CN106365942A - Mixing C4 conversion method - Google Patents

Abstract

The present invention provides a method for preparing high octane number gasoline components and butadiene from mixing C4. According to the present invention, according to the composition characteristics of rich n-butane, rich isobutane and rich olefin in the mixing C4, the method for producing high octane number gasoline components and butadiene by mainly carrying out an oxidative dehydrogenation, etherification and catalytic dehydrogenation combined process on the mixing C4 is provided; and with the method, the heavy influence of diolefin on the tertiary carbon olefin conversion rate during the etherification process, the high octane number gasoline yield and the etherification product content in the gasoline is overcome while a certain amount of the high value diolefin is produced, such that the economic benefits and the market competition of the process are improved.

Description

A kind of mixing carbon four method for transformation

Technical field

The present invention relates to a kind of work producing butadiene and high octane gasoline component by mixing carbon four conversion Process.

Background technology

Enter 12, with the oil refining of 20,000,000 tons/year of CNPC's Guangdong petrochemical industry, 10,000,000 tons of Kunming/ Year oil refining, Sichuan petrochemical industry Integrated Refinery And Petrochemical engineering, 800,000 tons/year of ethylene of Fushun petrochemical industry, Daqing petrochemical 120 The propulsion of the projects such as ten thousand tons/year of expansion of ethylene, the refining capacity of CNPC and ethylene production capacity also will enter one Step expands, and the yield of the catalytic cracking c4 of refinery's by-product and cracking c4 resource is also being significantly increased.C4 provides Source, in addition to part is used for producing mtbe, alkylate oil, polymerized monomer, is burnt mostly as domestic fuel. And c4 hydrocarbon and tops are not only cheap, and in cost of transportation height, transportation, loss is big, to refinery For belong to low-value product.

Developing rapidly with Chinese national economy, being continuously increased, to vehicle fuel gasoline of automobile pollution Demand increasing.Meanwhile, increasingly strict to gasoline quality standard also with environmental requirement, automobile-used Gasoline quality standard develops to low sulfur content, low olefin-content, low-steam pressure and high-octane direction. Market has pole to volume increase premium-type gasoline with to low-sulfur, low olefin-content, high octane value gasoline blending component Big demand, the technological development of this aspect also becomes the hot issue of domestic each research unit and enterprises pay attention.

Butadiene is elastomeric primary raw material, accounts for the 71% of total raw material, butadiene demand in 2015 It is up to 3,500,000 tons.Chinese butadiene source is more single, mainly uses carbon four extraction process, is filled by ethylene Put production, by 21,000,000 tons of calculating of ethylene ability in 2015, butadiene total resources is 284～2,940,000 Ton, butadiene will appear from serious breach.Another important sources of butadiene are butylene oxidation-dehydrogenation technology.Fourth Alkene oxidative dehydrogenation with positive structure butylene as raw material, domestic n-butene dehydrogenation being total to of relevant unit at home Under making great efforts, experienced ternary molybdenum series catalyst, hexa-atomic molybdenum series catalyst, h-198 ferrum system and b-o2 ferrum Series catalysts, also by initial deflector apron fluid bed development, two-stage nitration finally is axially adiabatic fixing for reaction bed Bed.Industrialized production proves h-198 Fe-series catalyst and deflector apron fluid bed group technology, b-o2 ferrum Series catalysts and the insulation fix bed group technology of two sections of axial directions can make domestic n-butene oxidative dehydrogenation device Production cost and environmental pollution are greatly lowered, and overall economic efficiency reaches same time advanced level.

But from the eighties in 20th century, with constantly newly-built, the butadiene of domestic large-scale ethylene plant Production technology progressively replaced by the less expensive carbon of cost four extraction process, numerous n-butene oxidative dehydrogenation dresses Put and gradually stop production, therefore domestic n-butene oxidative dehydrogenation technology could not further be developed.But it is long-range next See, affected by ethylene cracker raw material lighting, extraction process increase newly butadiene production capacity will be increasingly difficult to Meet the demand to butadiene for the following downstream synthetic rubber.From the point of view of production cost, n-butene oxidative dehydrogenation system The production cost of butadiene is higher than traditional extraction process by 30%～40%.

On the other hand, with increasing oil refining apparatus and ethylene unit newly-built and enlarging, domestic oil refining and The expansion further of ethylene production capacity, the catalytically cracked C four of refinery's by-product and cracking c_4 etc. mix carbon four resource Yield also will be significantly increased.Carbon four resource remove part be used for producing mtbe, alkylate oil, aromatization carburetion, Outside polymerized monomer, burn mostly as domestic fuel.In this part carbon four resource, except normal butane, different Outside butane, containing quite abundant n-butene and isobutene., it is the extraordinary raw material producing butadiene.

Phillips company develops normal butane two step method dehydrogenating technology at first and produces butadiene, and the first step is reacted Using chromium Al catalysts, by normal butane dehydrogenation, n-butene is dehydrogenated to fourth in the presence of steam by second step again Diene.This method raw material only has normal butane, for using produced mixing carbon in oil refining and chemical process For four, less applicable.

Basf company in order to improve the product yield of normal butane dehydrogenation butadiene, in phillips two step method Update on the basis of technique, add oxygen to second step dehydrogenation systems, make dehydrogenation reaction and oxidation reaction It is combined together, thus increasing substantially the conversion ratio of n-butene and the selectivity of butadiene, its technique stream Cheng Wei: the raw material containing normal butane is introduced the first dehydrogenation zone, and the catalytic dehydrogenation of normal butane non-oxidizable ground is First product gas flow of 1-butylene, 2-butylene and butadiene.First product gas flow is introduced the second dehydrogenation zone, And be butadiene by 1-butylene and the ground dehydrogenation of 2-butylene oxidisability, to obtain containing butadiene, normal butane etc. the Two product gas flow, then reclaim butadiene from the second product gas flow.The non-oxidizable catalytic dehydrogenation of normal butane Plate-type reactor is carried out with autothermal catalysis dehydrogenation, this reactor includes one or more continuously urging Agent bed, dehydrogenation is platinum group catalyst.N-butene oxidative dehydrogenation is l, and the catalyst of 3- butadiene is Molybdenum-bismuth-oxygen poly-metal deoxide system.Although after introducing oxygen, the product yield of two step method dehydrogenating technology has Larger raising, but this technique productions step is many, high cost, and steam consumption is very big.

