CN106867563B - A method of conversion plug oils lighter hydrocarbons - Google Patents

Abstract

The present invention provides a kind of methods of conversion plug oils lighter hydrocarbons.This method includes：The raw material and hydrogen that will be enriched in C4 C6 alkane carry out catalytic dehydrogenating reaction, obtain logistics a；Logistics a is sent into separative element I, isolated logistics b and logistics c；Logistics c, the logistics containing oxidant and water are subjected to oxidative dehydrogenation, obtain logistics d；Logistics e is obtained after logistics d is isolated alkadienes；Logistics e, logistics b and alcohols are subjected to etherification reaction, obtain gasoline component.For this method by combining catalytic dehydrogenation, oxidative dehydrogenation, etherificate, the raw material that will be enriched in C4 C6 alkane is converted into gasoline component, while preparing the butadiene of a certain amount of high value, and the conversion process of the plug oils raw material containing C4 C5 alkane is made more to refine.

Description

A method of conversion plug oils lighter hydrocarbons

Technical field

The present invention relates to a kind of methods preparing gasoline component by lighter hydrocarbons, belong to petrochemical industry.

Background technology

Since 12, with the 20000000 tons/year of oil refining of China Petroleum Guangdong petrochemical industry, 10,000,000 tons/year of Kunming oil refining, four The projects such as 1,200,000 tons/year of river petrochemical industry Integrated Refinery And Petrochemical engineering, 800,000 tons/year of ethylene of Fushun petrochemical industry, Daqing petrochemical expansion of ethylene Propulsion, the refining capacity and ethylene production capacity of China Petroleum will also further expand, tops, pentane oil, the coke of refinery's by-product The yield of naphtha etc. is also being significantly increased.It is main by the tops of key component, pentane oil, coking naphtha etc. of alkane It is gasoline by isomerization technique, the restructuring of high temperature aromatization technology, but generation dry gas amount is larger, loss is serious, and yield is not high. Tops, pentane oil etc. are not only cheap, and transportation cost is high, it is big to be lost in transportational process, belongs to for refinery at a low price It is worth product.

With the rapid development of Chinese national economy, car ownership is continuously increased, the demand to vehicle fuel gasoline It measures increasing.Meanwhile also with environmental requirement to the increasingly stringent of gasoline quality standard, motor petrol quality standard to Low sulfur content, low olefin-content, low-steam pressure and high-octane direction are developed.Market is to volume increase premium-type gasoline and to low Sulphur, low olefin-content, gasoline component blending component have very big demand, the technological development of this aspect also single as domestic each research The hot issue of position and enterprises pay attention.

Butadiene is the primary raw material of synthetic rubber, accounts for the 71% of total raw material, butadiene demand is up to 350 within 2015 Ten thousand tons.Chinese butadiene source is relatively simple, mainly uses four extraction process of carbon, is produced by ethylene unit, by ethylene energy in 2015 21,000,000 tons of calculating of power, butadiene total resources is ten thousand tons of 284-294, and serious notch will occur in butadiene.Butadiene it is another Important sources are butylene oxidation-dehydrogenation technologies.Butylene oxidation-dehydrogenation is using positive structure butylene as raw material, domestic n-butene catalysis dehydrogenation Agent is at home under the joint efforts of relevant unit, experienced ternary molybdenum series catalyst, hexa-atomic molybdenum series catalyst, H-198 iron system and B-O2 Fe-series catalysts, reaction bed are also insulation fix bed by the two sections of axial directions of initial deflector apron fluid bed development finally. It is continuous newly-built with domestic large-scale ethylene plant however since the 1980s, the production technology of butadiene gradually by Less expensive four extraction process of carbon of cost is replaced, and numerous n-butene oxidative dehydrogenation devices gradually stops production, therefore domestic n-butene Oxidative dehydrogenation technology could not further be developed.But it in the long run, is influenced, is extracted by ethylene cracker raw material lighting The newly-increased butadiene production capacity of method will be increasingly difficult to meet the needs of following downstream synthetic rubber is to butadiene.

Pentadiene chemical property is active, be production polyisoprene rubber, specific rubber, Petropols, pesticide, medicine, The important industrial chemicals of a variety of petrochemicals such as fragrance, curing agent, fire retardant and fine chemical product.Pentadiene is mainly It is obtained from the separating-purifying of petroleum cracking Crude products.deep process, thus its production capacity and utilization rate are by region dispersion and state of arts Serious limitation.

