alkadienes are mixed into aromatization Change in reactor, is 0.01 ︰ 1 in the molar ratio of hydrogen and the hydro carbons for entering aromatisation unit, 380 DEG C of reaction temperature, volume is empty Fast 0.1h^-1, aromatization is carried out under conditions of reaction pressure 2.2MPa.After isolating fixed gas, the receipts of aromatization products Rate is 44.6%, and wherein arene content is 34.5%.

Embodiment 6

Catalytic dehydrogenation catalyst uses the method preparation using embodiment 1 in patent CN 101618319.By 2.24 grams of oxygen Change calcium and 3.1 grams of polyethylene glycol to be dissolved in 120ml deionized water, 240 DEG C hydro-thermal process 24 hours, 600 DEG C after calcination 5 hours, It is uniformly mixed with appropriate dehydrated alcohol with 7.2 grams of chromic nitrates, 6 grams of aluminum oxides, is ground after 12 hours dry uniformly, It is spare after calcination 3 hours at 550 DEG C.Olefin oxidation dehydrogenation uses the preparation of embodiment 1 in patent CN103055890 Method preparation, the specific steps are as follows: the nitric acid that 280 grams of iron powder and 80.3 grams of zinc powder are added to 1000 milliliters of 1M first is molten In liquid, it is to be dissolved completely after, 97.1 grams of manganese nitrates and 3.3 grams of magnesium nitrates are added, after being completely dissolved, at 60 DEG C of solution temperature Under the conditions of, 20% ammonium hydroxide is added dropwise and is sufficiently stirred, until pH value, after 7.5, solution temperature continues to be kept for 60 DEG C, it is old to continue stirring Change 60 minutes, filtering slurries are simultaneously washed to pH value in 7.0~9.0 values, then by after filter cake extrusion, 200 DEG C drying 12 hours, 500 DEG C after calcining 48 hours, by strip catalyst it is short it is broken be 2~3 millimeters stand-by.Aromatized catalyst uses the prosperous macro chemical industry in Zibo Co., Ltd OCTC-02 aromatization of gas catalyst.Its main component is the cobalt of 40%ZSM-5 molecular sieve and 6%, remaining is Al₂O₃.Its shape is the cylindrical bars of diameter 2.5mm long 3mm, heap density 0.70g/ml, compression strength 90N/cm.Using raw material A, raw material C, raw material D, wherein raw material A, raw material C, raw material D mass ratio be 60:5:1.Raw material A is in dehydrogenation reactor, in hydrogen Gas and hydrocarbon material (raw material A) molar ratio are 0.5:1,570 DEG C of reaction temperature, volume space velocity 3.0h^-1, reaction pressure 1.7MPa's Under the conditions of carry out alkane catalytic dehydrogenating reaction, obtaining in product olefin(e) centent is 60.3%.Catalytic dehydrogenation product is single by separation After first I separation, light dydrocarbon and following hydrocarbon and the mixture of raw material C and raw material D, empty gas and water pass through preheating and enter oxidative dehydrogenation Device, at 380 DEG C, 50KPa, hydrocarbon material (light dydrocarbon isolated in separative unit I and following hydro carbons and raw material C, raw material D) volume Air speed 60h^-1, alkene: oxygen=1:0.85 (molar ratio), hydrocarbon material (light dydrocarbon isolated in separative unit I and following hydro carbons with Raw material C, raw material D): water=1:5 (mass ratio) carries out olefin oxidation dehydrogenation reaction under this condition.Alkadienes in reaction product Mass yield be 23.1%, the mass yield of alcohols is 0.64%, and the mass yield of ketone is 0.37%.Oxidative dehydrogenation The carbon six and the above hydro carbons isolated in product of the product after separative unit II isolates alkadienes and separative unit I are mixed into Enter in aromatization reactor, the molar ratio of hydrogen and hydro carbons be 1:1,600 DEG C of reaction temperature, volume space velocity 5h^-1, reaction pressure Aromatization is carried out under conditions of 2.8MP, after reaction product removes on-condensible gas, yield 73.2%, wherein aromatic hydrocarbons contains Amount is 41.7%.