Italian snamprogetti spa company adopts its original tubular reactor and cartridge reactor skill Art, develops the det technique of the Tertiary olefin etherificate in catalytic light gasoline, specifically includes that light gasoline divides From tower, selective hydrogenation reaction device, 2 methyltertiarvbutyl ether reactors, depentanizer, tame knockout tower, mpp Adsorber and non-Tertiary olefin skeletal isomerization reactor.

The tame technological process of production that IFP (ifp) develops includes purification of raw materials, etherificate Reaction and Methanol Recovery 3 part.Except that etherification reaction employs a main reactor, and (expanded bed is anti- Answer device) and an end reaction device (catalytic rectifying tower) be used in series, the 90% of wherein total material is swollen Carry out in swollen bed reactor.

The catalytic light gasoline etherification technology that Arco chemical technology company (arco) develops, is mainly used in giving birth to Produce mtbe coproduction tame.In Etherification of Light FCC Gasoline technique, etherification reaction adopts tandem fixed bed adiabatic anti- Answer device.Its technological process is divided into purification of raw materials, etherification reaction and 3 unit processes of Methanol Recovery.C5 is former Two fixed bed adiabatic reactions that material is connected with methanol mixed, entrance after washing, selection weighted BMO spaces In device, reacted in the presence of ion-exchange resin catalyst.

During producing butadiene using two step dehydridings, n-butene and normal butane do main contributions, isobutyl Alkene and iso-butane conversion ratio are relatively low.And during catalytic dehydrogenation, iso-butane is converted into turning of isobutene. Rate is higher.Tertiary olefin in logistics can be generated in the presence of catalyst accordingly using etherification technology Ether compound, Tertiary olefin conversion ratio, more than 95%, isobutene conversion is high-octane ether Class compound, as gasoline blend component.Different from n-butene and n-butane feedstock, in mixing carbon four, no Only abundant normal butane, the also suitable n-butene of content, isobutene., iso-butane, the present invention is by two steps The technique of butadiene is produced in dehydrogenation and etherification technology combines, and exploitation is a kind of to utilize mixing carbon four component next life Produce the process of butadiene and high octane gasoline component, the added value of mixing carbon four can be improved further.

Content of the invention

Present invention aims to positive iso-butane, positive isoolefine hydrocarbon content are relatively all richer in mixing carbon four Rich compositing characteristic, provides a kind of mixing carbon four mainly to combine through oxidative dehydrogenation, etherificate, catalytic dehydrogenation Technical process, the method producing butadiene and high octane gasoline component.

A kind of mixing carbon four method for transformation, is characterised by that conversion process at least comprises the steps: that the first step is mixed Close carbon four raw material, the logistics containing oxidant and water or water vapour enters oxidative dehydrogenation unit, in filling oxidation In the reactor of dehydrogenation react after, enter separative element i, by reacted logistics be divided into butadiene, Other C-4-fractions and other components；Second step is by the other C-4-fractions isolated in the first step and alcohols thing Streaming enters to be etherified unit, carries out etherification reaction in the reactor equipped with catalyst for etherification, and product enters divides From unit ii, reacted logistics is divided into carbon more than five component, C_4 hydrocarbon and other component；3rd step will Isolate C_4 hydrocarbon in second step and send into catalytic dehydrogenation unit with hydrogen, anti-equipped with catalytic dehydrogenation catalyst Answer and in device, carry out alkane catalytic dehydrogenating reaction, and the logistics after catalytic dehydrogenation is separated through separative element iii After going out on-condensible gas, send into oxidative dehydrogenation unit together with mixing carbon four raw material.

In the present invention, mixing carbon four raw material refers to refine oil the C_4 hydrocarbon with generation in chemical process, such as carbon after ether 4th, the separation component of catalytically cracked C four, cracking c_4 or light gasoline.Wherein C_4 hydrocarbon quality Content is not less than 95%, preferably not below 99%, and C 4 olefin mass content is not less than 40%, preferably not Less than 50%, the mass content of n-butene and normal butane and be not less than 35%, preferably not below 40%.Can To be raw material or the mixing of separate sources raw material in same source.

In the present invention, the catalyst of oxidative dehydrogenation unit does not also specially require, and can meet n-butene conversion not Less than 70%, preferably not below 75% requirement.The not specified percentage ratio of the present invention is matter Amount %.Oxydehydrogenation catalyst can be the main work loading specific ratios using some resistant to elevated temperatures framework materials Property component and help active component to complete.Wherein, resistant to elevated temperatures framing structure can be metal gauze, many Empty material all in one piece or aluminium oxide of different shapes, silicon dioxide, zirconium oxide, cordierite, titanium oxide, rich alumina minium Pillar, stable aluminium oxide, stable zirconium oxide etc. or two kinds of above exotic material or two Plant above mixture.The mode of loading of active component can for micro- wet impregnated with method, chemical vapour deposition technique, Coprecipitation etc..Main active component can be 3%～8% lanthanide element or lanthanide element Oxide, or being mutually mixed for several materials above, can be specifically samarium, cerium, praseodymium, terbium, and its One or several combination in oxide；Can also be 0.2%～1% platinum group and combinations thereof, Can be specifically ruthenium, one of palladium, osmium, iridium or platinum or several.Preferably also comprise in catalyst The metal of 0.01%～0.07% viii race, the metal-oxide of viii race or combinations thereof, tool Body is ferrum, ferrum oxide, nickel, nickel oxide, palladium, Palladium monoxide, platinum, platinum oxide, sail, vanadium oxide, chromium, Chromium oxide, manganese, one of manganese oxide etc. or several combinations.Less than 0.1% alkali can also be added Earth metal and rare earth element are as helping active component.Oxydehydrogenation catalyst is preferably coprecipitation method preparation There is spinelle or the ferrite of hexahedron structure and the catalyst of alpha-ferric oxide structure simultaneously.Ferrite In metal ion can be, zinc, barium, magnesium, calcium, strontium, nickel, one of copper or several.Relatively A kind of Oxydehydrogenation catalyst of the spinelle-alpha-ferric oxide structure of employing coprecipitation method preparation recommended In, spinelle content 45-60%, the content 2.8%～4.4% of zinc ferrite, other ferrous acid salt contents and not high In 3%.

In the present invention, the reaction condition of oxidative dehydrogenation unit is to be slightly different according to different catalyst, but It is well: temperature is 280 DEG C～410 DEG C, preferably 310 DEG C～395 DEG C, pressure 0～100kpa, preferably 0～ 40kpa, volume space velocity 10～500h^-1, preferably 60～400h^-1.The not specified air speed of the present invention is equal For volume space velocity during liquid.

