CN106866337A - One kind mixing trans-utilization technique of carbon four - Google Patents

Abstract

The present invention provides a kind of mixing trans-utilization technique of carbon four, and the technology utilization mixing carbon four prepares high octane gasoline component and butadiene.The present invention provide technique be according to mixing carbon four in normal butane, iso-butane and olefin(e) centent relative abundance the characteristics of, raw material mixing carbon four is set to sequentially pass through oxidative dehydrogenation unit, etherificate unit and catalytic dehydrogenation unit, to obtain butadiene and high octane gasoline component.Meanwhile, produce catalyst of alkadienes and preparation method thereof present invention also offers a kind of olefin oxidation dehydrogenation.The trans-utilization technique of mixing carbon four that the present invention is provided, while the conversion ratio of Tertiary olefin during alkadienes has a strong impact on etherification procedure, high-knock rating gasoline yield and etherification product content in gasoline is overcome, can also a certain amount of high value of by-product alkadienes, improve economic benefit and market competitiveness.

Description

One kind mixing trans-utilization technique of carbon four

Technical field

The invention belongs to oil Refining Technologies field, and in particular to one kind mixing trans-utilization technique of carbon four.

Background technology

Into 12, with the 20000000 tons/year of oil refining of CNPC's Guangdong petrochemical industry, the oil refining of 10,000,000 tons/year of Kunming, Sichuan petrochemical industry Integrated Refinery And Petrochemical engineering, 800,000 tons/year of ethene of Fushun petrochemical industry, 1,200,000 tons/year of ethene of Daqing petrochemical change expansion The propulsion of project such as build, the refining capacity and ethene production capacity of CNPC will also further expand, the catalysis of refinery's by-product The yield of cracking C4 and c4 cleavage resource is also being significantly increased.C4 resources are used to produce MTBE, alkyl except part Outside carburetion, polymerized monomer, burnt mostly as domestic fuel.And C4 hydrocarbon and tops are not only cheap, and Cost of transportation is high, loss is big in transportation, and low-value product is belonged to for refinery.

With developing rapidly for Chinese national economy, car ownership is continuously increased, to the demand of vehicle fuel gasoline Amount is increasing.Meanwhile, also with environmental requirement to the increasingly strict of gasoline quality standard, motor petrol quality standard Develop to low sulfur content, low olefin-content, low-steam pressure and high-octane direction.Market is to volume increase high-quality Gasoline and the technology that low-sulfur, low olefin-content, high octane value gasoline blending component have very big demand, this aspect is opened Hair also turns into the hot issue of domestic each research unit and enterprises pay attention.

Butadiene is the primary raw material of synthetic rubber, accounts for the 71% of total raw material, and butadiene demand is up within 2015 3500000 tons.Chinese butadiene source is relatively simple, main to use the extraction process of carbon four, is produced by ethylene unit, by 2015 Year 21000000 tons of calculating of ethene ability, butadiene total resources is ten thousand tons of 284-294, and butadiene will appear from serious lacking Mouthful.Another important sources of butadiene are butylene oxidation-dehydrogenation technologies.Butylene oxidation-dehydrogenation with positive structure butylene as raw material, Domestic n-butene dehydrogenation under the joint efforts of relevant unit, experienced ternary molybdenum series catalyst, six at home First molybdenum series catalyst, H-198 iron system and B-O2 Fe-series catalysts, reaction bed is also by initial deflector apron fluid bed Development two sections of axial directions finally are insulation fix bed.Industrialized production proves H-198 Fe-series catalysts and deflector apron stream Changing bed group technology, B-O2 Fe-series catalysts and two sections of insulation fix bed group technologies in axial direction can make domestic n-butene The production cost of oxidative dehydrogenation device and environmental pollution are greatly lowered, and overall economic efficiency reaches the same time and first intakes It is flat.

But since the eighties in 20th century, with continuous newly-built, the production of butadiene of domestic large-scale ethylene plant Technique is progressively replaced by the less expensive extraction process of carbon four of cost, and numerous n-butene oxidative dehydrogenation devices gradually stop production, Therefore domestic n-butene oxidative dehydrogenation technology could not further be developed.But in the long run, by ethylene cracker Raw material lighting influences, and the newly-increased butadiene production capacity of extraction process will be increasingly difficult to meet following downstream synthetic rubber to fourth The demand of diene.Original from being produced into, the production cost of n-butene oxidative dehydrogenation butadiene is than traditional extraction process Want 30%-40% high.

On the other hand, with increasing oil refining apparatus and ethylene unit it is newly-built and enlarging, the country oil refining and ethene produce The yield of the mixing resource of carbon four such as the further expansion of energy, catalytically cracked C four and cracking c_4 of refinery's by-product also will be big Width increases.The resource of carbon four except part be used for produce MTBE, alkylate oil, aromatization carburetion, polymerized monomer in addition to, big portion It is allocated as being burnt for domestic fuel.In this resource of part carbon four, in addition to normal butane, iso-butane, contain what is quite enriched N-butene and isobutene, are the raw materials of extraordinary production butadiene.

Phillips companies develop normal butane two step method dehydrogenating technology production butadiene at first, and first step reaction uses chromium Al catalysts, by normal butane dehydrogenation, n-butene is dehydrogenated to butadiene by second step in the presence of steam again.This side Method raw material only has normal butane, for using refining oil with for mixing carbon four produced in chemical process, being less applicable.

BASF AG in order to improve the product yield of normal butane dehydrogenation butadiene, in Phillips two-step processes On the basis of update, to second step dehydrogenation systems add oxygen, be combined together dehydrogenation reaction and oxidation reaction, So as to increase substantially the conversion ratio of n-butene and the selectivity of butadiene, its technological process is：By the original containing normal butane Material introduces the first dehydrogenation zone, and by the catalytic dehydrogenation of normal butane non-oxidizable ground is 1- butylene, 2- butylene and butadiene the One product gas flow.By the first product gas flow introduce the second dehydrogenation zone, and by 1- butylene and 2- butylene oxidations ground dehydrogenation It is butadiene, to obtain, containing the second product gas flows such as butadiene, normal butanes, then reclaiming fourth from the second product gas flow Diene.The non-oxidizable catalytic dehydrogenation of normal butane is carried out in plate-type reactor with autothermal catalysis dehydrogenation, the reaction Device includes one or more continuous catalyst beds, and dehydrogenation is platinum group catalyst.N-butene oxidative dehydrogenation is l, 3- The catalyst of butadiene is molybdenum-bismuth-oxygen poly-metal deoxide system.Although after introducing oxygen, two step method dehydrogenating technology Product yield is enhanced, but the technique productions step is more, high cost, and steam consumption is very big.

Italian Snamprogetti SPA companies use its original tubular reactor and cartridge reactor technology, exploitation The DET techniques of the Tertiary olefin etherificate in catalytic light gasoline, mainly include：Light petrol knockout tower, selection hydrogenation Reactor, 2 methyltertiarvbutyl ether reactors, depentanizer, TAME knockout towers, MPP absorbers and non-Tertiary olefin skeletons Isomerizing reactor.

IFP (IFP) exploitation the TAME technological process of productions include purification of raw materials, etherification reaction and The part of Methanol Recovery 3.Except that etherification reaction employs a main reactor (expanded bed reactor) and one End reaction device (catalytic rectifying tower) is used in series, wherein the 90% of total material is carried out in expanded bed reactor.

The catalytic light gasoline etherification technology of Arco chemical technology company (ARCO) exploitation, mainly for the production of MTBE Coproduction TAME.Etherification reaction uses tandem fixed bed adiabatic reactor in Etherification of Light FCC Gasoline technique.Its technological process It is divided into purification of raw materials, 3 unit processes of etherification reaction and Methanol Recovery.C5 raw materials are pre- by washing, selection hydrogenation Mix with methyl alcohol after treatment, into two fixed bed adiabatic reactors of series connection, in ion-exchange resin catalyst Reacted under effect.

In patent CN103361113A, a kind of raw material production high-knock rating gasoline rich in the light dydrocarbon carbon six of carbon four is disclosed Method, the raw material that now will be enriched in the light dydrocarbon carbon six of carbon four mixes with hydrogen and carries out catalytic dehydrogenating reaction.Catalytic dehydrogenation product By on-condensible gas separator, isolate after on-condensible gas, after mixing with the raw material rich in alkene, hydrogen, enter Entering aromatization reactor and being contacted with aromatized catalyst carries out aromatization, and reacted product can be divided by separating It is dry gas, liquefied gas, gasoline component and diesel component.

In patent CN103965002A, a kind of method of lower carbon number hydrocarbons oxidative dehydrogenation is disclosed, it is low-carbon (LC) hydrocarbon feed, oxygen-containing Gas and diluent by a certain percentage enter the first stage reactor after, reacting rear material again with second strand of low-carbon (LC) hydrocarbon feed and After the mixing of second strand of oxygen-containing gas, into the agent of next stage reactor dilution include water vapour, N2, CO2, He or its At least one in its inert gas.

Chinese patent CN102716754A discloses a kind of Oxidative Dehydrogenation of Butene fourth two for fluidized-bed reactor The preparation method of alkene catalyst, the method is anti-in the case where 10-90 DEG C, pH are for 5-11 by metal precursor and alkaline matter The slurry containing insoluble compound should be obtained, by slurries filtration and to wash to pH be 7-7.5；Add appropriate binding agent, Deionized water is stirred, and regulation slurry solid content is 10%-50%；Gained slurry is carried out by spraying drying granulating equipment Spray drying granulation, feeding temperature be 200 DEG C -400 DEG C, outlet temperature be 100 DEG C -160 DEG C, obtain catalyst Microballoon；Catalyst microspheres are dried into 1-24h at 80 DEG C -200 DEG C of drying temperature, is calcined at 500 DEG C -900 DEG C 4-24h, obtains finished catalyst.The formula for obtaining catalyst is FeX_aY_bZ_cO_d, wherein X be Ni, Co, Zn, One or more in Cu, Sn, Mn, Y is one or two in Bi, Mo, Cr, V, La, Zr More than, Z be Mg, Ca, Sr, Ba in one or more, a is 0.1-3, and b is 0-1, and c is 0-1, d Value meet the requirement of other metallic element chemical valences.The catalyst delays dehydrogenation butadiene for butylene, in temperature 300-400 DEG C of degree, normal pressure, water/alkene mol ratio 6-16, oxygen/alkene mol ratio 0.4-1.0, butylene volume space velocity 100-600h^-1 Under conditions of, butadiene yield is 76%-86%, and butadiene selective is 94-97%.The shortcoming of the catalyst is place Reason amount is smaller, and full airspeed is only 600h^-1；In addition, the catalyst has only carried out the evaluation test of 6h, catalyst Stability can not be guaranteed.