CN102716754A discloses a kind of butadiene catalyst made by butylene oxidation dehydrogen for fluidized-bed reactor Metal precursor and alkaline matter are obtained by the reaction in the case where 10-90 DEG C, pH is 5-11 containing insoluble chemical combination for preparation method, this method The slurry of object, by slurries filtration and wash to pH be 7-7.5；Appropriate binder, deionized water stirring is added, adjusts slurry and contains admittedly Amount is 10%-50%；Gained slurry by spraying drying granulating equipment carry out spray drying granulation, feeding temperature be 200 DEG C- 400 DEG C, outlet temperature be 100 DEG C -160 DEG C, obtain catalyst microspheres；By catalyst microspheres at 80 DEG C -200 DEG C of drying temperature Dry 1-24h, roasts 4-24h at 500 DEG C -900 DEG C, obtains finished catalyst.The general formula for obtaining catalyst is FeX_aY_bZ_cO_d, wherein X is one or more of Ni, Co, Zn, Cu, Sn, Mn, in Y Bi, Mo, Cr, V, La, Zr One or more, one or more of Z Mg, Ca, Sr, Ba, a 0.1-3, b 0-1, c 0-1's, d takes Value meets the requirement of other metallic element chemical valences.The catalyst delays dehydrogenation butadiene for butylene, in temperature 300-400 DEG C, normal pressure, water/alkene molar ratio 6-16, oxygen/alkene molar ratio 0.4-1.0, butylene volume space velocity 100-600h^-1Under conditions of, fourth two Alkene yield is 76%-86%, butadiene selective 94-97%.The shortcomings that catalyst is that treating capacity is smaller, and full airspeed is only For 600h^-1；In addition, the catalyst has only carried out the evaluation test of 6h, the stability of catalyst cannot 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, 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% (weights Amount).General 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, B is selected from Mg, Ca, Sr, one or both of Ba elements, and C is selected from Ni, a kind of member in Co Element, a=0.1-0.9, b=0.01-0.1, a+b+c=1, X=15-65% (weight).It does precipitating reagent with ammonium hydroxide, precipitates terminal PH is 8.2-8.7, and precipitation aging temperature is 50-95 DEG C, time 30min, filtration washing, and filter cake is done with 100-120 DEG C after filtering Dry, time 12-24h, activation temperature is 640-700 DEG C, time 10-20h.The catalyst is used for Oxidative Dehydrogenation of Butene fourth When diene shelf fluidized bed reactor, in 310-420 DEG C of temperature, normal pressure, water/alkene molar ratio 8-12, oxygen/alkene molar ratio 0.56- 0.9, butylene volume space velocity 150-600h^-1Under conditions of, butadiene yield 70-85%, butadiene selective 93-96%, The shortcomings that catalyst is the shelf fluidized bed reactor being only applied to using n-butene as raw material.

CN103055890A discloses a kind of iron catalyst of n-butene oxidative dehydrogenation butadiene, which is with Fe Main component, using Mg, Zn and extraction element as auxiliary agent, the quality group of catalyst becomes 48.80-60.53wt%Fe, 0.01- 18.0%Mg, 0.0-15.0wt%Zn and other element gross masses are 0.0-5.0wt%, remaining is oxygen element, other The one kind or more of element in Ba, Ca, Ni, Co, Cu, Cr, p, Si, Al, V, Ti, Mo, Sn, Sb, Zr, Mn, K and rare earth element Kind.When the catalyst is used for fixed bed Oxidative Dehydrogenation of Butene into Butadiene, in 260-445 DEG C of temperature, normal pressure, water/alkene molar ratio 12-25, oxygen/alkene molar ratio 0.42~0.90, butylene volume space velocity 180-600h^-1Under conditions of, the yield highest of butadiene is only It is 72.8%.The shortcomings that catalyst is that treating capacity is smaller, and full airspeed is only 600h^-1；In addition, the butadiene of the catalyst is received Rate is relatively low.

CN102824914A discloses a kind of method for n-butene oxidative dehydrogenation butadiene, this method using cobalt and Magnesium elements, which are modified, is made the oxidative dehydrogenation that iron acid zinc catalyst is used for n-butene.But the catalyst is only applicable to n-butene, in temperature Spend 400-450 DEG C, unstripped gas：Air：Water vapour volume ratio is 1:4:16,500~700h of butylene volume space velocity^-1Under conditions of, The yield of butadiene is only up to 77.8%.The treating capacity of catalyst is also smaller.

CN101674883 discloses a kind of iron acid zinc catalyst, is combined with simple zinc ferrite, it is difficult to reach and preferably urge Change effect, and catalyst is used for fixed bed reactors, catalyst bed temperature rises serious, high energy consumption, while can not solve to urge Wear problem of the agent on fluidized-bed reactor.

US3450788 and US3450787 describes a variety of different spinel structure ferric chromate butylene oxidation-dehydrogenations and urges Agent.Wherein spinelle ferric chromate catalyst has preferable Oxidative Dehydrogenation of Butene into Butadiene reactivity worth, butylene one way Molar yield is 70%, and butadiene molar selectivity is up to 92%.

CN1033013, CN101674883 and CN1184705 etc. describe the Oxidative Dehydrogenation of Butene based on ferrite The preparation method of butadiene catalyst.The molar yield of butylene is generally 70-80%, butadiene mole choosing on these catalyst Selecting property is 89-93%.Which part patent once obtains commercial Application at home, but by butadiene demand at that time and technological level institute Limit, is forced to stop production.

Therefore it provides a kind of plug oils lighter hydrocarbons method for transformation becomes one of this field urgent problem to be solved.

Invention content

In order to solve the above technical problems, the purpose of the present invention is to provide a kind of sides of that conversion plug oils lighter hydrocarbons Method, for this method by combining catalytic dehydrogenation, oxidative dehydrogenation, etherificate, the raw material that will be enriched in C4-C6 alkane is converted into gasoline group Point, while the butadiene of a certain amount of high value is prepared, keep the conversion process of the plug oils raw material containing C4-C5 alkane more smart Refinement.