In the present invention, the logistics containing oxidant of oxidative dehydrogenation unit can be oxygen, oxygen rich air, air etc. Containing oxygen molecule or contain oxidizing strong oxygen atom material stream, preferred air in the present invention, oxygen rich air and Oxygen.Particularly preferably oxygen rich air.Oxygen rich air between 32%～45% for the special recommendation oxygen content.Wherein, With oxymeter in logistics containing oxidant, the alkene of all hydrocarbon materials in oxygen and entrance oxidative dehydrogenation unit Hydrocarbon mol ratio is 0.1～1.0:1, preferably 0.3～0.85:1.In the fill process of oxidative dehydrogenation unit, add The water of certain ratio or vapor, lead to temperature with the coking and beds preventing catalyst due to coking Degree rises too fast problem.In water or steam oxidation dehydrogenation unit, the mass ratio of all hydrocarbon materials can be 0.5～30:1, preferably 5～20:1.

In the present invention reactor of oxidative dehydrogenation unit can for fixed bed reactors, fluidized-bed reactor, Moving-burden bed reactor, trickle bed reactor or catalystic rectifying reactor, fixed bed reaction tube bank, Can also be above reactor series connection and or parallel connection.Preferred reactor is two or multiple stage fixed bed reaction Device or the parallel way of fluidized-bed reactor, facilitate the regeneration of catalyst and the continuous of technical process.

In separative element i in the present invention, separation method can be extraction, rectification or extracting rectifying, Azeotropic distillation, membrance separation, chemical absorbing etc..Can be obtained using the ripe isolation technics of Technical comparing Qualified 1,3-butadiene product, and make the content of butadiene in other C-4-fractions of separating not It is more than not higher than 0.3%, preferably not higher than 0.1%.

It is not particularly limited catalyst for etherification it is desirable to the conversion ratio of isobutene. is not low in etherificate unit in the present invention In 95%.

Alcohols logistics in etherificate unit in the present invention refers to the low-carbon alcohols that carbon atom number is not more than 4, especially Recommend methanol, ethanol, preferably methanol.

When in the present invention, raw material enters etherification reaction unit, alcohols is etherified all hydrocarbon materials of unit with entering In isobutene. mol ratio be 0.8～1.5:1, preferably 1.1～1.3:1.

The reaction condition being etherified unit in the present invention is: 30～100 DEG C, preferably 45～80 DEG C, pressure is 0.1～2.0mpa, preferably 0.5～1.5mpa, volume space velocity is 0.1～5h^-1, preferably 1～2h^-1.

In the present invention, methyltertiarvbutyl ether reactor is not particularly limited, can be fixed bed, moving bed suspension bed, catalysis One of distillation reactor etc. or several combinations.It is desirable that being catalytic distillation technology, tertiary carbon can be made Alkene fully converts, and in separative element, the C-4-fraction of separating methanol tower top output sends into catalytic dehydrogenation unit, tower The as high octane gasoline component of kettle output, the methanol of recovery can also be recycled to methyltertiarvbutyl ether reactor entrance to be made With.

In separative element ii in the present invention, separation method is not limited, and can divide for rectification, extraction, film From etc., but compare and recommend rectification.Require in carbon four logistics isolate ethers, the quality of carbon four component Content is not less than 97%, preferably not below 99%.

It is not particularly limited dehydrogenation it is desirable to alkene in catalytic dehydrogenation product in catalytic dehydrogenation unit of the present invention Hydrocarbon content is not less than 35%, is preferably such that olefin(e) centent more than 45%.

In the present invention, the reaction condition of catalytic dehydrogenation unit is preferably: 480～700 DEG C, pressure 0.01～ 3mpa, liquid volume air speed is 0.1～10h^-1.The reaction condition of special recommendation is: 560～650 DEG C, pressure Power 0.4～1.2mpa, liquid volume air speed is 2～7h^-1.

Entering hydrogen and C_4 hydrocarbon mol ratio in catalytic dehydrogenation unit in the present invention is 0.01～1:1, preferably 0.1～0.5:1.

The catalytic dehydrogenating reaction device being related in the present invention is fixed bed reactors, can be a reactor list Solely use, two processes interval realizations are regenerated by reaction-catalyst it is also possible to two or more reactor Used in parallel be circulated operation, multiple reactors can also be divided in parallel and or series combination use.When one Catalyst in individual or several reactor due to carbon distribution serious inactivation, by switching material import and export, urge by inactivation Agent regeneration Posterior circle uses, and realizes reaction, the continuous operation of regenerative system.

The dry gas that on-condensible gas after catalytic dehydrogenation unit in the present invention, separative element ii separate can To direct cycle to catalytic dehydrogenation supplies of unit entrance, recycle.

In addition, the segregation apparatuss of on-condensible gas can be included in separative element, such as flash tank, absorption/parsing Tower, chiller and compressor etc..

The present invention more specifically embodiment is: is not less than 95% using C_4 hydrocarbon mass content, preferably not Less than 99%, C 4 olefin mass content is not less than 40%, preferably not below 50%, n-butene and positive fourth The mass content of alkane and be not less than 35%, preferably not below 40% mixing carbon four raw material.It is 280 in temperature DEG C～410 DEG C, pressure 0～100kpa, volume space velocity 10～500h^-1, oxygen with enter oxidative dehydrogenation list The olefin molar ratio of all hydrocarbon materials of unit is 0.1～1:1, water or water vapour with enter oxidative dehydrogenation unit The mass ratio of all hydrocarbon materials be under the process conditions of 0.5～30:1, with oxygen content 32%～ Oxygen-enriched stream mixing between 45% carries out oxidative dehydrogenation, after product isolates butadiene, with alcohol Class logistics enters etherificate unit, and alcohols with the isobutene. mol ratio in the hydrocarbon material entering methyltertiarvbutyl ether reactor is 0.8～1.5:1, preferably 1.1～1.3:1, in 30～100 DEG C of temperature, preferably 45～80 DEG C, pressure is 0.1～2.0mpa, preferably 0.5～1.5mpa, volume space velocity is 0.1～5h^-1, preferably 1～2h^-1 Under conditions of carry out etherification reaction after, after isolating ether compound in product and other components, remain Remaining C_4 hydrocarbon enters catalytic dehydrogenation unit, and in 480～700 DEG C of temperature, pressure 0.01～3mpa, volume is empty Speed is 0.1～10h^-1, hydrogen with enter catalytic dehydrogenation unit all hydrocarbon materials mol ratio be 0.01～ After carrying out catalytic dehydrogenating reaction under conditions of 1:1, enter oxidative dehydrogenation unit together with raw material mixing carbon four.