Comparative example

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 configuring 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 500 DEG C of constant temperature again 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, will be impregnated 20 minutes with burned sample, 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.Virtue Structure catalyst uses the method for CN 1586721A Catalyst Preparation Example 3 and active component Pr is added, specific preparation step It is rapid as follows: ZSM-11 zeolite powder is gone out using hydrothermal synthesis, dries 3 hours at 110 DEG C, 550 DEG C drying 24 hours.Then according to Pr (the NO of the drying of 70g zeolite 30g aluminium oxide butt and 7g₃)₂Powder hand mix is uniform, then with 10% dust technology kneading, Then with after double screw extruder extruded moulding at 110 DEG C it is 3 hours dry, after 550 DEG C constant temperature 3 hours.Then 1mol/ is used L, it is 5, each swap time 2 hours that exchange liquid, which consolidates volume ratio, is exchanged 3 times, liquid is changed in centre.It is washed with deionized water after the completion of exchange It washs, and 3 hours dry at 110 DEG C, it is cooling to use at 550 DEG C after constant temperature 5 hours.Using raw material A and raw material D, raw material A Mass ratio with raw material D is 100 ︰ 1.Raw material A is in dehydrogenation reactor, in hydrogen and hydrocarbons (raw material A) molar ratio 0.3:1,600 DEG C of reaction temperature, volume space velocity 5.0h^-1, reaction pressure 1.1MPa carries out alkane catalytic dehydrogenating reaction, and reaction obtains Olefin(e) centent is 66.7% in dehydrogenation product.Catalytic dehydrogenation product separation after, be directly entered in aromatization reactor, hydrogen with The molar ratio of hydro carbons be 0.3 ︰ 1,260 DEG C of reaction temperature, volume space velocity 8h^-1, react under the conditions of reaction pressure 4.1MPa.Reaction produces After object removes on-condensible gas, the yield of product is 65.0%, and wherein arene content is 35.6%.

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 (35)

1. a kind of method of lower carbon number hydrocarbons production high octane gasoline component, it is characterised in that: include at least following steps:

The first step, raw material and hydrogen rich in four light dydrocarbon carbon of carbon, six alkane enter the catalytic dehydrogenation list equipped with catalytic dehydrogenation catalyst Member obtains logistics a；

Second step, logistics a enter separative unit I, are divided into carbon six and the above hydrocarbon material flow b and light dydrocarbon and following hydrocarbon material flow c；

Third step, by logistics c with rich in alkene raw material, the logistics containing oxidant and water or vapor be sent into it is de- equipped with oxidation The oxidative dehydrogenation unit of hydrogen catalyst, production are rich in diene material d；

4th step, logistics d enter separative unit II, and logistics e is obtained after alkadienes is separated；

Logistics e and logistics b and hydrogen are sent into the low temperature aromatization unit that aromatized catalyst is housed, carry out low temperature by the 5th step Aromatization；

6th step, aromatization products enter separative unit III, and six or less hydro carbons of separation of carbon is simultaneously sent into catalytic dehydrogenation unit circulation and is made With other groups after removing on-condensible gas are divided into the gasoline component rich in aromatic compound.

2. according to the method described in claim 1, it is characterized in that the raw material rich in four light dydrocarbon carbon of carbon, six alkane refers to that refinery exists In production process institute's by-product using four light dydrocarbon carbon of carbon, six alkane as the hydro carbons of main component, or be rich in four light dydrocarbon carbon of carbon, six alkane Raw material paraffin content in 90wt% or more；Or raw material 95wt% in the raw material rich in four light dydrocarbon carbon of carbon, six alkane Boiling range is at 75 DEG C hereinafter, the content of n-alkane is not less than 20wt%.

3. according to the method described in claim 2, it is characterized in that the raw material rich in four light dydrocarbon carbon of carbon, six alkane is tops, coke Change light naphthar, oil field light hydrocarbon, pentane oil and or other devices recycling four light dydrocarbon carbon of carbon, six hydro carbons.

4. according to the method described in claim 2, it is characterized in that being rich in the raw material paraffin of four light dydrocarbon carbon of carbon, six alkane Content is 95wt%；Or in the raw material rich in four light dydrocarbon carbon of carbon, six alkane raw material 95wt% boiling range at 75 DEG C hereinafter, positive structure The content of alkane is not less than 20wt%.

5. according to the method described in claim 1, it is characterized in that the raw material rich in four light dydrocarbon carbon of carbon, six alkane is mixed with hydrogen Olefin(e) centent is not less than 35wt% in the logistics a obtained through catalytic dehydrogenation unit process.

6. according to the method described in claim 5, it is characterized in that the raw material rich in four light dydrocarbon carbon of carbon, six alkane is mixed with hydrogen Olefin(e) centent is in 45wt% or more in the logistics a obtained through catalytic dehydrogenation unit process.

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

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

9. according to the method described in claim 1, it is characterized in that into hydrogen in catalytic dehydrogenation unit and being rich in four light dydrocarbon of carbon The material molar ratio of six alkane of carbon is 0.01~1:1.

10. according to the method described in claim 1, it is characterized in that into hydrogen in catalytic dehydrogenation unit and being rich in four light dydrocarbon of carbon The material molar ratio of six alkane of carbon is 0.1~0.5:1.

11. according to the method described in claim 1, it is characterized in that carbon number is greater than 6 hydro carbons matter in logistics c in separative unit I It measures content and is not higher than 1%.