In order to achieve the above objectives, the present invention provides a kind of method of conversion plug oils lighter hydrocarbons, this method includes following Step：

The first step, the raw material that will be enriched in C4-C6 alkane and hydrogen are sent into catalytic dehydrogenation unit and carry out catalytic dehydrogenating reaction, Obtain the logistics a rich in alkene；

Second step, the logistics a for obtaining the first step are sent into separative element I, the hydrocarbon material flow b of isolated C6 or more with C5 hydrocarbon material flow c below；

Third step, will logistics c, the logistics containing oxidant and water be sent into oxidative dehydrogenation unit in carry out oxidative dehydrogenation it is anti- It answers, obtains the logistics d containing alkadienes；

Logistics d is sent into separative element II by the 4th step, and logistics e is obtained after alkadienes is detached；

5th step will carry out etherification reaction in logistics e, logistics b and alcohols feeding etherificate unit, obtain gasoline component；Its In,

In the third step, the composition of the Oxydehydrogenation catalyst used in oxidative dehydrogenation unit is shown in formula I：

A_aB_bC_cD_d·Fe_xO_eFormulas I

In Formulas I：A is 2-10, and b 0.01-0.5, c 0.01-0.5, d 0.01-0.2, x 4-20, e take satisfactionization The numerical value that conjunction valence requires；

A is Cu, Co or Cr；B is K, Zn or V；C is Ca, Sr, Ba or Mg；D is W.

In the present invention rich in C4-C6 alkane raw material refer to refinery in process of production institute's by-product with four light dydrocarbon carbon six of carbon Alkane is the hydro carbons of key component (as tops, coking light naphthar, oil field light hydrocarbon, pentane oil and other devices recycle Four light dydrocarbon carbon of carbon, six hydro carbons etc.), the content of general alkane is in 90% or more, preferably 95%.C4-C6 alkane is rich in the present invention In the raw material of hydrocarbon the boiling range of 95% part at 75 DEG C hereinafter, preferably at 70 DEG C hereinafter, can be same raw material, can also It is that different material is mixed to get.The not specified percentage of the present invention is quality %.

The raw material rich in C4-C6 alkane can be the raw material in same source, can also be by the raw material of separate sources It is mixed to get.

It is not particularly limited catalytic dehydrogenation catalyst in catalytic dehydrogenation unit of the present invention, it is desirable that catalytic dehydrogenation product (logistics A) content of alkene is not less than 35% in, it is preferable that the content of alkene is 45% or more in logistics a.

In the above-mentioned methods, it is preferable that in the first step, the reaction condition of catalytic dehydrogenation unit is：Temperature is 480-700 DEG C, pressure 0.01-3MPa, liquid volume air speed is 0.1-10h^-1；It is highly preferred that temperature is 560-650 DEG C, pressure 0.4- 1.2MPa, liquid volume air speed are 2-7h^-1。

In the above-mentioned methods, it is preferable that in the first step, hydrogen and all hydrocarbon materials in entrance oxidative dehydrogenation unit The molar ratio of (raw material for being rich in C4-C6 alkane) is (0.01-1):1, more preferably (0.1-0.5):1.

In the present invention in separative element I, it is desirable that the content of hydrocarbons of the carbon number more than 6 is not higher than 1% in logistics c, this Invention is not required separation method, but compares recommendation rectifying.

In the above-mentioned methods, it is preferable that in the third step, n-butene is converted into turning for alkadienes with n-pentene in logistics c Rate is not less than 70%, is preferably not less than 75%.During producing alkadienes using oxydehydro process, positive structure alkene Hydrocarbon does main contributions, and the utilization rate of isomery alkene is relatively low.

In the above-mentioned methods, it is preferable that in the third step, the reaction condition of oxidative dehydrogenation unit is：Temperature be 280 DEG C- 410 DEG C, preferably 310 DEG C -390 DEG C, pressure 0-100KPa, preferably 0-40KPa, volume space velocity 10-500h^-1, preferably For 60-400h^-1.Volume space velocity when the not specified air speed of the present invention is liquid.

In the above-mentioned methods, it is preferable that in the third step, the logistics containing oxidant is containing oxygen molecule or oxygen atom Material stream, preferably air, oxygen rich air or purity oxygen；More preferably oxygen mole content is the oxygen rich air of 32-45%；Further Preferably, in the logistics containing oxidant, oxidant is with oxymeter, the oxygen and owning in entrance oxidative dehydrogenation unit (molar ratio of the alkene in logistics c) is (0.1-1.0) to hydrocarbon material:1, preferably (0.3-0.85):1.It is provided by the invention Technical solution is by controlling the content of oxidant in the logistics containing oxidant, come oxygen atom, alkene in controlling into reaction system The time of contact of hydrocarbon and catalyst, and then control reaction residence time and not only can in the complex reaction of a variety of olefin oxidations Enough ensure that monoolefine is fully converted into alkadienes, and the generation of alcohols and aldehydes can be efficiently controlled, improves alkadienes Yield and selectivity.

In the above-mentioned methods, it is preferable that in the third step, the water and all hydrocarbons in entrance oxidative dehydrogenation unit (mass ratio of logistics c) is (0.5-30) to material:1, more preferably (5-20):1.Certain ratio is added in oxidative dehydrogenation Water can prevent the problem that the temperature rise that catalyst coking and catalyst bed are generated due to coking is too fast.