During mixing carbon four modification utilizes, overcoming isomerization technique, it produced advantages of the present invention Unfriendly to environment in journey, high temperature aromatization technology dry gas production rate is high by 20%, technical process easily The shortcomings of economic benefit can be subject to no small loss, during etherification technology continues deeper into research and utilization, Produce diene units and alkadienes separative element by increasing oxidative dehydrogenation, both overcome the serious shadow of alkadienes While ringing conversion ratio, the ether compound yield that monoolefine is etherified, the diene of a certain amount of high value of by-product Hydrocarbon, thus improve economic benefit and the market competitiveness of this technique, the also utilization low-carbon (LC) for more becoming more meticulous Alkanes provide another technique.In addition, in oxidative dehydrogenation process, due to the generation of side reaction, A small amount of ketone and aldehyde can be produced.The amount of aldehyde and ketone generation is too high, directly affects alkadienes optionally simultaneously, Process washing aldehyde and the waste water process of ketone generation also can increase process costs.In the present invention, oxygen-enriched by controlling In air-flow, oxygen content enters reaction system material total amount to control, and to control oxygen atom in reaction system, alkene The contact with catalyst for the hydrocarbon, controls reaction time from still further aspect.This method not only can guarantee that list Alkene is fully converted into alkadienes, and effectively controls the generation of alcohols and aldehydes, improves two The yield of alkene and selectivity.

Brief description

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

In figure: r1- oxidative dehydrogenation reactor, r2- methyltertiarvbutyl ether reactor, r3- catalytic dehydrogenating reaction device, t1, T2, t3- are reactor r1, r2, r3 piece-rate system i, ii below, iii.

Specific embodiment

Below by embodiment in detail the present invention is described in detail.Table 1, table 2 by embodiment employing mixing carbon four raw material Property, mixing carbon four a is catalyzed workshop mixing carbon four for Lanzhou Petrochemical Company, and mixing carbon four b refines for grand celebration Change company one urges mixing carbon four again.Methanol adopts the methanol that commercially available Cangzhou Zheng Yuan Chemical Co., Ltd. produces, its The mass content of middle methanol is 99.5%.Ethanol adopts the nothing that commercially available Yixing City Qiu Yun Chemical Co., Ltd. produces The mass content of water-ethanol, wherein ethanol is 99.5%.

Table 1 mixes the composition (w%) of carbon four a

Table 2 mixing carbon four b composition (w%)

Component	ω %	Component	ω %
				Propane	0.00	Isobutene.	12.45
Propylene	0.00	Cis-butene-2	12.79
				Iso-butane	34.29	Isopentane	0.06
Normal butane	10.38	1,3- butadiene	0.07
				Trans-butene-2	17.33	2- methyl-2-butene	0.02
1-butylene	12.63	1- amylene	0.04

All using technique as shown in Figure 1, in embodiment, catalytic dehydrogenating reaction device pressurizes embodiment for 200ml Two reactor cycles of fixed bed reactors use, and oxidative dehydrogenation unit adopts the suspension bed reaction of 100ml Device, etherification reaction system adopts catalytic distillation reaction unit, and pre- methyltertiarvbutyl ether reactor is 200ml fixed bed, In reactive distillation column, loaded catalyst is 150ml.Analysis sample is the instantaneous sample after reacting 3 hours.Point The rectifying column being 18 using theoretical cam curve in unit i (t1).Adopt in separative element ii (t2) After cyclone separator dehydration, flash distillation removes on-condensible gas, and extraction isolates alkadienes.Separative element iii (t3) rectifying column being 10 using number of theoretical plate.

Prepare in the raw material that catalyst is adopted in embodiment, sesbania powder is technical grade, other is commercially availableization Learn pure reagent.

Water is deionized-distilled water.

Oxygen-enriched stream is by technical grade pure oxygen and air mixed configuration.

In embodiment, the content of alkene, the yield of alkadienes, the yield of aromatization products, arene content Computational methods are as follows:

In the quality/catalytic dehydrogenation product of produced butylene, amylene in the content of alkene=catalytic dehydrogenation product Quality * 100 of all hydro carbons

The mass yield of alcohols=alcohols quality produced by oxidative dehydrogenation unit and/entrance oxidative dehydrogenation unit Quality * 100 of middle hydrocarbon material

The mass yield of ketone=ketone quality produced by oxidative dehydrogenation unit and/entrance oxidative dehydrogenation unit Quality * 100 of middle hydrocarbon material

The mass yield of alkadienes=alkadienes quality produced by oxidative dehydrogenation unit/entrance oxidative dehydrogenation list Quality * 100 of hydrocarbon material in unit

Quality after yield=etherificate all product removal on-condensible gas of etherification product/entrance etherificate unit hydrocarbon Quality * 100 of class material