CN1184705A discloses a kind of fluid bed iron group catalyst for producing butadiene by oxidative dehydrogenation of bytylene, the catalyst By three kinds or more bivalent metal ion and Fe³⁺Composition, its general structure is, A_a ²⁺B_b ²⁺C_c ²⁺Fe₂O₄·X(α-Fe₂O₃), (when catalyst Formula is：Zn_aCa_b-Co_eFe₂O₄·X(α-Fe₂O₃) when, a =0.8-0.9, a+b+c=1, X=15-65% (weight).Formula Zn_aCa_bCo_cFe₂O₄·X(α-Fe₂O₃) in, a= 0.8-0.9, b=0.03-0.08, a+b+c=1, X=20-40% (weight)), A is Zn in formula, and B is selected from Mg, One or two elements in Ca, Sr, Ba, C be selected from Ni, a kind of element in Co, a=0.1-0.9, b=0.01-0.1, A+b+c=1, X=15-65% (weight).It does precipitating reagent with ammoniacal liquor, and precipitation terminal pH is 8.2-8.7, and precipitation is old It is 50-95 DEG C to change temperature, time 30min, filtration washing, filter cake and 100-120 DEG C of drying after filtering, and the time is 12-24h, activation temperature is 640-700 DEG C, and the time is 10-20h.The catalyst is used for Oxidative Dehydrogenation of Butene fourth two During alkene shelf fluidized bed reactor, in 310-420 DEG C of temperature, normal pressure, water/alkene mol ratio 8-12, oxygen/alkene mol ratio 0.56-0.9, butylene volume space velocity 150-600h^-1Under conditions of, butadiene yield is 70-85%, butadiene selective It is 93-96%, the shortcoming of the catalyst is to be only applied to the shelf fluidized bed reactor with n-butene as raw material.

CN103055890A discloses a kind of iron catalyst of n-butene oxidative dehydrogenation butadiene, the catalyst with Fe is main component, and with Mg, Zn and extraction element as auxiliary agent, the quality group of catalyst turns into 48.80-60.53wt% Fe, 0.01-18.0wt%Mg, 0.0-15.0wt%Zn, and other described element gross masses are 0.0-5.0wt%, its Remaining is oxygen element, other elements be selected from Ba, Ca, Ni, Co, Cu, Cr, p, Si, Al, V, Ti, Mo, One or more in Sn, Sb, Zr, Mn, K and rare earth element.The catalyst is de- for fixed bed butylene oxidation During hydrogen butadiene, in 260-445 DEG C of temperature, normal pressure, water/alkene mol ratio 12-25, oxygen/alkene mol ratio 0.42-0.90, Butylene volume space velocity 180-600h^-1Under conditions of, the yield of butadiene is only up to 72.8%.The shortcoming of the catalyst It is smaller treating capacity, full airspeed is only 600h^-1；In addition, the butadiene yield of the catalyst is relatively low.

CN102824914A discloses a kind of method for n-butene oxidative dehydrogenation butadiene, and the method utilizes cobalt Prepared iron acid zinc catalyst is modified for the oxidative dehydrogenation of n-butene with magnesium elements.But the catalyst is only applicable to positive fourth Alkene, in 400-450 DEG C of temperature, unstripped gas：Air：Water vapour volume ratio is 1:4:16th, butylene volume space velocity 500-700h^-1 Under conditions of, the yield of butadiene is only up to 77.8%.The treating capacity of catalyst is also smaller.

CN101674883A discloses a kind of iron acid zinc catalyst, is combined with simple zinc ferrite, it is difficult to reach ideal Catalytic effect, and catalyst is used for fixed bed reactors, and beds temperature rise is serious, high energy consumption, while simultaneously Wear problem of the catalyst on fluidized-bed reactor can not be solved.

United States Patent (USP) US3450788 and US3450787 disclose various different spinel structure ferric chromate butylene Oxydehydrogenation catalyst.Wherein there is spinelle ferric chromate catalyst preferable Oxidative Dehydrogenation of Butene into Butadiene to react Performance, butylene one way molar yield is 70%, and butadiene molar selectivity is up to 92%.

CN1033013A, CN101674883A and CN1184705A etc. disclose the butylene oxygen based on ferrite The preparation method of fluidized dehydrogenation butadiene catalyst.The molar yield of butylene is generally 70-80% on these catalyst, Butadiene molar selectivity is 89-93%.Which part patent once obtains commercial Application at home, but by fourth two at that time Alkene demand and technological level are limited, and are forced to stop production.

The content of the invention

To overcome above mentioned problem, it is an object of the invention to provide one kind mixing trans-utilization technique of carbon four.The present invention is provided Technical scheme be directed to mixing carbon four in positive iso-butane, positive isoolefine hydrocarbon content relatively all than more rich compositing characteristic, Mix the main technical process being combined by oxidative dehydrogenation, etherificate, catalytic dehydrogenation of carbon four there is provided a kind of, can be used for Production butadiene and high octane gasoline component.

To reach above-mentioned purpose, the invention provides one kind mixing the trans-utilization technique of carbon four, the technique at least include with Lower step：

The first step：By mixing carbon four raw material, the logistics containing oxidant and water or water vapour feeding oxidative dehydrogenation unit Alkanes oxidative dehydrogenation reaction is carried out, product feeding separative element I is separated into butadiene, its in addition to butadiene Its C-4-fraction and remaining ingredient；Second step：Other C-4-fractions and alcohol in addition to butadiene that the first step is obtained Class logistics feeding etherificate unit carry out etherification reaction, by product feeding separative element II be separated into light dydrocarbon and more than Component, C_4 hydrocarbon and remaining ingredient；3rd step：The C_4 hydrocarbon that second step is obtained sends into catalytic dehydrogenation list with hydrogen Unit carries out alkane catalytic dehydrogenating reaction, and product feeding separative element III is separated into on-condensible gas and remaining ingredient, Remaining ingredient returns to the oxidative dehydrogenation unit of the first step；In the above-mentioned first step, the Oxydehydrogenation catalyst for being used is such as Shown in formula (I)：

A_aB_bC_cD_d·Fe_xO_eFormula (I)

In formula (I)：A is Cu, Zn or Cr；B is Co, Mn, Ni or Mo；C be Ca, Sr, Ba or Mg；A is 1-6, and b is 0.01-0.3, and c is 0.1-1.0, and d is 0.01-0.1, and x is 4-18, and e takes and meets chemical valence It is required that any number.

During using two step dehydridings production butadiene, n-butene and normal butane do main contributions, isobutene It is relatively low with iso-butane conversion ratio.And during catalytic dehydrogenation, the conversion ratio that iso-butane is converted into isobutene is higher. The Tertiary olefin in logistics can be generated corresponding ether compound, uncle in the presence of catalyst using etherification technology Isobutene conversion is high-octane ether compound, as gasoline mediation group more than 95% by carbene hydrocarbon conversion rate Point.Different from n-butene and n-butane feedstock, in mixing carbon four, the normal butane not enriched only, also content is suitable N-butene, isobutene, iso-butane, the present invention provides and two step dehydrogenations produced the technique and etherification technology knot of butadiene Altogether, develop it is a kind of produce the technique of butadiene and high octane gasoline component using the component of carbon four is mixed, enter One step improves the added value of mixing carbon four.

In the trans-utilization technique of above-mentioned mixing carbon four, it is preferable that in formula (I)：A is 3-5, and b is 0.05-0.15, C is 0.3-0.6, and d is 0.04-0.08, and x is 7-13.

Percentage not specified in the present invention is mass percent.

In the trans-utilization technique of above-mentioned mixing carbon four, mixing carbon four raw material includes the carbon produced in oil refining and chemical process The separation component of carbon four, catalytically cracked C four, cracking c_4, or light petrol after four hydrocarbon, such as ether.Preferably, C_4 hydrocarbon mass content in the mixing raw material of carbon four is not less than 95%, preferably not below 99%；C 4 olefin quality contains Amount is not less than 40%, preferably not below 50%；The mass content of n-butene and normal butane and it is not less than 35%, it is best It is not less than 40%.It can be raw material, or separate sources the raw material mixing in same source.

In the trans-utilization technique of above-mentioned mixing carbon four, it is preferable that the reaction condition of the oxidative dehydrogenation unit is：Temperature 280 DEG C -410 DEG C, preferably 310 DEG C -390 DEG C of degree；Pressure 0-100KPa, 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.

In the trans-utilization technique of above-mentioned mixing carbon four, the logistics containing oxidant of oxidative dehydrogenation unit can in the 3rd step Think the material stream containing oxygen molecule or containing oxidizing strong oxygen atom such as oxygen, oxygen rich air, air；Preferably Air, oxygen rich air and oxygen；More preferably oxygen rich air；More preferably oxygen content is between 32%-45% Oxygen rich air.Wherein, in the logistics containing oxidant oxidant with oxymeter, oxygen with enter institute in oxidative dehydrogenation unit The mol ratio for having alkene in hydrocarbon material is 0.1-1.0:1, preferably 0.3-0.85:1.In the charging of oxidative dehydrogenation unit During, add certain ratio water or water vapour, can prevent catalyst coking and beds due to coking Temperature is caused to rise too fast problem.The mass ratio of water or water vapour and all hydrocarbon materials into oxidative dehydrogenation unit Can be 0.5-30:1, preferably 5-20:1.

In the trans-utilization technique of above-mentioned mixing carbon four, the reactor of oxidative dehydrogenation unit includes fluidized-bed reactor or solid Fixed bed reactor, preferably fluidized-bed reactor；Reactor can be separate unit intermittently operated, or two more Platform is connected or parallel way is carried out.