The reactor of oxidative dehydrogenation unit is fixed bed reactors in the present invention, a reactor can be used to carry out interval Operation can also will carry out circulate operation after two or more reactor series connection and/or parallel connection；The present invention is preferably by two or more Reactor parallel connection after operated, on the one hand facilitate catalyst regeneration, on the other hand production technology can be made continuous.

Separation method in separative element II of the present invention includes in extraction, rectifying, azeotropic distillation, UF membrane, chemical absorbing One or more of combinations, but not limited to this, it is recommended to use and the isolation technics of Technical comparing maturation, to obtain the fourth two of qualification Alkene product；Separator in separative element II can be the combination of diversified forms.

In the above-mentioned methods, it is preferable that in the 4th step, the mass content of alkadienes is not high in isolated logistics e In 0.3%；More preferably not above 0.1%, occurring for alkadienes can be to being subsequently etherified the conversion of isomeric olefine in unit, gasoline The content etc. of ether compound impacts in the yield and gasoline of component, and technical solution provided by the invention is in oxidative dehydrogenation Between two reaction members of etherificate, separative element II is added, the alkadienes in oxidative dehydrogenation product is detached, on the one hand The alkadienes that can obtain high value improves the economic benefit and market competitiveness of technique, on the other hand can prevent alkadienes Into in follow-up etherificate unit, etherification reaction is impacted.

It is etherified in unit in the present invention and is not particularly limited catalyst for etherification, it is desirable that enter all hydro carbons in etherificate unit The conversion ratio of Tertiary olefin is not less than 92% in material (being made of logistics e and logistics b)；All hydro carbons into etherificate unit Normal olefine hardly converts in material.

In the above-mentioned methods, it is preferable that in the 5th step, the alcohols refers to the low-carbon that carbon atom number is not more than four Alcohol；More preferably methanol and/or ethyl alcohol；Further preferably methanol.

In the above-mentioned methods, it is preferable that the alcohols and all hydrocarbon materials (logistics e and the object in entrance etherificate unit The molar ratio of Tertiary olefin in flowing b) is (0.8-1.5):1；More preferably (0.95-1.3):1.

In the above-mentioned methods, it is preferable that in the 5th step, the reaction condition of the etherificate unit includes：Temperature is 45-90 DEG C, pressure 0.4-3.0MPa, volume space velocity 0.1-5h^-1；It is highly preferred that temperature is 55-75 DEG C, pressure 0.5-2MPa, Volume space velocity is 1-2h^-1。

In the above-mentioned methods, it is preferable that in the 5th step, the reactor of the etherificate unit is fixed bed, moving bed, hangs One or several kinds of combinations in floating bed and catalytic distillation reactor；Preferably catalytic distillation reactor, so that Tertiary olefin Convert more abundant.The entrance that methyltertiarvbutyl ether reactor can be recycled in the alcohols of etherificate unit recycling recycles.

The separator of on-condensible gas can also be added in the separative element of the present invention, as flash tank, absorption/Analytic Tower, Cooling device and compression set etc..

In the present invention, the recommendation of olefin oxidation dehydrogenation is made by the following two kinds preparation method, wherein：

The first preparation method of olefin oxidation dehydrogenation includes the following steps：

Step 1: first, the presoma of metal A, B, C, D to be ground to the microspheroidal of 40-100 mesh respectively；Secondly, it will grind The presoma parts by weights of the metal A of milled is two parts, and the presoma of metal B, C and D are uniformly mixed；

Step 2: the iron nitrate solution of configuration 0.1-2mol/L, under agitation, by the presoma of first part of metal A It is added in iron nitrate solution, reacts 30-90 minutes, add the presoma of mixed metal B, C and D, 30-90 points of reaction The presoma of second part of metal A is added after clock, reaction is added after 20-80 minutes accounts for the viscous of metal precursor gross mass 0.5-6% Agent is tied, the slurry of presoma sediment is obtained；

Step 3: stirring slurry is gradually added into the ammonium hydroxide that volumetric concentration is 10-25% for 20-60 minutes into slurry, adjust The pH value of slurry is 7.5-10；

Step 4: carrying out heat modification in the environment of slurry is placed in 80-95 DEG C, modification time is 60-180 minutes；

Step 5: filter slurry makes the pH value of slurry reach 7-7.5 with washings filtering stock；

Step 6: filter slurry, molding obtains molding catalyst, and being preferably shaped to for the catalyst is cylindric or three Leaf grass-like；

Step 7: catalyst after molding is roasted modification by calcination 6-12 hours at 100-200 DEG C at 200-300 DEG C It burns and is modified 4-8 hours, modification by calcination 1-4 hours at 300-400 DEG C, modification by calcination 1-4 hours at 400-500 DEG C, obtain Finished catalyst.