Embodiment 1

Olefin oxidation dehydrogenation adopts the preparation method system of embodiment 2 in patent cn102671714a Standby, concrete preparation method is as follows: 17 grams of magnesium nitrate hexahydrates is dissolved in 20ml distilled water, then Add 20 grams of zirconium oxides, above-mentioned mixed solution be evaporated be dried 12 hours afterwards in Muffle furnace at 80 DEG C, The solid sample of heating gained 3 hours in air atmosphere at 550 DEG C, then use metavanadic acid ammonia spirit to soak Stain sample.Metavanadic acid ammonia spirit is by steaming 5 grams of metavanadic acid ammonia and 10.6 grams of dissolving oxalic acid a small amount of Prepare in distilled water.It is being dried 12 hours at 80 DEG C through the sample of metavanadic acid ammonia solution dipping, Ran Hou In Muffle furnace, heat the solid sample 3 hours of gained in the air atmosphere at 550 DEG C, final sizing is 40～80 mesh are stand-by.Catalyst for etherification adopts the kc-116 type resin catalyst that Kai Rui chemical company produces, Its particle size range >=99% (0.355～1.250mm), wet true density 1150～1250g/l, total exchange capacity ≥1.7mmol/ml[h⁺], mechanical strength >=98% (H type).Catalytic dehydrogenation catalyst adopts Haitai company Htpb-dh dehydrogenation, wherein with al₂o₃For carrier with pt and cl as active component, wherein pt Mass content be 1%, chlorine mass content be 2%, specific surface area be 200m²/ g, pore volume 0.5ml/g, A diameter of 1.59mm, heap density 0.6g/cm³.Raw material a enters oxidative dehydrogenation with empty gas and water through preheating In reactor, at 340 DEG C, atmospheric pressure, air speed 400h^-1, enter all hydrocarbons of oxidation deacidification unit Alkene in material: oxygen=1:0.68 (mol ratio), enter all hydrocarbon materials of oxidative dehydrogenation unit: water Reacted under the process conditions of=1:12 (mass ratio).In product, the mass yield of alkadienes is 55.4%, the mass yield of alcohols is 0.52%, and the mass yield of ketone is 0.45%.Product is passed through Separative element i, after isolating butadiene, by other C-4-fractions enter methyltertiarvbutyl ether reactor in, etherificate anti- The condition is answered to be: 45 DEG C of reaction temperature, volume space velocity 2h^-1, reaction pressure 1.5mpa, wherein methanol with enter The mol ratio entering isobutene. in hydrocarbon material in methyltertiarvbutyl ether reactor is 1.2:1.In product, ethers chemical combination The mass yield of thing is 49.2%.After separative element ii isolates ether compound, C_4 hydrocarbon enters and urges In fluidized dehydrogenation reactor, in hydrogen with all hydrocarbon material mol ratios entering catalytic deoxidation unit it is 0.25:1, in 480 DEG C of reaction temperature, volume space velocity 0.1h^-1, it is catalyzed under conditions of reaction pressure 0.01mpa Dehydrogenation, it is 37.1% that reaction obtains olefin(e) centent in dehydrogenation product.

Embodiment 2

Olefin oxidation dehydrogenation adopts the preparation of catalyst in embodiment 1 in patent cn99106660.x Method, its concrete preparation method is as follows: by the manganese dioxide powder of 43.5g with 1000ml water in same appearance In device, agitating heating, after 10 minutes, adds 1.09 grams of antimony trioxide powder, system is heated to after 80 DEG C Then temperature is heated to 90 DEG C and is stirred for 4 hours by stirring 2 hours, when System forming pastel, It is dried 14 hours at 120 DEG C, makes powder, molding, final sizing is that 40～80 mesh are stand-by.Etherificate is urged Agent adopts the d005-ii resin catalyst that Dandong Mingzhu Special Type Resin Co., Ltd. produces.Its particle size range 0.315～1.25mm, wet true density 1180～1200g/l, total exchange capacity >=5.2mmol/g [h⁺], machine Tool intensity >=95% (H type).Catalytic dehydrogenation catalyst adopts the side of embodiment 4 in cn101940922a Prepared by method.It concretely comprises the following steps: first weighs 117.5 grams of chromium oxide, is dissolved in deionized water and being sufficiently stirred for, Being configured to weight concentration is 47% oxidation chromium solution.It is reconfigured at the potassium nitrate that weight concentration is 3.86% water-soluble Liquid.Then by 55.0 grams of boehmites, 2.2 grams of bentonite, the oxidation chromium solution preparing with 7.59 grams It is sufficiently mixed, mediate, be extruded into bead.Then it is dried 3 hours at 120 DEG C, then in 500 DEG C of constant temperature 3 hours, in 620 DEG C of constant temperature 2 hours, finally 760 DEG C of roastings 4 hours under 20% water and 80% air. Take 11.39 grams of the oxidation chromium solution preparing again, roasting sample is impregnated 20 minutes, at 120 DEG C It is dried 3 hours, in 550 DEG C of constant temperature calcinings 5 hours.The Alkitrate preparing is taken to impregnate again, 120 DEG C of dryings 3 hours, standby in 620 DEG C of constant temperature calcinings 6 hours.Raw material b with oxygenous 45% richness Oxygen stream, water enter in oxidative dehydrogenation reactor through preheating, at 350 DEG C, pressure 100kpa, and volume Air speed 10h^-1, enter the alkene in the hydrocarbon material of oxidation unit: oxygen=1:0.3 (mol ratio), enter oxidation The hydrocarbon material of unit: reacted under the process conditions of water=1:30 (mass ratio).In product, diene The mass yield of hydrocarbon is 49.2%, and the mass yield of alcohols is 0.47%, and the mass yield of ketone is 0.23%. Product, through separative element i, isolates butadiene, and other C-4-fractions enter in methyltertiarvbutyl ether reactor, The reaction condition of etherificate is: 80 DEG C of reaction temperature, volume space velocity 3.0h^-1, reaction pressure 1.0mpa, its Middle methanol is 1.1:1 with the mol ratio entering isobutene. in hydrocarbon material in methyltertiarvbutyl ether reactor.In product, The mass yield of ether compound is 44.8%.After separative element ii isolates ether compound, carbon four Hydrocarbon enter catalytic dehydrogenating reaction device in, hydrogen with enter catalytic deoxidation unit all hydrocarbon material mol ratios For 0.1:1, in 700 DEG C of reaction temperature, volume space velocity 1.0h^-1, reaction pressure 0.15mpa reacted, It is 51.6% that reaction obtains olefin(e) centent in dehydrogenation product.