12. according to the method described in claim 1, it is characterized in that the raw material rich in alkene refers to the carbon generated in chemical process Four hydrocarbon, including carbon four after ether, catalytically cracked C four, cracking c_4, light petrol separation component and or other devices separate The raw material rich in alkene；The boiling range of raw material 95wt% is at 75 DEG C or less in raw material rich in alkene；In raw material rich in alkene The sum of mass content of normal olefine and isomeric olefine is not less than 35wt%.

13. according to the method for claim 12, it is characterised in that the boiling range of raw material 95wt% exists in the raw material rich in alkene 70 DEG C or less；The sum of mass content of normal olefine and isomeric olefine is not less than 45wt% in raw material rich in alkene.

14. according to the method described in claim 1, it is characterized in that being rich in the raw material of four light dydrocarbon carbon of carbon, six alkane and being rich in alkene Material quality ratio be 0.001~100:1.

15. according to the method for claim 14, it is characterised in that raw material rich in four light dydrocarbon carbon of carbon, six alkane be rich in alkene The material quality ratio of hydrocarbon is 0.3~50:1.

16. according to the method described in claim 1, it is characterized in that n-butene and n-pentene conversion ratio divide in oxidative dehydrogenation unit It Bu Diyu not 70wt%.

17. according to the method for claim 16, it is characterised in that n-butene and n-pentene conversion ratio in oxidative dehydrogenation unit It is not less than 75wt% respectively.

18. according to the method described in claim 1, it is characterized in that the condition of oxidative dehydrogenation unit are as follows: temperature be 280 DEG C~ 410 DEG C, 0~100KPa of pressure, 10~500h of volume space velocity^-1。

19. according to the method for claim 18, it is characterised in that the condition of oxidative dehydrogenation unit are as follows: temperature be 310 DEG C~ 395 DEG C, 0~40KPa of pressure, 60~400h of volume space velocity^-1。

20. according to the method described in claim 1, it is characterized in that the oxidant of oxidative dehydrogenation unit is containing oxidizing strong Oxygen atom material stream.

21. according to the method for claim 20, it is characterised in that the oxidant of oxidative dehydrogenation unit be air, oxygen rich air or Oxygen.

22. according to the method described in claim 1, it is characterized in that with oxymeter in the logistics containing oxidant, oxygen with into The olefin molar ratio for entering all hydrocarbon materials in oxidative dehydrogenation unit is 0.1~1.0:1.

23. according to the method for claim 22, it is characterised in that with oxymeter in the logistics containing oxidant, oxygen with into The olefin molar ratio for entering all hydrocarbon materials in oxidative dehydrogenation unit is 0.3~0.85:1.

24. according to the method described in claim 1, it is characterized in that in oxidative dehydrogenation unit vapor and enter oxidative dehydrogenation list The mass ratio of all hydrocarbon materials is 0.5~30:1 in member.

25. according to the method for claim 24, it is characterised in that in oxidative dehydrogenation unit vapor with enter oxidative dehydrogenation The mass ratio of all hydrocarbon materials is 5~20:1 in unit.

26. according to the method described in claim 1, it is characterized in that the reactor of oxidative dehydrogenation unit is two or more fixations Bed reactor or fluidized-bed reactor, using parallel way.

27. according to the method described in claim 1, it is characterized in that two in logistics after isolating alkadienes in separative unit II The mass content of alkene is not higher than 0.3%.

28. according to the method for claim 27, it is characterised in that in the logistics after isolating alkadienes in separative unit II The mass content of alkadienes is not higher than 0.1%.

29. according to the method described in claim 1, it is characterized in that the aromatisation conversion ratio of alkene is not less than in aromatisation unit 92wt%.

30. according to the method described in claim 1, it is characterized in that hydrogen in aromatisation unit and entering in aromatisation unit All hydrocarbon material molar ratios are 0.01~1:1.

31. according to the method for claim 30, it is characterised in that hydrogen and entrance aromatisation unit in aromatisation unit In all hydrocarbon material molar ratios be 0.1~0.5:1.

32. according to the method described in claim 1, it is characterized in that the reaction condition of low temperature aromatization reaction are as follows: 260~600 DEG C, pressure is 0.5~5.0MPa, and volume space velocity is 0.1~10h^-1。

33. according to the method for claim 32, it is characterised in that the reaction condition of low temperature aromatization reaction are as follows: 300~520 DEG C, pressure is 1.4~3.0MPa, and volume space velocity is 1~4h^-1。

34. according to the method described in claim 1, it is characterized in that being recycled to after separation in the separative unit of aromatization products In catalytic dehydrogenation unit in six or less logistics of carbon, carbon six and the above hydro carbons mass content are not higher than 2%.

35. according to the method described in claim 34, it is characterised in that in the separative unit of aromatization products, be recycled to and urge after separation In fluidized dehydrogenation unit in six or less logistics of carbon, carbon six and the above hydro carbons mass content are not higher than 0.5%.