Second of preparation method of olefin oxidation dehydrogenation includes the following steps：

Step 1: first, the presoma of metal A, B, C to be ground to the microspheroidal of 40-100 mesh respectively；Secondly, it will grind Two parts of the presoma parts by weights of good metal A；The presoma of metal B and C are uniformly mixed；

Step 2: the iron nitrate solution of configuration 0.1-2mol/L, under agitation, by the presoma of first part of metal A It is added in iron nitrate solution, reacts 30-90 minutes, add the presoma of mixed metal B and C, react 30-90 minutes The presoma of second part of metal A is added afterwards, reaction is added binder and activated carbon after 20-80 minutes, obtains presoma sediment Slurry；The additive amount of binder is the 0.5-6% of metal precursor gross mass, and the additive amount of activated carbon is that metal precursor is total The 0.5-4% of quality；

Step 3: stirring slurry is gradually added into the ammonium hydroxide that volumetric concentration is 10-25% for 20-60 minutes into slurry, adjust The pH value of slurry is 7.5-10；

Step 4: carrying out heat modification in the environment of slurry is placed in 80-95 DEG C, modification time is 60-180 minutes；

Step 5: filter slurry makes the pH value of slurry reach 7-7.5 with washings filtering stock；

Step 6: filter slurry, molding obtains catalyst after molding, the catalyst be preferably shaped to it is cylindric or Trilobes；

Step 7: catalyst after molding is roasted modification by calcination 6-12 hours at 100-200 DEG C at 200-300 DEG C It burns and is modified 4-8 hours, modification by calcination 1-4 hours at 300-400 DEG C, modification by calcination 1-4 hours at 400-500 DEG C；

Step 8: by being impregnated in the solution of the presoma of the catalyst input metal D after modification by calcination, metal D is tungsten, tungsten Source is WO₃, the precursor solution of metal D is the ammonium tungstate solution of a concentration of 0.01-0.6mol/L；Dipping temperature is 15-95 DEG C, Dip time is 1-24 hours, takes out catalyst drying 6-24 hours at 80-160 DEG C, it is small that 8-24 is activated at 400-550 DEG C When, obtain finished catalyst.

In being prepared at first and second kinds of above-mentioned olefin oxidation dehydrogenation, it is preferable that in step 1, will grind When the presoma parts by weights of good metal A is two parts, first part of weight percent is 55-80%, second part of weight hundred Divide than being 20-45%.

In being prepared at first and second kinds of above-mentioned olefin oxidation dehydrogenation, it is preferable that in step 2, the nitre A concentration of 0.4-1.2mol/L of sour ferrous solution.

In being prepared at first and second kinds of above-mentioned olefin oxidation dehydrogenation, it is preferable that the binder in step 2 Additive amount be metal precursor gross mass 2-4%.

In being prepared at first and second kinds of above-mentioned olefin oxidation dehydrogenation, it is preferable that in step 3, ammonium hydroxide Mass concentration is 15-20%, and the pH value for adjusting slurry is 8.0-9.0.

In being prepared at first and second kinds of above-mentioned olefin oxidation dehydrogenation, it is preferable that in step 4, when modified Between be 90-120 minutes.

In being prepared at first and second kinds of above-mentioned olefin oxidation dehydrogenation, it is preferable that before described metal A, B, C Drive the combination that body is respectively selected from one or more of their nitrate, chloride, sulfate and oxide.

In the first preparation of above-mentioned olefin oxidation dehydrogenation, it is preferable that in step 2,40-60 points of reaction Binder is added after clock；The binder is one kind or several in sesbania powder, polyacrylamide, methylcellulose and polyvinyl alcohol The combination of kind.

In second of preparation of above-mentioned olefin oxidation dehydrogenation, it is preferable that in step 2,40-60 points of reaction Binder and activated carbon are added after clock；The binder is in sesbania powder, polyacrylamide, methylcellulose and polyvinyl alcohol One or more of combinations.

In second of preparation of above-mentioned olefin oxidation dehydrogenation, it is preferable that in step 2, the activated carbon Addition is the 1.0-3.0% of metal precursor gross mass.

In being prepared at first and second kinds of above-mentioned olefin oxidation dehydrogenation, it is preferable that described to wash in step 5 Wash the combination that water is one or more of deionized water, distilled water, desalted water, tap water.

The preferably more specific embodiment of the present invention is：

The first step, the raw material that will be enriched in C4-C6 alkane and hydrogen are sent into catalytic dehydrogenation unit, are 480-700 in temperature DEG C, pressure 0.01-3MPa, volume space velocity 0.1-10h^-1Under conditions of carry out catalytic dehydrogenating reaction, obtain rich in alkene Logistics a；Wherein,

(raw material for being as rich in C4-C6 alkane) of the hydrogen and all hydrocarbon materials entered in catalytic dehydrogenation unit Molar ratio be (0.1-1):1；

The boiling range of the raw material 95% rich in C4-C6 alkane is at 75 DEG C or less；

Second step, the logistics a for obtaining the first step are sent into separative element I, the hydrocarbon material flow b of isolated C6 or more with C5 hydrocarbon material flow c below；

Logistics c, the logistics containing oxidant and water vapour are sent into oxidative dehydrogenation unit by third step, are 280 in temperature DEG C -410 DEG C, pressure 0-100KPa, volume space velocity 10-500h^-1Under conditions of carry out oxidative dehydrogenation, obtain containing two The logistics d of alkene；Wherein,

Oxidant in logistics containing oxidant is with oxymeter, the oxygen and owning in entrance oxidative dehydrogenation unit (molar ratio for being the alkene in logistics c) is (0.1-1.0) to hydrocarbon material:1；The logistics containing oxidant contains for oxygen Amount is the oxygen-enriched stream of 32-45%；The water vapour and the mass ratio of all hydrocarbon materials entered in oxidative dehydrogenation unit are (0.5-30):1；

Logistics d is sent into separative element II by the 4th step, and logistics e is obtained after alkadienes is detached；

Logistics e, logistics b and alcohols are sent into etherificate unit by the 5th step, are 45-90 DEG C in temperature, pressure 0.4- 3.0MPa, volume space velocity 0.1-5h^-1Under conditions of carry out etherification reaction, obtain gasoline component；Wherein,

(Tertiary olefin in logistics e and logistics b) rubs the alcohols with all hydrocarbon materials for being etherified in unit are entered You are than being (0.8-1.5):1.