Embodiment 3

Olefin oxidation dehydrogenation adopts the method for preparation example 2 in patent 200780013916.9 to be obtained, It specifically comprises the following steps that and 69 grams of ammonium molybdate is dissolved in stirring in 500ml distilled water, then by 108.1 Gram bismuth nitrate be added in 5.3% salpeter solution and stir to after be completely dissolved, be added drop-wise to ammonium molybdate solution In.Then Deca ammonia makes the ph to 1.5 of above-mentioned solution, and after stirring 1 hour, decompression sucking filtration obtains solid Body sample, then at 100 DEG C, solid sample is dried after 26 hours, at 475 DEG C in Muffle furnace, Calcining 24 hours, last crushing and screening is that 20～80 mesh are stand-by.Catalyst for etherification adopts Nankai University's chemical industry The nkc-9 cation exchange resin catalyst that factory produces.Its particle size range >=95% (0.4～1.25mm), Specific surface area 77m²/ g, pore volume 0.27ml/g, total exchange capacity >=4.7mmol/g [h⁺].Dehydrogenation Using the method preparation using embodiment 1 in patent cn 101618319.By 2.24 grams of calcium oxide and 3.1 Gram Polyethylene Glycol is dissolved in 120ml deionized water, 240 DEG C of hydrothermal treatment consists 24 hours, and 600 DEG C of calcinations 5 are little Shi Hou, is used appropriate dehydrated alcohol to mix homogeneously with 7.2 grams of chromic nitrates, 6 grams of aluminium sesquioxide, is dried Grind uniformly after 12 hours, standby after calcination 3 hours at 550 DEG C.With oxygenous 35% oxygen rich air Stream, water enter in oxidative dehydrogenation reactor through preheating, at 380 DEG C, 50kpa, volume space velocity 60h^-1, Enter the alkene in the hydrocarbon material of oxidation unit: oxygen=1:0.1 (mol ratio), enter the hydro carbons of oxidation unit Material: reacted under the process conditions of water=1:5 (mass ratio).In product, the mass yield of alkadienes For 56.1%, the mass yield of alcohols is 0.39%, and the mass yield of ketone is 0.18%.Product warp Cross separative element i, isolate butadiene, other carbon four components enter in methyltertiarvbutyl ether reactor, the reaction of etherificate Condition is: 65 DEG C of reaction temperature, volume space velocity 4h^-1, reaction pressure 0.5mpa, wherein methanol and entrance In hydrocarbon material in methyltertiarvbutyl ether reactor, the mol ratio of isobutene. is 1.3:1.In product, ether compound Mass yield be 58.8%.After separative element ii isolates ether compound, C_4 hydrocarbon enters catalysis In dehydrogenation reactor, hydrogen is 0.01:1 with all hydrocarbon material mol ratios entering catalytic deoxidation unit, 570 DEG C of reaction temperature, volume space velocity 3.0h^-1, reacted under conditions of reaction pressure 1.7mpa, reaction Obtaining olefin(e) centent in dehydrogenation product is 54.9%.

Embodiment 4

Olefin oxidation dehydrogenation adopts the method system preparing embodiment 2 in patent 200880014941.3 , it specifically comprises the following steps that and for 14.2 grams of zinc chloride and 56.1 grams of ferric chloride hexahydrates to be dissolved in 800ml In distilled water, it is stirred well to after being completely dissolved, the sodium hydrate aqueous solution of Deca 3m adjusts above-mentioned solution Ph value to 8, after being then stirred at room temperature 12 hours, decompression sucking filtration obtains solid sample.By solid-like Product are dried 16 hours at 175 DEG C, calcine 12 hours at 650 DEG C, and last crushing and screening is 20～65 Mesh is stand-by.The macropore strong acid that catalyst for etherification is produced using Jiangsu AudioCodes petrochemistry Technology Co., Ltd. Resin catalyst, its granularity is 0.315-1.25mm, bulk density 0.77-0.85g/ml, and specific surface area is big In 20-70m²/ g, aperture is more than 20-50nm, and pore volume is more than 0.3-0.5cc/g.Dehydrogenation adopts The method preparation of embodiment 4 in cn101940922a.It concretely comprises the following steps: first weighs 117.5 grams of oxygen Change chromium, be dissolved in deionized water and being sufficiently stirred for, being configured to weight concentration is 47% oxidation chromium solution.Join again Put the Alkitrate that weight concentration is 3.86%.Then by 55.0 grams of boehmites, 2.2 grams of swellings Soil, the oxidation chromium solution being prepared with 7.59 grams is sufficiently mixed, and mediates, is extruded into bead.Then again 120 It is dried at DEG C 3 hours, then in 500 DEG C of constant temperature 3 hours, in 620 DEG C of constant temperature 2 hours, finally 20% Water and lower 760 DEG C of roastings of 80% air 4 hours.Take 11.39 grams of the oxidation chromium solution preparing again, will roast Burned sample impregnates 20 minutes, in 120 DEG C of dryings 3 hours, in 550 DEG C of constant temperature calcinings 5 hours. The Alkitrate preparing is taken to impregnate, in 120 DEG C of dryings 3 hours, in 620 DEG C of constant temperature calcinings 6 again Hour is standby.Raw material b enters oxidative dehydrogenation with oxygenous 40% oxygen-enriched stream, water through preheating In device, at 390 DEG C, 20kpa, volume space velocity 500h^-1, enter the alkene in the hydrocarbon material of oxidation unit Hydrocarbon: oxygen=1:0.8 (mol ratio), enter the hydrocarbon material of oxidation unit: the process conditions of water=1:16 (mass ratio) Under reacted.In product, the mass yield of alkadienes is 46.7%, and the mass yield of alcohols is 0.41%, the mass yield of ketone is 0.20%.Product, through separative element i, isolates butadiene, Other C-4-fractions enter in methyltertiarvbutyl ether reactor, and the reaction condition of etherificate is: 75 DEG C of reaction temperature, volume Air speed 5h^-1, isobutyl in hydrocarbon material in reaction pressure 1.2mpa, wherein methanol and entrance methyltertiarvbutyl ether reactor The mol ratio of alkene is 1.5:1.In product, the mass yield of ether compound is 50.5%.Through undue Isolate after ether compound from unit ii, C_4 hydrocarbon enters in catalytic dehydrogenating reaction device, hydrogen and entrance All hydrocarbon material mol ratios of catalytic deoxidation unit are 0.3:1, in 600 DEG C of reaction temperature, volume space velocity 5.0h^-1, reacted under reaction pressure 1.1mpa, it is 64.0% that reaction obtains olefin(e) centent in dehydrogenation product.