In the trans-utilization technique of above-mentioned mixing carbon four, it is preferable that separation method can be extraction in separative element I, Rectifying, or extracting rectifying, azeotropic distillation, UF membrane or chemical absorbing etc..Can be with selected technology comparative maturity Isolation technics, obtain qualified product butadiene, and cause other C-4-fractions in addition to butadiene separated The mass content of middle butadiene is not higher than 0.3%, preferably not higher than 0.1%.

In the trans-utilization technique of above-mentioned mixing carbon four, it is preferable that the alcohols logistics in etherificate unit is carbon atom number No more than 4 low-carbon alcohols, preferably methyl alcohol, ethanol, more preferably methyl alcohol.

In the trans-utilization technique of above-mentioned mixing carbon four, it is preferable that enter etherification reaction unit when, alcohols with enter ether The mol ratio for changing the isobutene in all hydrocarbon materials of unit is 0.8-1.5:1, preferably 1.1-1.3:1.

In the trans-utilization technique of above-mentioned mixing carbon four, it is preferable that etherificate unit reaction condition be：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 It is 1-2h^-1。

In the trans-utilization technique of above-mentioned mixing carbon four, catalyst for etherification is not particularly limited in etherificate unit, it is preferable that The conversion ratio of isobutene is not less than 92%, preferably not lower than 95%.

In the trans-utilization technique of above-mentioned mixing carbon four, methyltertiarvbutyl ether reactor is not particularly limited, can be fixed bed, shifting One or several combination in dynamic bed suspension bed, catalytic distillation reactor etc..But preferably catalytic distillation technology, Tertiary olefin can be made fully to convert, the C-4-fraction feeding catalytic dehydrogenation unit of dealcoholysis tower top output in separative element, Tower reactor output can be used as high octane gasoline component, and the alcohol of recovery can also be recycled to methyltertiarvbutyl ether reactor entrance and use.

In the trans-utilization technique of above-mentioned mixing carbon four, in separative element II, separation method is not limited, Ke Yiwei Rectifying, extraction, UF membrane etc., but compare and recommend rectifying.Preferably, in the C_4 hydrocarbon isolated, four groups of carbon The mass content divided is not less than 97%, preferably not lower than 99%.

In the trans-utilization technique of above-mentioned mixing carbon four, dehydrogenation is not particularly limited in catalytic dehydrogenation unit, it is excellent Selection of land, alkene mass content is not less than 35% in catalytic dehydrogenation product, and preferably alkene mass content is more than 45%.

In the trans-utilization technique of above-mentioned mixing carbon four, the reaction condition of the catalytic dehydrogenation unit is：Temperature 480-700 DEG C, pressure 0.01-3MPa, volume space velocity 0.1-10h during liquid^-1；It is further preferred that the catalytic dehydrogenation unit Reaction condition is：560-650 DEG C of temperature, pressure 0.4-1.2MPa, volume space velocity 2-7h during liquid^-1。

In the trans-utilization technique of above-mentioned mixing carbon four, during into catalytic dehydrogenation unit, hydrogen with enter catalytic dehydrogenation list The mol ratio of all hydrocarbon materials is 0.01-1 in unit:1, preferably 0.1-0.5:1.

In the trans-utilization technique of above-mentioned mixing carbon four, catalytic dehydrogenating reaction device is preferably fixed bed reactors, Ke Yishi One reactor is used alone, and regenerating two process intervals by reaction-catalyst realizes, it is also possible to two or more Reactor is used in parallel to be circulated operation, multiple reactors can also be divided in parallel and or series combination use.When one , due to carbon distribution serious inactivation, by switching material import and export, decaying catalyst is again for catalyst in individual or several reactors Raw Posterior circle is used, and realizes reaction, the continuous operation of regenerative system.

In the trans-utilization technique of above-mentioned mixing carbon four, it is preferable that on-condensible gas that separative element III is isolated, point The dry gas (methane, ethane close propane) separated from unit II can direct cycle to catalytic dehydrogenation supplies of unit Entrance, recycles.

In the trans-utilization technique of above-mentioned mixing carbon four, it is preferable that fixed gas can be included in involved separative element The separator of body, such as flash tank, absorption/Analytic Tower, cooling device and compression set.

In the trans-utilization technique of above-mentioned mixing carbon four, a kind of preferred embodiment that the present invention is provided is：Use carbon four Hydrocarbon mass 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 35%, preferably not below 40% mixing carbon four are not less than Raw material；It is 280 DEG C -410 DEG C, pressure 0-100KPa, volume space velocity 10-500h in temperature^-1, oxygen and entrance are aoxidized The olefin molar ratio of all hydrocarbon materials of dehydrogenation unit is 0.1-1:1, water or water vapour with enter oxidative dehydrogenation unit The mass ratio of all hydrocarbon materials is 0.5-30:It is oxygen-enriched between 32%-45% with oxygen content under 1 process conditions Air-flow mixing carries out oxidative dehydrogenation, after product isolates butadiene, etherificate unit is entered with alcohols logistics, Alcohols is 0.8-1.5 with the isobutene mol ratio in the hydrocarbon material for entering methyltertiarvbutyl ether reactor: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, and volume is empty Speed is 0.1-5h^-1, preferably 1-2h^-1Under conditions of carry out etherification reaction after, isolate the ethers in product After compound and other components, remaining C_4 hydrocarbon enters catalytic dehydrogenation unit, in 480-700 DEG C of temperature, pressure 0.01-3MPa, volume space velocity is 0.1-10h^-1, hydrogen with enter catalytic dehydrogenation unit all hydrocarbon materials mole Than being 0.01-1:After carrying out catalytic dehydrogenating reaction under conditions of 1, oxidative dehydrogenation unit is entered together with raw material mixing carbon four.

In the trans-utilization technique of above-mentioned mixing carbon four, it is preferable that Oxydehydrogenation catalyst used by oxidative dehydrogenation unit Preparation process is at least comprised the following steps：

(1) presoma of metal A, B, C and D used is ground to the microspheroidal of 40-100 mesh respectively；And It it is two parts by the presoma parts by weights of ground metal A；Meanwhile, the presoma of metal B, C and D is mixed Close uniform；

(2) iron nitrate solution of 0.1-2mol/L is configured, under agitation, by first part of presoma of metal A It is added gradually in iron nitrate solution, reaction adds the forerunner of well mixed metal B, C and D after 30-90 minutes Body, second part of presoma of metal A is added after continuing to react 30-90 minutes, is added after continuing to react 20-80 minutes Binding agent, obtains the slurry of presoma sediment；

(3) it is 10-25% to concentration is gradually added into slurry after slurry agitation 20-60 minutes being obtained in step (2) Ammoniacal liquor, to adjust slurry pH value to 7.5-10；

(4) heat modification is carried out in the environment of the slurry adjusted after pH in step (3) being placed in into 80-95 DEG C, is changed Property the time be 60-180 minutes；

(5) slurry modified in step (4) is filtered, then with washing water washing, is made slurry pH value 7-7.5 is reached, and adjusts slurry solid content for 5-40%, then spray shaping, 6-12 is calcined at 400-500 DEG C Hour, obtain finished catalyst；

Or filtered slurry modified in step (4), then with washing water washing, and make slurry pH Value reaches 7-7.5, is then calcined 6-12 hours at 100-200 DEG C, is calcined 4-8 hours at 200-300 DEG C, It is calcined 1-4 hours at 300-400 DEG C, is calcined 1-4 hours at 400-500 DEG C, grinding obtains finished catalyst.

In the preparation method of above-mentioned Oxydehydrogenation catalyst, it is preferable that in step (1) before first part of metal A It is the 55-70% of the presoma gross weight of metal A to drive body.

In the preparation method of above-mentioned Oxydehydrogenation catalyst, it is preferable that metal A, B, C in step (1) and The presoma of D is respectively selected from one or more in the nitrate of respective metal, chloride, sulfate and oxide Combination.

In the preparation method of above-mentioned Oxydehydrogenation catalyst, it is preferable that the binding agent in step (2) includes sesbania The combination of one or more in powder, polyacrylamide, methylcellulose and polyvinyl alcohol；It is further preferred that institute The addition for stating binding agent is the 0.1-4%, preferably 1-2% of metal precursor gross mass.

In the preparation method of above-mentioned Oxydehydrogenation catalyst, it is preferable that the regulation slurry pH value of step (3) to 8.0-9.0。

In the preparation method of above-mentioned Oxydehydrogenation catalyst, it is preferable that the concentration of step (2) iron nitrate solution is 0.3-1.0mol/L。

In the preparation method of above-mentioned Oxydehydrogenation catalyst, it is preferable that step (2) add binding agent time be Reaction is added after 40-60 minutes.

In the preparation method of above-mentioned Oxydehydrogenation catalyst, it is preferable that adjusted the slurry after pH in step (4) The modification time of material is 90-120 minutes.

In the preparation method of above-mentioned Oxydehydrogenation catalyst, it is preferable that the spray shaping preferably using spray tower come Complete, the feeding temperature of spray tower is preferably 300-500 DEG C, and discharging opening temperature is preferably 100-150 DEG C.

In the preparation method of above-mentioned Oxydehydrogenation catalyst, it is preferable that in step (5) washings can using go from One or more in sub- water, distilled water, desalted water and running water.

The present invention provide the trans-utilization technique of mixing carbon four, its advantage be mixing carbon four modification utilize during, Overcome high easily to the unfriendly of environment, high temperature aromatization technology dry gas production rate in isomerization technique its production process The shortcomings of the economic benefit of 20%, technical process can be subject to no small loss, research profit is continued deeper into etherification technology During, diene units and alkadienes separative element are produced by increasing oxidative dehydrogenation, both overcome alkadienes Conversion ratio, the problem of ether compound yield of monoolefine etherificate are had a strong impact on, again can be while a certain amount of high price of by-product The alkadienes of value, so as to improve the economic benefit and market competitiveness of this technique, also for the utilization for more becoming more meticulous is low Carbon alkane class provides another technique.In addition, in oxidative dehydrogenation process, due to the generation of side reaction, can produce Life a small amount of ketone and aldehyde.If the amount that aldehyde and ketone are produced is too high, diene hydrocarbon-selective can be not only directly affects, and The waste water process that treatment washing aldehyde and ketone are produced can also increase process costs.In the scheme that the present invention is provided, due to using A kind of special olefin oxidation dehydrogenation, the method for preparing catalyst particularly recommended with the present invention first will Metal precursor grinding used, and be 55-70% and two parts of 30-45% by metal precursor A parts by weights, substep adds Enter；Metal precursor B, C and D are pre-mixed uniformly；Each active component in catalyst preparation process can be enable Enough homogeneous nucleations, improve the stability of catalyst；In addition, adding pro-oxidant tungsten in catalyst preparation process, can have Effect improves the activity of catalyst.Oxygen content is total into reaction system material to control in by controlling oxygen-enriched stream Amount controls the contact of oxygen atom, alkene with catalyst in reaction system, when being stopped from still further aspect control reaction Between.Not only can guarantee that monoolefine is fully converted into alkadienes using above-mentioned technique, and effectively control alcohols With the generation of aldehydes, the yield and selectivity of alkadienes are improve.