Beneficial effects of the present invention：

Technical solution provided by the invention will be enriched in C4-C6 alkane by combining catalytic dehydrogenation, oxidative dehydrogenation, etherificate Raw material be converted into gasoline component, while preparing the butadiene of a certain amount of high value, keep the plug oils containing C4-C5 alkane former The conversion process of material more refines；

At the same time, technical solution provided by the invention carries out the technique of catalytic dehydrogenation, oxidative dehydrogenation, etherificate respectively It improves, improves the utilization rate and economic benefit of the plug oils raw material containing C4-C5 alkane.

Description of the drawings

Fig. 1 is the process flow diagram of the embodiment of the present invention；

Main Reference label declaration：

R1：：Catalytic dehydrogenating reaction device；R2：Oxidative dehydrogenation reactor；R3：Methyltertiarvbutyl ether reactor；

T1：Separative element I；T2：Separative element II.

Specific implementation mode

In order to which technical characteristic, purpose and the advantageous effect to the present invention are more clearly understood, now to the skill of the present invention Art scheme carry out it is described further below, but should not be understood as to the present invention can practical range restriction.

For raw material used in following embodiment as shown in table 1-2, raw material A is that circulating water plant of Dushanzi Refinery is hydrocracked lighter hydrocarbons, raw material B For circulating water plant of Dushanzi Refinery pentane oil；Methanol uses the methanol of commercially available Cangzhou Zheng Yuan Chemical Co., Ltd.s production, the wherein matter of methanol It is 99.5% to measure content；Ethyl alcohol uses the absolute ethyl alcohol of commercially available Yixing City Qiu Yun Chemical Co., Ltd.s production, the wherein matter of ethyl alcohol It is 99.5% to measure content.

1 raw material A of table forms (W%)

2 raw material B compositions (W%) of table

The technological process of following embodiment as shown in Figure 1 is operated, wherein：

Catalytic dehydrogenating reaction device and methyltertiarvbutyl ether reactor are to use single fixed bed reactor in embodiment 1-3 (200mL) carries out intermittently operated；Oxidative dehydrogenation unit uses the fixed bed reactors of 100mL；Catalytic dehydrogenation is anti-in embodiment 4-6 It is that two fixed bed reactors (each reactor is 200mL) is used to carry out circulate operation to answer device and methyltertiarvbutyl ether reactor, Oxidative dehydrogenation unit uses the fixed bed reactors of 100mL.

It is the instantaneous sample after reacting 2.5 hours that sample is analyzed in following embodiment.

Used in separative element I (T1) in following embodiment theoretical cam curve for 18 rectifying column；Separative element II (T2) After the middle dehydration using cyclone separator, flash distillation removes on-condensible gas, and extraction isolates alkadienes.

It is prepared in raw material used by catalyst in following embodiment, sesbania powder is technical grade, and other is commercially available chemistry Pure reagent；Water is deionized-distilled water；Oxygen-enriched stream is by technical grade pure oxygen and air mixed configuration.

In following embodiment, the calculating of the content of alkene, the yield of alkadienes, the yield of aromatization products, arene content Method is as follows：

Own in quality/catalytic dehydrogenation product of generated butylene, amylene in the content of alkene=catalytic dehydrogenation product Quality × 100 of hydro carbons；

The gross mass of alcohols caused by the mass yield of alcohols=oxidative dehydrogenation unit/enter oxidative dehydrogenation unit In all hydrocarbon materials quality × 100；

The gross mass of ketone caused by the mass yield of ketone=oxidative dehydrogenation unit/enter oxidative dehydrogenation unit In all hydrocarbon materials quality × 100；

The quality of alkadienes caused by the mass yield of alkadienes=oxidative dehydrogenation unit/enter in oxidative dehydrogenation unit Quality × 100 of all hydrocarbon materials；

Quality after all product removal on-condensible gases of yield=etherificate of etherification product/enter institute in etherification reaction unit There are quality × 100 of hydrocarbon material；

The quality of quality/generated etherification product of the content of ether compound=generated all ether materials × 100。

Embodiment 1

Present embodiments provide a kind of method of conversion plug oils lighter hydrocarbons comprising following steps：

1) catalytic dehydrogenation catalyst uses the HTPB-DH dehydrogenations of Liaoning Haitai development in science and technology Co., Ltd production, The catalyst is with Al₂O₃For carrier, using Pt and Cl as active component, wherein the mass content of Pt is that the mass content of 1%, Cl is 2%, specific surface area 200m²/ g, Kong Rongwei 0.5ml/g, a diameter of 1.59mm, heap density is 0.6g/cm³。