Embodiment 5

Olefin oxidation dehydrogenation adopts method in embodiment 4 in cn96113127 to be obtained, concrete steps 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, and the quick ammonia stirring lower instillation 20% sinks Form sediment, in precipitation process, add 1 gram of sesbania powder.When ph value is to 8.5 in solution, terminates ammonia and instill. Precipitate is in 80 DEG C of heat ageings 1 hour, aging 30 minutes at 55 DEG C, filters, uses 1000ml every time Water washing, altogether twice.Filter cake, in 110 DEG C of dryings 12 hours, is calcined 14 hours at 650 DEG C, is finally sieved It is divided into 40～80 mesh stand-by.Catalyst for etherification adopts the etherified resin catalysis that Kai Rui Chemical Co., Ltd. produces Agent, its particle size range 0.335～1.25mm, wet true density 0.75～0.85g/ml, total exchange capacity >=5.2 Mmol/g, mechanical strength >=95%.Dehydrogenation adopts embodiment 9 in patent cn96121452.x Method preparation.Weigh 17 grams of cr (no₃)₃·9h₂O, 1.1 grams of cu (no₃)₂·3h₂O, 80.8 grams al(no₃)₃·9h₂O, prepares catalyst with coprecipitation, and 10% koh (or naoh) selected by precipitant Solution, nitrate is dissolved in distilled water, adds precipitant while stirring so as to form gel completely, and Ph value is 8.5～9, aging 3 hours, filters, and at 110 DEG C, is dried 20 hours, roasts at 650 DEG C Burn 7 hours, rear standby after crushing and screening.Raw material a is passed through in advance with oxygenous 32% oxygen-enriched stream, water Heat enters in oxidative dehydrogenation reactor, at 280 DEG C, 10kpa, volume space velocity 300h^-1, enter oxidation single Alkene in the hydrocarbon material of unit: oxygen=1:0.55 (mol ratio), enter the hydrocarbon material of oxidation unit: water Reacted under the process conditions of=1:10 (mass ratio).In product, the mass yield of alkadienes is 55.6%, the mass yield of alcohols is 0.43%, and the mass yield of ketone is 0.21%.Product is passed through Separative element i, after isolating butadiene, other C-4-fractions enter in methyltertiarvbutyl ether reactor, the reaction of etherificate Condition is: 55 DEG C of reaction temperature, volume space velocity 0.1h^-1, reaction pressure 2.0mpa, wherein ethanol with enter Entering isobutene. mol ratio in hydrocarbon material in methyltertiarvbutyl ether reactor is 1.2:1.In product, ether compound Mass yield be 48.5%.After separative element ii isolates ether compound, C_4 hydrocarbon enters catalysis In dehydrogenation reactor, hydrogen is 0.15:1 with all hydrocarbon material mol ratios entering catalytic deoxidation unit, 650 DEG C of reaction temperature, volume space velocity 8.0h^-1, reacted under conditions of reaction pressure 2.4mpa, reaction Obtaining olefin(e) centent in dehydrogenation product is 35.6%.

Embodiment 6

Olefin oxidation dehydrogenation adopts the preparation method preparation of embodiment 1 in patent cn103055890, Specifically comprise the following steps that and first the zinc powder of 280 grams of iron powder and 80.3 grams is added to 1000 milliliters of 1m's In salpeter solution, to be dissolved completely after, add 97.1 grams of manganese nitrates and 3.3 grams of magnesium nitrates, be completely dissolved Afterwards, under conditions of 60 DEG C of solution temperature, the ammonia of Deca 20% is simultaneously sufficiently stirred for, to ph value 7.5 Afterwards, solution temperature continues to keep 60 DEG C, continues aging 60 minutes of stirring, filters serosity and washs to ph Value in 7.0～9.0 values, then by after filter cake extrusion, 200 DEG C of dryings 12 hours, 500 DEG C of calcinings 48 are little Shi Hou, by short for strip catalyst broken be 2～3 millimeters stand-by.Catalyst for etherification buys petrochemical industry academy of science The rze-3 zeolite catalyst for etherification of research and development, profile is that diameter 8mm is spherical, bulk density 0.71g/cm³, Specific surface area 487m²/ g, pore volume 0.464ml/g, average pore size 175nm, intensity > 20n.Dehydrogenation is urged Agent prepares catalyst using the step of catalyst preparation in embodiment 1 in patent cn 101623633a. Zsm-5 molecular screen primary powder is placed in the sncl of 0.16m first₂·2h₂10hr is impregnated in 80 DEG C in o solution, The load capacity making the sn in catalyst reaches 4wt%, then 6hr is dried at 120 DEG C.Dried Sample roasting 4hr under 550 DEG C of air atmosphere.Powder after roasting is in the h of 0.03m₂ptcl₆·6h₂o Impregnate 4hr in solution at 80 DEG C, make catalyst that pt content be 20wt% to be finally obtained, then 120 6hr is dried, roasting 4hr at 550 DEG C at DEG C.Standby in 550 DEG C of hydrogen reducing 12hr afterwards.With pure oxygen Gas and water enters in oxidative dehydrogenation reactor through preheating, at 340 DEG C, 70kpa, volume space velocity 250h^-1, Enter the alkene in the hydrocarbon material of oxidation unit: oxygen=1:0.1 (mol ratio), enter the hydrocarbon of oxidation unit Material: reacted under the process conditions of water=1:0.5 (mass ratio).In product, the quality of alkadienes is received Rate is 41.7%, and the mass yield of alcohols is 0.82%, and the mass yield of ketone is 0.66%.Product Through separative element i, isolate butadiene, other carbon four components enter in methyltertiarvbutyl ether reactor, etherification reaction Condition is: 30 DEG C of reaction temperature, volume space velocity 0.5h^-1, reaction pressure 1.7mpa, wherein methanol with enter The mol ratio entering isobutene. in hydrocarbon material in methyltertiarvbutyl ether reactor is 0.95:1.In product, ethers The mass yield of compound is 42.5%.After separative element ii isolates ether compound, C_4 hydrocarbon enters In catalytic dehydrogenating reaction device, hydrogen is 0.5:1 with all hydrocarbon material mol ratios entering catalytic deoxidation unit, In 550 DEG C of reaction temperature, volume space velocity 10.0h^-1, reacted under conditions of reaction pressure 3.0mpa, It is 44.7% that reaction obtains olefin(e) centent in dehydrogenation product.

Comparative example

Catalyst for etherification buys the rze-3 zeolite catalyst for etherification of petrochemical industry academy of science research and development, and profile is Diameter 8mm is spherical, bulk density 0.71g/cm³, specific surface area 487m²/ g, pore volume 0.464ml/g, Average pore size 175nm, intensity > 20n.Dehydrogenation adopts in patent cn 101623633a to be implemented In example 1, the step of catalyst preparation prepares catalyst.Zsm-5 molecular screen primary powder first is placed in 0.16m's sncl₂·2h₂In 80 DEG C of dipping 10hr so that the load capacity of sn in catalyst reaches 4wt% in o solution, Then 6hr is dried at 120 DEG C.Dried sample roasting 4hr under 550 DEG C of air atmosphere.After roasting Powder 0.03m h₂ptcl₆·6h₂Impregnate 4hr at 80 DEG C in o solution, make finally to be obtained pt Content is the catalyst of 20wt%, then 6hr is dried at 120 DEG C, roasting 4hr at 550 DEG C.Exist afterwards 550 DEG C of hydrogen reducing 12hr are standby.Raw material b and methanol mixed enter in methyltertiarvbutyl ether reactor, etherification reaction bar Part is: 73 DEG C of reaction temperature, volume space velocity 1.4h^-1, reaction pressure 1.7mpa, wherein methanol and entrance In hydrocarbon material in methyltertiarvbutyl ether reactor, the mol ratio of iso-butane is 0.95:1.Through separative element, isolate Ether compound, its yield is 34.1%.Hydrogen and the institute entering catalytic deoxidation unit in dehydrogenation reactor Hydrocarbon material mol ratio is had to be 0.5:1, in 550 DEG C of reaction temperature, volume space velocity 10.0h^-1, reaction pressure Reacted under conditions of 3.0mpa, it is 42.5% that reaction obtains olefin(e) centent in dehydrogenation product.