Brief description of the drawings

Fig. 1 is embodiment 9-16, the process flow diagram of comparative example 3.

In Fig. 1：R1 is oxidative dehydrogenation reactor, and R2 is etherificate dehydrogenation reactor, and R3 is catalyst oxidation reactor, T1, T2, T3 correspond to piece-rate system I, piece-rate system II, piece-rate system III respectively.

Specific embodiment

In order to be more clearly understood to technical characteristic of the invention, purpose and beneficial effect, now to skill of the invention Art scheme carry out it is described further below, but it is not intended that to it is of the invention can practical range restriction.

, by embodiment is using the property of the mixing raw material of carbon four, the mixing A of carbon four is urged for Lanzhou Petrochemical Company for table 1, table 2 Change workshop mixing carbon four, the mixing B of carbon four urges mixing carbon four again for Daqing Refinery company one.Methyl alcohol uses commercially available Cangzhou The methyl alcohol of Zheng Yuan Chemical Co., Ltd.s production, the wherein mass content of methyl alcohol are 99.5%.Ethanol uses commercially available Yixing City The absolute ethyl alcohol of Qiu Yun Chemical Co., Ltd.s production, the wherein mass content of ethanol are 99.5%.

Embodiment 9-16, comparative example 3 use technique as shown in Figure 1, and catalytic dehydrogenating reaction device is 200ml in embodiment Two reactor cycles of fixed bed reactor are used；Oxidative dehydrogenation unit uses 100ml in embodiment 9 and 14 Fixed bed reactors, in embodiment 10-13 oxidative dehydrogenation unit using 100ml fluidized-bed reactor；It is each to implement Etherification reaction system in example uses catalytic distillation reaction unit, and pre- methyltertiarvbutyl ether reactor is 200ml fixed beds, and reaction is steamed Loaded catalyst is 150ml in evaporating tower.Analysis sample is the instantaneous sample after reacting 3 hours.Separative element I (T1) It is middle use theoretical cam curve for 18 rectifying column.After being dehydrated using cyclone separator in separative element II (T2), dodge On-condensible gas is evaporated off, extraction isolates alkadienes.Separative element III (T3) use number of theoretical plate for 10 essence Evaporate tower.

Prepared in embodiment catalyst raw material in, sesbania powder is technical grade, and other are commercially available chemically 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 mass yield of alkadienes, the yield of etherification product computational methods it is as follows：

All hydrocarbon in the quality/catalytic dehydrogenation product of produced butylene, amylene in the content of alkene=catalytic dehydrogenation product Quality × 100 of class；

Hydro carbons in alcohols quality and/entrance oxidative dehydrogenation unit produced by the mass yield of alcohols=oxidative dehydrogenation unit Quality × 100 of material；

Hydro carbons in ketone quality and/entrance oxidative dehydrogenation unit produced by the mass yield of ketone=oxidative dehydrogenation unit Quality × 100 of material；

Hydrocarbon in alkadienes quality/entrance oxidative dehydrogenation unit produced by the mass yield of alkadienes=oxidative dehydrogenation unit Quality × 100 of class material；

Quality/entrance etherificate unit hydrocarbon material after all product removal on-condensible gases of yield=etherificate of etherification product Quality × 100.

The composition (w%) of the mixing carbon four of table 1 A

Component	W%	Component	W%
				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-butenes	0.01
1- butylene	13.39	1- amylenes	0.01

The mixing carbon four B compositions of table 2 (w%)

Component	W%	Component	W%
				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-butenes	0.02
1- butylene	12.63	1- amylenes	0.04

Embodiment 1

A kind of Oxydehydrogenation catalyst is present embodiments provided, the specific preparation process of the catalyst is comprised the following steps：

(1) presoma six of presoma the zinc nitrate hexahydrate 1785g, B of metal A used is hydrated nitre first The presoma tungstic acid 5g of presoma six the calcium chloride hydrate 197.1g, D of sour nickel 90g, C is ground to 50 purposes Microspheroidal；Secondly, zinc nitrate hexahydrate is divided into two parts of 1071g and 714g in 60% and 40% ratio, by six Nitric hydrate nickel, six calcium chloride hydrates and tungstic acid are well mixed；

(2) iron nitrate solution of configuration 8.5L 2mol/L, under agitation, first by 1071g zinc nitrate hexahydrates It is added gradually in iron nitrate solution, reacts 70 minutes, is slow added into Nickelous nitrate hexahydrate, six calcium chloride hydrates With the mixture of tungstic acid, the zinc nitrate hexahydrate of 714g is slow added into after reacting 90 minutes, reacts 50 points Binding agent methylcellulose 36g is added after clock, the slurry of presoma sediment is obtained；

(3) it is 25% to concentration is gradually added into slurry after slurry agitation being obtained 20 minutes in step (2) Ammoniacal liquor, to adjust slurry pH value to 8.0；

(4) heat modification is carried out in the environment of the slurry adjusted after pH in step (3) being placed in into 85 DEG C, when being modified Between be 180 minutes；

(5) slurry modified in step (4) is filtered, then with running water and distillation water washing, is made slurry Material pH value reaches 7.2；Filter cake modification by calcination 12 hours at 200 DEG C, modification by calcination 4 hours at 300 DEG C, Modification by calcination 4 hours at 400 DEG C, modification by calcination 4 hours at 400 DEG C；Ground after cooling, screen out 60-100 Purpose catalyst microspheres, it is Zn to obtain main composition₆Ni_0.3Ca_0.9W_0.02·Fe₁₇O_32.7Finished catalyst.

Embodiment 2

A kind of Oxydehydrogenation catalyst is present embodiments provided, the specific preparation process of the catalyst is comprised the following steps：

(1) first by the presoma cabaltous nitrate hexahydrate of presoma the copper nitrate 622.5g, B of metal A used The presoma tungstic acid 12g of presoma the barium chloride 20.8g, D of 116.4g, C is ground to the microspheroidal of 70 mesh； Secondly, copper nitrate is divided into two parts of 404.6g and 217.9g in 65% and 35% ratio, by cabaltous nitrate hexahydrate, Barium chloride and tungstic acid are well mixed；

(2) iron nitrate solution of configuration 36L 0.5mol/L, under agitation, by 404.6g copper nitrates gradually first It is added in iron nitrate solution, reacts 60 minutes, is slow added into Nickelous nitrate hexahydrate, six calcium chloride hydrates and three The mixture of tungsten oxide, reaction is slow added into the copper nitrate of 217.9g after 70 minutes, reaction is added after 50 minutes Binding agent methylcellulose 0.8g, obtains the slurry of presoma sediment；

(3) it is 20% to concentration is gradually added into slurry after slurry agitation being obtained 30 minutes in step (2) Ammoniacal liquor, to adjust slurry pH value to 8.5；

(4) heat modification is carried out in the environment of the slurry adjusted after pH in step (3) being placed in into 80 DEG C, when being modified Between be 90 minutes；

(5) slurry modified in step (4) is filtered, then with originally water washing, is made slurry pH value 7.5 are reached, regulation solid content is 20%, is then passed to spray shaping tower, control inlet temperature for 380 DEG C, Outlet temperature is 130 DEG C；Modification by calcination 12 hours at 400 DEG C again, obtaining main composition is Cu_2.5Co_0.4Ba_0.1W_0.06·Fe₁₈O_30.2Finished catalyst.

Embodiment 3

A kind of Oxydehydrogenation catalyst is present embodiments provided, the specific preparation process of the catalyst is comprised the following steps：

(1) presoma one of presoma the zinc nitrate hexahydrate 297.5g, B of metal A used is hydrated sulphur first The presoma tungstic acid 13.9g of presoma the Strontium dichloride hexahydrate 266g, D of sour manganese 25.4g, C is ground to 40 mesh Microspheroidal；Secondly, zinc nitrate hexahydrate is divided into two parts of 208.3g and 89.2g in 70% and 30% ratio, Manganous sulfate monohydrate, Strontium dichloride hexahydrate and tungstic acid are well mixed；

(2) iron nitrate solution of configuration 10L 0.7mol/L, under agitation, first by the nitric hydrates of 208.3g six Zinc is added gradually in iron nitrate solution, is reacted 30 minutes, is slow added into Manganous sulfate monohydrate, six chloride hydrates The mixture of strontium and tungstic acid, reaction is slow added into the zinc nitrate hexahydrate of 89.2g, reaction 40 after 90 minutes Binding agent methylcellulose 13.9g is added after minute, the slurry of presoma sediment is obtained；

(3) it is 25% to concentration is gradually added into slurry after slurry agitation being obtained 50 minutes in step (2) Ammoniacal liquor, to adjust slurry pH value to 10.0；

(4) heat modification is carried out in the environment of the slurry adjusted after pH in step (3) being placed in into 85 DEG C, when being modified Between be 100 minutes；

(5) slurry modified in step (4) is filtered, is then washed with deionized, made slurry pH Value reaches 7.0, and regulation solid content is 35%, is then passed to spray shaping tower, controls inlet temperature for 500 DEG C, Outlet temperature is 150 DEG C；Modification by calcination 10 hours at 450 DEG C again, obtaining main composition is Zn₁Mn_0.15Sr₁W_0.06·Fe₇O_12.8Finished catalyst.