2) preparation of olefin oxidation dehydrogenation

1. by the presoma six of oxidation of precursor potassium 1g, C of presoma cabaltous nitrate hexahydrate 582g, B of metal A used Calcium chloride hydrate 11g is ground to the microspheroidal of 80 mesh；Secondly, metal precursor cabaltous nitrate hexahydrate is pressed to 65% and 35% ratio Example is divided into two parts of 378.3g and 203.7g；Potassium oxide, six calcium chloride hydrates are uniformly mixed；

2. configure the iron nitrate solution of 10L 0.4mol/L, under agitation, by the cabaltous nitrate hexahydrate of 378.3g by It is gradually added in iron nitrate solution, reacts 50 minutes, be slow added into the mixture of potassium oxide and six calcium chloride hydrates, reaction 30 The cabaltous nitrate hexahydrate of 203.7g is added after minute, activated carbon 51.4g, sesbania powder 6.3g is added after 50 minutes in reaction；

3. stirring the ammonium hydroxide for being added dropwise that volumn concentration is 13% in 30 minutes backward slurries, the pH value for adjusting slurry is 8.5；

4. slurry is placed under 90 DEG C of constant temperature and carries out heat modification 100 minutes to slurry；

5. filter slurry is simultaneously washed with distilled water slurry, slurry pH value is made to reach 7.0；

6. filter slurry, extruded moulding is 3mm long, trilobes thick 1mm；

7. modification by calcination 10 hours at 100 DEG C of the catalyst after extrusion, modification by calcination 8 hours at 210 DEG C, 330 Modification by calcination 4 hours at DEG C, modification by calcination 3 hours at 460 DEG C；

8. the catalyst after roasting impregnates 16 hours in the ammonium tungstate solution of 3L, 0.15mol/L, dipping temperature 95 DEG C, catalyst drying 6 hours at 160 DEG C are taken out, are activated 8 hours at 500 DEG C, obtaining main group becomes Co₂K_0.01Ca_0.05W_0.04·Fe₄O_8.2Finished catalyst.

3) the novel ether catalysts that catalyst for etherification is produced for southern big synthesis Chemical Co., Ltd., granularity are 16-50 mesh, bulk density 0.55-0.65g/ml, specific surface area are more than 20m²/ g, aperture be more than 10nm, large pore volume in 0.2cc/g。

4) implementing process

1. in catalytic dehydrogenating reaction device (R1), the molar ratio of hydrogen and raw material A is 0.5:1, it is 570 in reaction temperature DEG C, volume space velocity 3.0h^-1, reaction pressure is carries out catalytic dehydrogenating reaction under conditions of 1.7MPa, obtained catalytic dehydrogenation production The content of alkene is 58.6% in object；

2. catalytic dehydrogenation product is separated into the hydrocarbon material flow and light dydrocarbon of six or more carbon after separative element I (T1) separation Hydrocarbon material flow below；

3. light dydrocarbon hydrocarbon material flow below, air and water vapour enter after preheating in oxidative dehydrogenation reactor (R2) (the alkene in light dydrocarbon hydrocarbon material flow below:Oxygen=1:0.85 (molar ratio), light dydrocarbon hydrocarbon material flow below:Water=1:5 (mass ratio)), at 380 DEG C, 50KPa, volume space velocity 60h^-1Under conditions of carry out oxidative dehydrogenation, obtained oxidative dehydrogenation Product；

4. oxidative dehydrogenation product enters in separative element II (T2), alkadienes (mass yield 28.9%), alcohol are isolated Class (mass yield 0.83%), ketone (mass yield 0.48%)；

5. the hydrocarbon of the oxidative dehydrogenation product and six or more carbon isolated in separative element I after step 4. separating treatment Enter in methyltertiarvbutyl ether reactor (R3) after class logistics mixing, in methanol with all hydrocarbon materials into methyltertiarvbutyl ether reactor (by through step Suddenly 4. the hydrocarbon material flow of the oxidative dehydrogenation product after separating treatment and six or more carbon isolated in separative element I is constituted) in Tertiary olefin molar ratio be 1.2:1, reaction temperature is 45 DEG C, volume space velocity 2h^-1, reaction pressure is the condition of 1.5MPa Under reacted, obtain etherification product；After reaction product is removed on-condensible gas, obtaining gasoline component, (mass yield is 98.6%), wherein the content of ether compound is 36.4%.

Embodiment 2

Present embodiments provide a kind of method of conversion plug oils lighter hydrocarbons comprising following steps：

1) catalytic dehydrogenation catalyst is prepared using the method for embodiment 4 in CN101940922A, and specific steps include：

The chromium oxide for weighing 117.5 grams, is dissolved in deionized water and being sufficiently stirred, and it is 47% chromium oxide to be configured to weight concentration Solution.It is reconfigured the potassium nitrate aqueous solution that weight concentration is 3.86%；By 55.0 grams of boehmites, 2.2 grams of bentonites, with 7.59 grams of prepared oxidation chromium solutions are sufficiently mixed, 3 hours dry at 120 DEG C after mediating, being extruded into bead, then 500 DEG C constant temperature 3 hours, then in 620 DEG C of constant temperature 2 hours, finally under 20% water and 80% air 760 DEG C roast 4 hours, roasted Burned sample；Prepared 11.39 grams of oxidation chromium solution is taken again, roasting sample is impregnated 20 minutes, in 120 DEG C of dryings 3 hours, in 550 DEG C of constant temperature calcinings 5 hours；Prepared potassium nitrate aqueous solution is taken to impregnate again, it is 3 hours dry at 120 DEG C, 620 DEG C of constant temperature calcinings 6 hours are spare.