Certainly, the present invention also can have other various embodiments, without departing substantially from present invention spirit and its essence In the case of, those of ordinary skill in the art can make various corresponding changes according to the present invention and become Shape, but these corresponding changes and deformation all should belong to the protection domain of the claims in the present invention.

Claims (17)

1. a kind of mixing carbon four method for transformation is it is characterised in that conversion process at least comprises the steps: the One step mixing carbon four raw material, the logistics containing oxidant and water or water vapour enter oxidative dehydrogenation unit, in dress After filling out reaction in the reactor of Oxydehydrogenation catalyst, enter separative element i, reacted logistics is divided into Butadiene, other C-4-fraction and other components；Second step is by the other C-4-fractions isolated in the first step Send into etherificate unit with alcohols logistics, carry out etherification reaction in the reactor equipped with catalyst for etherification, reaction is produced Thing enters separative element ii, and reacted logistics is divided into carbon more than five component, C_4 hydrocarbon and other component； 3rd step sends into catalytic dehydrogenation unit by isolating C_4 hydrocarbon in second step with hydrogen, is urging equipped with catalytic dehydrogenation Carry out alkane catalytic dehydrogenating reaction in the reactor of agent, and by the logistics after catalytic dehydrogenation through separative element After iii isolates on-condensible gas, send into oxidative dehydrogenation unit together with mixing carbon four raw material.

2. mixing carbon four method for transformation according to claim 1 is it is characterised in that mix carbon four raw material Refer to refine oil the C_4 hydrocarbon with generation in chemical process, carbon four, catalytically cracked C four, cracking preferably after ether Carbon four and or light gasoline separation component；Or C_4 hydrocarbon mass content is not less than 95% in mixing carbon four, In preferably not below 99%, or mixing carbon four, alkene mass content is not less than 40%, preferably not below 50%, Or the mass content of n-butene and normal butane and be not less than 35%, preferably not below 40% in mixing carbon four.

3. mixing carbon four method for transformation according to claim 1 is it is characterised in that oxidative dehydrogenation unit N-butene conversion be not less than 70%, preferably not below 75%.

4. mixing carbon four method for transformation according to claim 1 is it is characterised in that oxidative dehydrogenation unit Reaction condition be: temperature be 280 DEG C～410 DEG C, pressure be 0～100kpa, volume space velocity be 10～ 500h^-1, preferred reaction condition is: temperature is 310 DEG C～395 DEG C, and pressure is 0～40kpa, volume Air speed is 60～400h^-1.

5. mixing carbon four method for transformation according to claim 1 is it is characterised in that oxidative dehydrogenation unit Oxidant be material stream containing oxygen molecule or containing oxidizing strong oxygen atom, preferably air, oxygen-enriched Gas or oxygen.

6. mixing carbon four method for transformation according to claim 1 is it is characterised in that containing oxidant With oxymeter in logistics, oxygen with the olefin molar ratio entering all hydrocarbon materials in oxidative dehydrogenation unit is 0.1～1.0:1, preferably 0.3～0.85:1.

7. mixing carbon four method for transformation according to claim 1 is it is characterised in that oxidative dehydrogenation unit Vapor is 0.5～30 with butylene mass ratio in all hydrocarbon materials of entrance oxidative dehydrogenation unit, preferably 5～20.

8. mixing carbon four method for transformation according to claim 1 is it is characterised in that separative element i divides The content separating out butadiene in the C-4-fraction after butadiene is not higher than 0.3%, and preferably not higher than 0.1%.

9. mixing carbon four method for transformation according to claim 1 is it is characterised in that etherification reaction unit Middle isobutene conversion is not less than 92%.

10. mixing carbon four method for transformation according to claim 1 is it is characterised in that etherification reaction unit Middle alcohols logistics refers to low-carbon alcohols, special recommendation methanol, ethanol.

11. mixing carbon four method for transformation according to claim 1 are it is characterised in that enter etherification reaction In unit, alcohols with enter etherification reaction unit all hydrocarbon materials in isobutene. mol ratio be 0.8～ 1.5:1, preferably 1.1～1.3:1.

12. according to claim 1 mixing carbon four method for transformation it is characterised in that etherification reaction anti- The condition is answered to be: temperature is 30～100 DEG C, pressure is 0.1～2.0mpa, volume space velocity is 0.1～5h^-1； Preferably temperature is 45～80 DEG C, and pressure is 0.5～1.5mpa, and volume space velocity is 1～2h^-1.

13. mixing carbon four method for transformation according to claim 1 are it is characterised in that separated unit ii Isolate in the C_4 hydrocarbon after carbon five and above component, the mass content of C_4 hydrocarbon class is not less than 97%, It is not less than 99% well.

14. mixing carbon four method for transformation according to claim 1 are it is characterised in that catalytic dehydrogenation unit In middle catalytic dehydrogenation product, olefin(e) centent is not less than 35%, is preferably such that olefin(e) centent more than 45%.

15. mixing carbon four method for transformation according to claim 1 are it is characterised in that catalytic dehydrogenation unit Reaction condition be preferably: temperature be 480～700 DEG C, pressure be 0.01～3mpa, liquid volume air speed For 0.1～10h^-1；Preferably temperature is 560～650 DEG C, and pressure is 0.4～1.2mpa, and liquid volume is empty Speed is 2～7h^-1.

16. mixing carbon four method for transformation according to claim 1 are it is characterised in that enter catalytic dehydrogenation In unit, hydrogen is 0.01～1:1 with the mol ratio of all hydrocarbon materials entering catalytic dehydrogenation unit, It is well 0.1～0.5:1.

17. mixing carbon four method for transformation according to claim 1 are it is characterised in that catalytic dehydrogenation unit In catalytic dehydrogenating reaction device be two or more fixed bed reactors used in parallel.