Embodiment 4

A kind of Oxydehydrogenation catalyst is present embodiments provided, the specific preparation process of the catalyst is comprised the following steps：

(1) presoma six of presoma the zinc nitrate hexahydrate 1785g, B of metal A used is hydrated nitre first The presoma tungstic acid 23.1g of presoma six the calcium chloride hydrate 21.9g, D of sour nickel 14.9g, C is ground to 50 Purpose microspheroidal；Secondly, zinc nitrate hexahydrate is divided into two parts of 1071g and 714g in 60% and 40% ratio, Nickelous nitrate hexahydrate, six calcium chloride hydrates and tungstic acid are well mixed；

(2) iron nitrate solution of configuration 13L 1.0mol/L, under agitation, first by the nitric hydrates of 1071g six Zinc is added gradually in iron nitrate solution, is reacted 90 minutes, is slow added into Nickelous nitrate hexahydrate, six chloride hydrates The mixture of calcium and tungstic acid, reaction is slow added into the zinc nitrate hexahydrate of 714g, reaction 80 after 30 minutes Binding agent polyacrylamide 55.9g is added after minute, the slurry of presoma sediment is obtained；

(3) it is 10% to concentration is gradually added into slurry after slurry agitation being obtained 60 minutes in step (2) Ammoniacal liquor, to adjust slurry pH value to 7.5；

(4) heat modification is carried out in the environment of the slurry adjusted after pH in step (3) being placed in into 90 DEG C, when being modified Between be 120 minutes；

(5) slurry modified in step (4) is filtered, then with running water and distillation water washing, is made slurry Material pH value reaches 7.5, and regulation solid content is 40%, is then passed to spray shaping tower, controls the inlet temperature to be 300 DEG C, outlet temperature is 100 DEG C；Modification by calcination 12 hours at 400 DEG C again, obtaining main composition is Zn₆Ni_0.05Ca_0.1W_0.1·Fe₁₃O₂₆Finished catalyst.

Embodiment 5

A kind of Oxydehydrogenation catalyst is present embodiments provided, the specific preparation process of the catalyst is comprised the following steps：

(1) first by the presoma Cobalt monosulfate heptahydrate of presoma the chromium sulfate 1200g, B of metal A used It is micro- that the presoma tungstic acid 2.3g of presoma the Magnesium dichloride hexahydrate 101g, D of 87.3g, C is ground to 90 purposes It is spherical；Secondly, chromium sulfate is divided into two parts of 660g and 540g in 55% and 45% ratio, by seven hydrated sulfuric acids Cobalt, Magnesium dichloride hexahydrate and tungstic acid are well mixed；

(2) iron nitrate solution of configuration 60L 0.3mol/L, under agitation, first gradually adds 660g chromium sulfates Enter in iron nitrate solution, react 90 minutes, be slow added into Cobalt monosulfate heptahydrate, Magnesium dichloride hexahydrate and three oxygen Change the mixture of tungsten, reaction is slow added into the chromium sulfate of 540g after 60 minutes, reaction is added after 60 minutes and bonded Agent polyvinyl alcohol 8.7g, obtains the slurry of presoma sediment；

(3) it is 20% to concentration is gradually added into slurry after slurry agitation being obtained 40 minutes in step (2) Ammoniacal liquor, to adjust slurry pH value to 8.5；

(4) heat modification is carried out in the environment of the slurry adjusted after pH in step (3) being placed in into 80 DEG C, when being modified Between be 70 minutes；

(5) slurry modified in step (4) is filtered, is then washed with desalted water and deionized water, made Slurry pH value reaches 7.2, and regulation solid content is 5%, is then passed to spray shaping tower, controls the inlet temperature to be 400 DEG C, outlet temperature is 125 DEG C；Modification by calcination 6 hours at 500 DEG C again, obtaining main composition is Cr₃Co_0.3Mg_0.5W_0.01·Fe₁₈O_30.8Finished catalyst.

Embodiment 6

A kind of Oxydehydrogenation catalyst is present embodiments provided, the specific preparation process of the catalyst is comprised the following steps：

(1) presoma six of presoma the Salzburg vitriol 1245g, B of metal A used is hydrated nitre first It is micro- that the presoma tungstic acid 18.5g of oxidation of precursor the calcium 33.6g, D of sour cobalt 2.9g, C is ground to 100 purposes It is spherical；Secondly, Salzburg vitriol is divided into two parts of 747g and 498g in 60% and 40% ratio, by six water Close cobalt nitrate, calcium oxide and tungstic acid well mixed；

(2) iron nitrate solution of configuration 40L 0.1mol/L, under agitation, first by 747g Salzburg vitriols It is added gradually in iron nitrate solution, reacts 60 minutes, is slow added into cabaltous nitrate hexahydrate, calcium oxide and three oxygen Change the mixture of tungsten, reaction is slow added into the Salzburg vitriol of 498g after 90 minutes, reaction adds after 20 minutes Enter binding agent sesbania powder 55.9g, obtain the slurry of presoma sediment；

(3) it is 15% to concentration is gradually added into slurry after slurry agitation being obtained 60 minutes in step (2) Ammoniacal liquor, to adjust slurry pH value to 9.0；

(4) heat modification is carried out in the environment of the slurry adjusted after pH in step (3) being placed in into 95 DEG C, when being modified Between be 60 minutes；

(5) slurry modified in step (4) is filtered, then with distilled water and desalination water washing, is made slurry Material pH value reaches 7.0；By filter cake at 100 DEG C modification by calcination 6 hours, modification by calcination 8 hours at 200 DEG C, Modification by calcination 1 hour at 300 DEG C, modification by calcination 1 hour at 550 DEG C is ground after cooling, screens out 60-100 Purpose catalyst microspheres, it is Cu to obtain main composition₅Co_0.01Ca_0.6W_0.08·Fe₄O_11.9Finished catalyst.

Embodiment 7

Present embodiments provide a kind of Oxydehydrogenation catalyst, the catalyst essentially according to embodiment 1 preparation technology and Prepared by material ratio, differ only in：Treatment is not ground to each metal precursor in the step of the present embodiment (1).

Embodiment 8

Present embodiments provide a kind of Oxydehydrogenation catalyst, the catalyst essentially according to embodiment 1 preparation technology and Prepared by material ratio, differ only in：In step (1), precursor A is not drawn to be divided to two parts；In step (2) In, after the presoma of metal A is disposably added iron nitrate solution, react 160 minutes, then add six nitric hydrates The mixture of nickel, six calcium chloride hydrates and tungstic acid.

Comparative example 1

This comparative example provides a kind of Oxydehydrogenation catalyst contrasted with embodiment 1-8 product, the catalyst Prepared by preparation technology and material ratio essentially according to embodiment 1, difference is：Do not used in catalyst preparation process Metal D (tungsten).

Embodiment 9

A kind of mixing trans-utilization technique of carbon four is present embodiments provided, material used and catalyst are as follows in technique：

Olefin oxidation dehydrogenation prepares catalyst prepared by embodiment 1 using olefin oxidation dehydrogenation, its master Constitute and be：Zn₆Ni_0.3Ca_0.9W_0.02·Fe₁₇O_32.7.The KC-116 that catalyst for etherification is produced using Kai Rui chemical companies Type resin catalyst, its particle size range >=99% (0.355-1.250mm), wet true density 1150-1250g/l is total to exchange Capacity >=1.7mmol/ml [H⁺], mechanical strength >=98% (H types).Catalytic dehydrogenation catalyst uses Haitai company HTPB-DH dehydrogenations, wherein with Al₂O₃It is carrier with Pt and Cl as active component, the wherein quality of Pt Content is 1%, and chlorine mass content is 2%, and specific surface area is 200m²/ g, pore volume 0.5ml/g, a diameter of 1.59mm, Heap density 0.6g/cm³。

Mixing carbon four raw material is raw material A (concrete composition is shown in Table 1).

The technique that the present embodiment is provided at least is comprised the following steps：

The first step：Feeding oxidative dehydrogenation reactor (R1) carries out alkane after the preheating of the raw material of carbon four, air and water will be mixed Hydrocarbon oxidative dehydrogenation, wherein, the reaction condition of oxidative dehydrogenation is：Temperature is 340 DEG C, and pressure is atmospheric pressure, body Product air speed is 400h^-1；It is into the alkene in all hydrocarbon materials in oxidative dehydrogenation reactor and the mol ratio of oxygen 1:0.68；The mass ratio of all hydrocarbon materials and water into oxidative dehydrogenation unit is 1:12；In product, diene The mass yield of hydrocarbon is 61.3%, and the mass yield of alcohols is 0.81%, and the mass yield of ketone is 0.55%；

The product of oxidative dehydrogenation is sent into separative element I (T1) and is separated into butadiene, other in addition to butadiene C-4-fraction and remaining ingredient；

Second step：Other C-4-fractions in addition to butadiene that the first step is obtained are sent into methyltertiarvbutyl ether reactor with methyl alcohol (R2) etherification reaction is carried out, wherein, the reaction condition of etherificate is：45 DEG C of reaction temperature, volume space velocity 2h^-1, Reaction pressure 1.5MPa, methyl alcohol is 1.2 with the mol ratio for entering the isobutene in methyltertiarvbutyl ether reactor in hydrocarbon material:1； In etherification reaction product, the mass yield of ether compound is 42.7%；

Etherification product is sent into separative element II (T2) and is separated into light dydrocarbon and above component, C_4 hydrocarbon and remaining ingredient (mainly containing ether compound)；

3rd step：The C_4 hydrocarbon that second step is obtained carries out alkane and urges with hydrogen feeding catalytic dehydrogenating reaction device (R3) Fluidized dehydrogenation reacts, wherein, reaction condition is：480 DEG C of reaction temperature, volume space velocity 0.1h^-1, reaction pressure 0.01MPa, Hydrogen is 0.25 with all hydrocarbon material mol ratios for entering catalytic deoxidation unit:1；In reacted catalytic dehydrogenation product Olefin(e) centent is 37.4%；

Product is sent into separative element III (T3) and is separated into on-condensible gas and remaining ingredient (predominantly C_4 hydrocarbon), Remaining ingredient returns to the oxidative dehydrogenation unit of the first step.

Embodiment 10

A kind of mixing trans-utilization technique of carbon four is present embodiments provided, material used and catalyst are as follows in technique：

Olefin oxidation dehydrogenation prepares catalyst prepared by embodiment 2 using olefin oxidation dehydrogenation, its master Constitute and be：Cu_2.5Co_0.4Ba_0.1W_0.06·Fe₁₈O_30.2.Catalyst for etherification uses Dandong Mingzhu Special Type Resin Co., Ltd. The D005-II resin catalysts of production.Its particle size range 0.315-1.25mm, wet true density 1180-1200g/l, always Exchange capacity >=5.2mmol/g [H⁺], mechanical strength >=95% (H types).Catalytic dehydrogenation catalyst is used In CN101940922A prepared by the method for embodiment 4.It is concretely comprised the following steps：117.5 grams of chromium oxide is first weighed, It is dissolved in deionized water and is sufficiently stirred for, it is 47% oxidation chromium solution to be configured to weight concentration.Being reconfigured at weight concentration is 3.86% Alkitrate.Then by 55.0 grams of boehmites, 2.2 grams of bentonites, prepared with 7.59 grams Oxidation chromium solution be sufficiently mixed, mediate, be extruded into bead.Then dried 3 hours at 120 DEG C, then 500 DEG C constant temperature 3 hours, in 620 DEG C of constant temperature 2 hours, finally under 20% water and 80% air 760 DEG C be calcined 4 hours. 11.39 grams of the oxidation chromium solution for preparing is taken again, and roasting sample is impregnated 20 minutes, it is small in 120 DEG C of dryings 3 When, in 550 DEG C of constant temperature calcinings 5 hours.The Alkitrate dipping for preparing is taken again, it is small in 120 DEG C of dryings 3 When, it is standby in 620 DEG C of constant temperature calcinings 6 hours.

Mixing carbon four raw material is raw material B (concrete composition is shown in Table 2).

The technique that the present embodiment is provided at least is comprised the following steps：

The first step：Oxidative dehydrogenation will be sent into after mixing carbon four raw material, oxygenous 45% oxygen-enriched stream and water preheating Device (R1) carries out alkanes oxidative dehydrogenation reaction, wherein, the reaction condition of oxidative dehydrogenation is：Temperature is 350 DEG C, pressure Power is 100KPa, and volume space velocity is 10h^-1；Alkene and oxygen into all hydrocarbon materials in oxidative dehydrogenation reactor The mol ratio of gas is 1:0.3；The mass ratio of all hydrocarbon materials and water into oxidative dehydrogenation unit is 1:30；Reaction In product, the mass yield of alkadienes is 52.4%, and the mass yield of alcohols is 0.51%, and the mass yield of ketone is 0.27%；

The product of oxidative dehydrogenation is sent into separative element I (T1) and is separated into butadiene, other in addition to butadiene C-4-fraction and remaining ingredient；

Second step：Other C-4-fractions in addition to butadiene that the first step is obtained are sent into methyltertiarvbutyl ether reactor with methyl alcohol (R2) etherification reaction is carried out, wherein, the reaction condition of etherificate is：80 DEG C of reaction temperature, volume space velocity 3.0h^-1, Reaction pressure 1.0MPa, methyl alcohol is 1.1 with the mol ratio for entering the isobutene in methyltertiarvbutyl ether reactor in hydrocarbon material:1； In etherification reaction product, the mass yield of ether compound is 40.6%；

Etherification product is sent into separative element II (T2) and is separated into light dydrocarbon and above component, C_4 hydrocarbon and remaining ingredient (mainly containing ether compound)；

3rd step：The C_4 hydrocarbon that second step is obtained carries out alkane and urges with hydrogen feeding catalytic dehydrogenating reaction device (R3) Fluidized dehydrogenation reacts, wherein, reaction condition is：700 DEG C of reaction temperature, volume space velocity 1.0h^-1, reaction pressure 0.15Mpa, Hydrogen is 0.1 with all hydrocarbon material mol ratios for entering catalytic deoxidation unit:1；In reacted catalytic dehydrogenation product Olefin(e) centent is 51.8%；

Product is sent into separative element III (T3) and is separated into on-condensible gas and remaining ingredient (mainly containing C_4 hydrocarbon), Remaining ingredient returns to the oxidative dehydrogenation unit of the first step.

Embodiment 11

A kind of mixing trans-utilization technique of carbon four is present embodiments provided, material used and catalyst are as follows in technique：

Olefin oxidation dehydrogenation prepares catalyst prepared by embodiment 3 using olefin oxidation dehydrogenation, its master Constitute and be：Zn₁Mn_0.15Sr₁W_0.06·Fe₇O_12.8.The NKC-9 that catalyst for etherification is produced using Chemical Plant of Nankai Univ. Cation exchange resin catalyst.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 is using using real in patent CN101618319 It is prepared by the method for applying example 1.2.24 grams of calcium oxide and 3.1 grams of polyethylene glycol are dissolved in 120ml deionized waters, 240 After DEG C hydro-thermal process 24 hours, 600 DEG C of calcinations 5 hours, appropriate absolute ethyl alcohol and 7.2 grams of chromic nitrates, 6 are used Gram alundum (Al2O3) is well mixed, and grinding is uniform after drying 12 hours, standby after calcination 3 hours at 550 DEG C.

The technique that the present embodiment is provided at least is comprised the following steps：

The first step：After the preheating of the raw material A of carbon four (composition is shown in Table 1), oxygenous 35% oxygen-enriched stream and water will be mixed Feeding oxidative dehydrogenation reactor (R1) carries out alkanes oxidative dehydrogenation reaction, wherein, the reaction condition of oxidative dehydrogenation is： Temperature is 380 DEG C, and pressure is 50KPa, and volume space velocity is 60h^-1；Into all hydro carbons in oxidative dehydrogenation reactor Alkene and the mol ratio of oxygen are 1 in material:0.1；Into all hydrocarbon materials and the quality of water of oxidative dehydrogenation unit Than being 1:5；In product, the mass yield of alkadienes is 59.3%, and the mass yield of alcohols is 0.43%, ketone The mass yield of class is 0.20%；

The product of oxidative dehydrogenation is sent into separative element I (T1) and is separated into butadiene, other in addition to butadiene C-4-fraction and remaining ingredient；

Second step：Other C-4-fractions in addition to butadiene that the first step is obtained are sent into methyltertiarvbutyl ether reactor with methyl alcohol (R2) etherification reaction is carried out, wherein, the reaction condition of etherificate is：65 DEG C of reaction temperature, volume space velocity 4h^-1, Reaction pressure 0.5MPa, methyl alcohol is 1.3 with the mol ratio for entering the isobutene in methyltertiarvbutyl ether reactor in hydrocarbon material:1； In etherification reaction product, the mass yield of ether compound is 55.7%；

Etherification product is sent into separative element II (T2) and is separated into light dydrocarbon and above component, C_4 hydrocarbon and remaining ingredient (mainly containing ether compound)；

3rd step：The C_4 hydrocarbon that second step is obtained carries out alkane and urges with hydrogen feeding catalytic dehydrogenating reaction device (R3) Fluidized dehydrogenation reacts, wherein, reaction condition is：570 DEG C of reaction temperature, volume space velocity 3.0h^-1, reaction pressure 1.7MPa, Hydrogen is 0.01 with all hydrocarbon material mol ratios for entering catalytic deoxidation unit:1；In reacted catalytic dehydrogenation product Olefin(e) centent is 55.3%；

Product is sent into separative element III (T3) and is separated into on-condensible gas and remaining ingredient (predominantly C_4 hydrocarbon), Remaining ingredient returns to the oxidative dehydrogenation unit of the first step.

Embodiment 12

A kind of mixing trans-utilization technique of carbon four is present embodiments provided, material used and catalyst are as follows in technique：

Olefin oxidation dehydrogenation prepares catalyst prepared by embodiment 4 using olefin oxidation dehydrogenation, its master Constitute and be：Zn₆Ni_0.05Ca_0.1W_0.1·Fe₁₃O₂₆.Catalyst for etherification uses the Jiangsu AudioCodes limited public affairs of petrochemistry technology The produced macropore strong acid resin catalyst of department, its granularity is 0.315-1.25mm, bulk density 0.77-0.85g/ml, Specific surface area is more than 20-70m²/ g, aperture is more than 20-50nm, and pore volume is more than 0.3-0.5cc/g.Dehydrogenation is used In CN101940922A prepared by the method for embodiment 4.It is concretely comprised the following steps：117.5 grams of chromium oxide is first weighed, It is dissolved in deionized water and is sufficiently stirred for, it is 47% oxidation chromium solution to be configured to weight concentration.Being reconfigured at weight concentration is 3.86% Alkitrate.Then by 55.0 grams of boehmites, 2.2 grams of bentonites, prepared with 7.59 grams Oxidation chromium solution be sufficiently mixed, mediate, be extruded into bead.Then dry 3 hours at 120 DEG C again, then 500 DEG C constant temperature 3 hours, in 620 DEG C of constant temperature 2 hours, finally under 20% water and 80% air 760 DEG C be calcined 4 hours. 11.39 grams of the oxidation chromium solution for preparing is taken again, and roasting sample is impregnated 20 minutes, it is small in 120 DEG C of dryings 3 When, in 550 DEG C of constant temperature calcinings 5 hours.The Alkitrate dipping for preparing is taken again, it is small in 120 DEG C of dryings 3 When, it is standby in 620 DEG C of constant temperature calcinings 6 hours.

Mixing carbon four raw material is raw material B (concrete composition is shown in Table 2).

The technique that the present embodiment is provided at least is comprised the following steps：

The first step：Oxidative dehydrogenation will be sent into after mixing carbon four raw material, oxygenous 40% oxygen-enriched stream and water preheating Device (R1) carries out alkanes oxidative dehydrogenation reaction, wherein, the reaction condition of oxidative dehydrogenation is：Temperature is 390 DEG C, pressure Power is 20KPa, and volume space velocity is 500h^-1；Alkene and oxygen into all hydrocarbon materials in oxidative dehydrogenation reactor The mol ratio of gas is 1:0.8；The mass ratio of all hydrocarbon materials and water into oxidative dehydrogenation unit is 1:16；Reaction In product, the mass yield of alkadienes is 53.4%, and the mass yield of alcohols is 0.63%, and the mass yield of ketone is 0.31%；

The product of oxidative dehydrogenation is sent into separative element I (T1) and is separated into butadiene, other in addition to butadiene C-4-fraction and remaining ingredient；

Second step：Other C-4-fractions in addition to butadiene that the first step is obtained are sent into methyltertiarvbutyl ether reactor with methyl alcohol (R2) etherification reaction is carried out, wherein, the reaction condition of etherificate is：75 DEG C of reaction temperature, volume space velocity 5h^-1, Reaction pressure 1.2MPa, methyl alcohol is 1.5 with the mol ratio for entering the isobutene in methyltertiarvbutyl ether reactor in hydrocarbon material:1； In etherification reaction product, the mass yield of ether compound is 45.2%；

Etherification product is sent into separative element II (T2) and is separated into light dydrocarbon and above component, C_4 hydrocarbon and remaining ingredient (mainly containing ether compound)；

3rd step：The C_4 hydrocarbon that second step is obtained carries out alkane and urges with hydrogen feeding catalytic dehydrogenating reaction device (R3) Fluidized dehydrogenation reacts, wherein, reaction condition is：600 DEG C of reaction temperature, volume space velocity 5.0h^-1, reaction pressure 1.1Mpa, Hydrogen is 0.3 with all hydrocarbon material mol ratios for entering catalytic deoxidation unit:1；In reacted catalytic dehydrogenation product Olefin(e) centent is 63.6%；

Product is sent into separative element III (T3) and is separated into on-condensible gas and remaining ingredient (predominantly C_4 hydrocarbon), Remaining ingredient returns to the oxidative dehydrogenation unit of the first step.

Embodiment 13

A kind of mixing trans-utilization technique of carbon four is present embodiments provided, material used and catalyst are as follows in technique：

Olefin oxidation dehydrogenation prepares catalyst prepared by embodiment 5 using olefin oxidation dehydrogenation, its master Constitute and be：Cr₃Co_0.3Mg_0.5W_0.01·Fe₁₈O_30.8.The ether that catalyst for etherification is produced using Kai Rui Chemical Co., Ltd.s Change resin catalyst, its particle size range 0.335-1.25mm, wet true density 0.75-0.85g/ml, total exchange capacity >= 5.2mmol/g, mechanical strength >=95%.The method that dehydrogenation uses embodiment 9 in patent CN96121452.X Prepare.Weigh 17 grams of Cr (NO₃)₃·9H₂O, 1.1 grams of Cu (NO₃)₂·3H₂O, 80.8 grams of Al (NO₃)₃·9H₂O, Catalyst is prepared with coprecipitation, precipitating reagent selects 10% KOH (or NaOH) solution, nitrate to be dissolved in distillation In water, precipitating reagent is added while stirring, it is formed gel completely, and pH value is 8.5-9, aging 3 hours, mistake Filter, at 110 DEG C, dries 20 hours, is calcined at 650 DEG C 7 hours, rear standby after crushing and screening.

Mixing carbon four raw material is raw material A (concrete composition is shown in Table 1).

The technique that the present embodiment is provided at least is comprised the following steps：

The first step：Oxidative dehydrogenation will be sent into after mixing carbon four raw material, oxygenous 32% oxygen-enriched stream and water preheating Device (R1) carries out alkanes oxidative dehydrogenation reaction, wherein, the reaction condition of oxidative dehydrogenation is：Temperature is 280 DEG C, pressure Power is 10KPa, and volume space velocity is 300h^-1；Alkene and oxygen into all hydrocarbon materials in oxidative dehydrogenation reactor The mol ratio of gas is 1:0.55；The mass ratio of all hydrocarbon materials and water into oxidative dehydrogenation unit is 1:10；Reaction In product, the mass yield of alkadienes is 57.8%, and the mass yield of alcohols is 0.47%, and the mass yield of ketone is 0.30%；

The product of oxidative dehydrogenation is sent into separative element I (T1) and is separated into butadiene, other in addition to butadiene C-4-fraction and remaining ingredient；

Second step：Other C-4-fractions in addition to butadiene that the first step is obtained are sent into methyltertiarvbutyl ether reactor with ethanol stream (R2) etherification reaction is carried out, wherein, the reaction condition of etherificate is：55 DEG C of reaction temperature, volume space velocity 0.1h^-1, Reaction pressure 2.0MPa, ethanol is 1.2 with the mol ratio for entering the isobutene in methyltertiarvbutyl ether reactor in hydrocarbon material:1； In etherification reaction product, the mass yield of ether compound is 45.1%；

Etherification product is sent into separative element II (T2) and is separated into light dydrocarbon and above component, C_4 hydrocarbon and remaining ingredient (mainly containing ether compound)；

3rd step：The C_4 hydrocarbon that second step is obtained carries out alkane and urges with hydrogen feeding catalytic dehydrogenating reaction device (R3) Fluidized dehydrogenation reacts, wherein, reaction condition is：650 DEG C of reaction temperature, volume space velocity 8.0h^-1, reaction pressure 2.4Mpa, Hydrogen is 0.15 with all hydrocarbon material mol ratios for entering catalytic deoxidation unit:1；In reacted catalytic dehydrogenation product Olefin(e) centent is 35.3%；

Product is sent into separative element III (T3) and is separated into on-condensible gas and remaining ingredient ((predominantly carbon four Hydrocarbon)), remaining ingredient returns to the oxidative dehydrogenation unit of the first step.

Embodiment 14

A kind of mixing trans-utilization technique of carbon four is present embodiments provided, material used and catalyst are as follows in technique：

Olefin oxidation dehydrogenation prepares catalyst prepared by embodiment 6 using olefin oxidation dehydrogenation, its master Constitute and be：Cu₅Co_0.01Ca_0.6W_0.08·Fe₄O_11.9.The RZE-3 of catalyst for etherification purchase petrochemical industry academy of sciences research and development Zeolite catalyst for etherification, 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 uses patent CN101623633A In middle embodiment 1 catalyst is prepared the step of catalyst preparation.ZSM-5 molecular sieve original powder is placed in 0.16M's first SnCl₂·2H₂10hr is impregnated in 80 DEG C so that the load capacity of the Sn in catalyst reaches 4wt%, so in O solution Afterwards 6hr is dried at 120 DEG C.Dried sample is calcined 4hr under 550 DEG C of air atmospheres.Powder after roasting exists The H of 0.03M₂PtCl₆·6H₂4hr is impregnated at 80 DEG C in O solution, makes Pt contents urging for 20wt% is finally obtained Agent, then dries 6hr at 120 DEG C, and 4hr is calcined at 550 DEG C.It is standby in 550 DEG C of hydrogen reducing 12hr afterwards.

The technique that the present embodiment is provided at least is comprised the following steps：

The first step：After the preheating of the raw material A of carbon four (composition is shown in Table 1), oxygenous 32% oxygen-enriched stream and water will be mixed Feeding oxidative dehydrogenation reactor (R1) carries out alkanes oxidative dehydrogenation reaction, wherein, the reaction condition of oxidative dehydrogenation is： Temperature is 340 DEG C, and pressure is 70KPa, and volume space velocity is 250h^-1；Into all hydrocarbon in oxidative dehydrogenation reactor Alkene and the mol ratio of oxygen are 1 in class material:0.1；Into all hydrocarbon materials and the matter of water of oxidative dehydrogenation unit Amount is than being 1:0.5；In product, the mass yield of alkadienes is 47.0%, and the mass yield of alcohols is 1.01%, The mass yield of ketone is 0.79%；

The product of oxidative dehydrogenation is sent into separative element I (T1) and is separated into butadiene, other in addition to butadiene C-4-fraction and remaining ingredient；

Second step：Other C-4-fractions in addition to butadiene that the first step is obtained are sent into methyltertiarvbutyl ether reactor with alcohols logistics (R2) etherification reaction is carried out, wherein, the reaction condition of etherificate is：30 DEG C of reaction temperature, volume space velocity 0.5h^-1, Reaction pressure 1.7MPa, methyl alcohol is 0.95 with the mol ratio for entering the isobutene in methyltertiarvbutyl ether reactor in hydrocarbon material:1； In etherification reaction product, the mass yield of ether compound is 35.6%；

Etherification product is sent into separative element II (T2) and is separated into light dydrocarbon and above component, C_4 hydrocarbon and remaining ingredient (mainly containing ether compound)；

3rd step：The C_4 hydrocarbon that second step is obtained carries out alkane and urges with hydrogen feeding catalytic dehydrogenating reaction device (R3) Fluidized dehydrogenation reacts, wherein, reaction condition is：550 DEG C of reaction temperature, volume space velocity 10.0h^-1, reaction pressure 3.0Mpa, Hydrogen is 0.5 with all hydrocarbon material mol ratios for entering catalytic deoxidation unit:1；In reacted catalytic dehydrogenation product Olefin(e) centent is 44.3%；

Product is sent into separative element III (T3) and is separated into on-condensible gas and remaining ingredient (predominantly C_4 hydrocarbon), Remaining ingredient returns to the oxidative dehydrogenation unit of the first step.

Embodiment 15

A kind of mixing trans-utilization technique of carbon four is present embodiments provided, technique is substantially the same manner as Example 9, and difference exists In：The Oxydehydrogenation catalyst for using is the Oxydehydrogenation catalyst that embodiment 7 is prepared.

The parameter of portioned product in technique：

In the first step, the mass yield of alkadienes is 40.2%, and the mass yield of alcohols is 0.81%, the quality of ketone Yield is 0.43%；

In second step, in etherification reaction product, the mass yield of ether compound is 63.5%；

In 3rd step, olefin(e) centent is 37.6% in reacted catalytic dehydrogenation product.

Embodiment 16

A kind of mixing trans-utilization technique of carbon four is present embodiments provided, technique is substantially the same manner as Example 9, and difference exists In：The Oxydehydrogenation catalyst for using is the Oxydehydrogenation catalyst that embodiment 8 is prepared.

The parameter of portioned product in technique：

In the first step, the mass yield of alkadienes is 38.4%, and the mass yield of alcohols is 0.81%, the quality of ketone Yield is 0.43%；

In second step, in etherification reaction product, the mass yield of ether compound is 65.3%；

In 3rd step, olefin(e) centent is 37.6% in reacted catalytic dehydrogenation product.

Comparative example 2

This comparative example provide it is a kind of contrasted with embodiment 9-16 it is existing mix the conversion process of carbon four, specifically Process is as follows：

The RZE-3 zeolite catalyst for etherification of catalyst for etherification purchase petrochemical industry academy of sciences research and development, 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 is using catalyst preparation the step of system in embodiment 1 in patent CN101623633A Standby catalyst.ZSM-5 molecular sieve original powder is placed in the SnCl of 0.16M first₂·2H₂In 80 DEG C of dippings in O solution 10hr so that the load capacity of the Sn in catalyst reaches 4wt%, then dries 6hr at 120 DEG C.It is dried Sample is calcined 4hr under 550 DEG C of air atmospheres.The H of powder after roasting in 0.03M₂PtCl₆·6H₂In O solution 4hr is impregnated at 80 DEG C, makes the catalyst that Pt contents are 20wt% is finally obtained, then dry 6hr at 120 DEG C, 4hr is calcined at 550 DEG C.It is standby in 550 DEG C of hydrogen reducing 12hr afterwards.

Mixing carbon four raw material is raw material B (composition is shown in Table 2).Raw material B is mixed into methyltertiarvbutyl ether reactor with methyl alcohol, Etherification reaction condition is：73 DEG C of reaction temperature, volume space velocity 1.4h^-1, reaction pressure 1.7MPa, wherein methyl alcohol with The mol ratio of iso-butane is 0.95 in hydrocarbon material into methyltertiarvbutyl ether reactor:1.By separative element, ethers is isolated Compound, its yield is 34.1%.Hydrogen and all hydrocarbon materials for entering catalytic deoxidation unit in dehydrogenation reactor Mol ratio is 0.5:1, in 550 DEG C of reaction temperature, volume space velocity 10.0h^-1, enter under conditions of reaction pressure 3.0Mpa Row reaction, olefin(e) centent is 42.5% during reaction obtains dehydrogenation product.

Comparative example 3

Present embodiments provide a kind of trans-utilization technique of mixing carbon four contrasted with embodiment 9-16, the technique Substantially using the technique in embodiment 9, difference is：The Oxydehydrogenation catalyst for using is that comparative example 1 is obtained urges Agent.

The parameter of portioned product in technique：

In the first step, the mass yield of alkadienes is 24.1%, and the mass yield of alcohols is 0.74%, the quality of ketone Yield is 0.50%；

In second step, in etherification reaction product, the mass yield of ether compound is 36.1%；

In 3rd step, olefin(e) centent is 37.5% in reacted catalytic dehydrogenation product.

Claims (19)

1. it is a kind of to mix the trans-utilization technique of carbon four, it is characterised in that the technique is at least comprised the following steps：

The first step：By mixing carbon four raw material, the logistics containing oxidant and water or water vapour feeding oxidative dehydrogenation unit Alkanes oxidative dehydrogenation reaction is carried out, product feeding separative element I is separated into butadiene, its in addition to butadiene Its C-4-fraction and remaining ingredient；

Second step：Other C-4-fractions in addition to butadiene that the first step is obtained are entered with alcohols logistics feeding etherificate unit Row etherification reaction, light dydrocarbon and above component, C_4 hydrocarbon and residue are separated into by product feeding separative element II Component；

3rd step：It is anti-that the C_4 hydrocarbon that second step is obtained carries out alkane catalytic dehydrogenation with hydrogen feeding catalytic dehydrogenation unit Should, product feeding separative element III is separated into on-condensible gas and remaining ingredient, remaining ingredient returns to the first step Oxidative dehydrogenation unit；

In the above-mentioned first step, shown in the Oxydehydrogenation catalyst such as formula (I) that the oxidative dehydrogenation unit is used：

A_aB_bC_cD_d·Fe_xO_eFormula (I)

In formula (I)：A is Cu, Zn or Cr；B is Co, Mn, Ni or Mo；C be Ca, Sr, Ba or Mg；A is 1-6, and b is 0.01-0.3, and c is 0.1-1.0, and d is 0.01-0.1, and x is 4-18, and e takes and meets chemical valence It is required that any number.

2. trans-utilization technique according to claim 1, it is characterised in that in formula (I)：A is 3-5, B is 0.05-0.15, and c is 0.3-0.6, and d is 0.04-0.08, and x is 7-13.

3. trans-utilization technique according to claim 1, it is characterised in that in the raw material of mixing carbon four just Butylene is not less than 35%, preferably not lower than 40% with the mass content sum of normal butane.

4. the trans-utilization technique according to claim 1-3 any one, it is characterised in that the oxidation takes off The reaction condition of hydrogen unit is：280 DEG C -410 DEG C of temperature, pressure 0-100KPa, volume space velocity 10-500h^-1；

Preferably, the reaction condition of the oxidative dehydrogenation unit is：310 DEG C -390 DEG C of temperature, pressure 0-40KPa, Volume space velocity 60-400h^-1。

5. the trans-utilization technique according to claim 1-3 any one, it is characterised in that described containing aerobic The logistics of agent is the material stream containing oxygen molecule or containing oxidizing strong oxygen atom, preferably air, oxygen rich air Or oxygen；

It is further preferred that during into oxidative dehydrogenation unit, oxidant with oxymeter, oxygen with enter oxidative dehydrogenation list The mol ratio of alkene is 0.1-1.0 in all hydrocarbon materials of unit:1, preferably 0.3-0.85:1.

6. trans-utilization technique according to claim 1, it is characterised in that when entering oxidative dehydrogenation unit, Water or water vapour and the mass ratio of butylene in all hydrocarbon materials for entering oxidative dehydrogenation unit are 0.5-30, preferably 5-20。

7. trans-utilization technique according to claim 1, it is characterised in that other in addition to butadiene The mass content of butadiene is not higher than 0.3%, preferably not higher than 0.1% in C-4-fraction.

8. trans-utilization technique according to claim 1, it is characterised in that when entering etherification reaction unit, Alcohols is 0.8-1.5 with the mol ratio of isobutene in all hydrocarbon materials for entering etherification reaction unit:1, preferably 1.1-1.3:1。

9. trans-utilization technique according to claim 1, it is characterised in that the reaction bar of the etherificate unit Part is：Temperature is 30-100 DEG C, and pressure is 0.1-2.0MPa, and volume space velocity is 0.1-5h^-1；

Preferentially, the reaction condition of the etherificate unit is：Temperature is 45-80 DEG C, and pressure is 0.5-1.5MPa, body Product air speed is 1-2h^-1。

10. trans-utilization technique according to claim 1, it is characterised in that isobutene turns in etherificate unit Rate is not less than 92%.

11. trans-utilization techniques according to claim 1, it is characterised in that separative element II is isolated In C_4 hydrocarbon, the mass content of the component of carbon four is not less than 97%, preferably not lower than 99%.

12. trans-utilization techniques according to claim 1, it is characterised in that the reaction of catalytic dehydrogenation unit is produced Alkene mass content is not less than 35% in thing, and preferably quality olefin content is more than 45%.

13. trans-utilization techniques according to claim 1, it is characterised in that the catalytic dehydrogenation unit it is anti- The condition is answered to be：480-700 DEG C of temperature, pressure 0.01-3MPa, volume space velocity 0.1-10h during liquid^-1；

Preferably, the reaction condition of the catalytic dehydrogenation unit is：560-650 DEG C of temperature, pressure 0.4-1.2MPa, Volume space velocity 2-7h during liquid^-1；

It is further preferred that during into catalytic dehydrogenation unit, hydrogen with enter all hydrocarbon materials in catalytic dehydrogenation unit Mol ratio be 0.01-1:1, preferably 0.1-0.5:1.

14. trans-utilization techniques according to claim 1, it is characterised in that be two in catalytic dehydrogenation unit Or multiple fixed-bed catalytic dehydrogenation reactor is used in parallel.

The 15. trans-utilization technique according to claim 1-14 any one, it is characterised in that the oxidation The preparation process of dehydrogenation is comprised the following steps：

(1) presoma of metal A, B, C and D used is ground to the microspheroidal of 40-100 mesh respectively；And It it is two parts by the presoma parts by weights of ground metal A；Meanwhile, the presoma of metal B, C and D is mixed Close uniform；

(2) iron nitrate solution of 0.1-2mol/L is configured, under agitation, by first part of presoma of metal A It is added gradually in iron nitrate solution, reaction adds the forerunner of well mixed metal B, C and D after 30-90 minutes Body, second part of presoma of metal A is added after continuing to react 30-90 minutes, is added after continuing to react 20-80 minutes Binding agent, obtains the slurry of presoma sediment；

(3) it is 10-25% to concentration is gradually added into slurry after slurry agitation 20-60 minutes being obtained in step (2) Ammoniacal liquor, to adjust slurry pH value to 7.5-10.0；

(4) heat modification is carried out in the environment of the slurry adjusted after pH in step (3) being placed in into 80-95 DEG C, is changed Property the time be 60-180 minutes；

(5) slurry modified in step (4) is filtered, then with washing water washing, is made slurry pH value 7-7.5 is reached, and adjusts slurry solid content for 5-40%, then spray shaping, 6-12 is calcined at 400-500 DEG C Hour, obtain finished catalyst；

Or filtered slurry modified in step (4), then with washing water washing, and make slurry pH Value reaches 7-7.5, is then calcined 6-12 hours at 100-200 DEG C, is calcined 4-8 hours at 200-300 DEG C, It is calcined 1-4 hours at 300-400 DEG C, is calcined 1-4 hours at 400-500 DEG C, grinding obtains finished catalyst.

16. trans-utilization techniques according to claim 15, it is characterised in that in Oxydehydrogenation catalyst In step (1) in preparation process, first part of presoma of metal A is the presoma gross weight of metal A 55-70%.

17. trans-utilization techniques according to claim 15, it is characterised in that in Oxydehydrogenation catalyst In step (1) in preparation process, the presoma of described metal A, B, C and D is respectively selected from respective metal The combination of one or more in nitrate, chloride, sulfate and oxide.

18. described trans-utilization techniques according to claim 15, it is characterised in that in oxidative dehydrogenation catalysis In step (2) in the preparation process of agent, the binding agent includes sesbania powder, polyacrylamide, methylcellulose With the combination of one or more in polyvinyl alcohol；

Preferably, the addition of the binding agent is the 0.1-4% of metal precursor gross mass.

19. described trans-utilization techniques according to claim 15, it is characterised in that in oxidative dehydrogenation catalysis In step (5) in the preparation process of agent, in the spray shaping, the feeding temperature of spray tower is 300-500 DEG C, Discharging opening temperature is 100-150 DEG C.