2) preparation of olefin oxidation dehydrogenation

The catalyst is prepared according to the preparation method of the olefin oxidation dehydrogenation in embodiment 1, configuration The iron nitrate solution of 40L0.1mol/L, metal precursor are ground to the microspheroidal of 100 mesh, and the presoma of metal A is divided into 70% He 30% two part, the reaction time that two minor tick of metal precursor is added is respectively 80 minutes and 70 minutes, each metal precursor Dosage is：The forerunner that the presoma of metal A is cabaltous nitrate hexahydrate 582g, the presoma of metal B is potassium oxide 9.4g, metal C Body is six calcium chloride hydrate 2.2g；Activated carbon 88.4g, sesbania powder 132g is added in reaction after twenty minutes；Stirring is after twenty minutes to slurry The ammonium hydroxide that volumn concentration is 10% is added dropwise in material, the pH value for adjusting slurry is 7.5, and is carried out to slurry under 80 DEG C of constant temperature Heat modification 180 minutes；Filter slurry and with desalted water and tap water filtering stock, makes slurry pH value reach 7.5；Filter slurry is simultaneously It is extruded into 3mm long, cylindrical type thick 1mm, modification by calcination 9 hours at 150 DEG C, then modification by calcination 5 hours at 200 DEG C, then Modification by calcination 2 hours at 450 DEG C, finally modification by calcination 1 hour at 500 DEG C；Catalyst after roasting is in 2L, 0.6mol/L Ammonium tungstate solution in impregnate 1 hour, dipping temperature be 60 DEG C, take out catalyst activated 24 hours at 80 DEG C, at 400 DEG C Activation 24 hours, obtaining mainly organizing becomes Co₂K_0.1Ca_0.01W_0.2·Fe₄O_8.66Finished catalyst.

3) catalyst for etherification uses the D005-II resin catalysts that Dandong Mingzhu Special Type Resin Co., Ltd. produces；Its grain Degree is 0.315-1.25mm, wet true density 1180-1200g/L, total exchange capacity >=5.2mmol/g [H⁺], mechanical strength >= 95% (H-type).

4) implementing process

Using raw material B；

1. in catalytic dehydrogenating reaction device (R1), the molar ratio of hydrogen and raw material B are 0.3:1, reaction temperature is 600 DEG C, Volume space velocity is 5.0h^-1, reaction pressure 1.1MPa, the content of alkene is 66.3% in catalytic dehydrogenation product obtained by the reaction；

2. catalytic dehydrogenation product passes through separative element I (T1), it is separated into light dydrocarbon hydrocarbon material flow below and six or more carbon Hydrocarbon material flow；

3. light dydrocarbon hydrocarbon material flow below, oxygenous 35% oxygen-enriched stream, water are mixed into oxidative dehydrogenation reactor (R2) (the alkene in light dydrocarbon hydrocarbon material flow below in:Oxygen=1:1 (molar ratio), light dydrocarbon hydrocarbon material flow below:Water=1: 16 (mass ratioes)), at 390 DEG C, atmospheric pressure, volume space velocity 500h^-1Under conditions of carry out olefin oxidation dehydrogenation reaction, obtain oxygen Fluidized dehydrogenation product；

4. oxidative dehydrogenation product enters in separative element II (T2), alkadienes (mass yield 42.1%), alcohol are isolated Class (mass yield 0.61%), ketone (mass yield 0.40%)；

5. the hydrocarbon of the oxidative dehydrogenation product and six or more carbon isolated in separative element I after step 4. separating treatment Class logistics is mixed into methyltertiarvbutyl ether reactor (R3), in methanol with all hydrocarbon materials into methyltertiarvbutyl ether reactor (by through step 4. the oxidative dehydrogenation product and the hydrocarbon material flow of six or more carbon isolated in separative element I after separating treatment are constituted) in The molar ratio of Tertiary olefin is 1.1:1, reaction temperature is 80 DEG C, volume space velocity 3.0h^-1, reaction pressure is the condition of 1.0MPa Under reacted, obtain etherification product；After reaction product is removed on-condensible gas, obtaining gasoline component, (mass yield is 80.5%), wherein the content of ether compound is 39.6%.

Embodiment 3

Present embodiments provide a kind of method of conversion plug oils lighter hydrocarbons comprising following steps：

1) catalytic dehydrogenation catalyst is prepared using the method for embodiment 1 in patent CN101618319, specific steps packet It includes：

2.24 grams of calcium oxide and 3.1 grams of polyethylene glycol are dissolved in 120mL deionized waters, 240 DEG C of hydro-thermal process 24 hours, After 600 DEG C of calcinations 5 hours, it is uniformly mixed with appropriate absolute ethyl alcohol with 7.2 grams of Chromium nitrate (Cr(NO3)3),nonahydrates, 6 grams of alundum (Al2O3)s, Ground after dry 12 hours it is uniform, it is spare after calcination 3 hours at 550 DEG C.

2) preparation of olefin oxidation dehydrogenation

The catalyst is prepared according to the preparation method of the olefin oxidation dehydrogenation in embodiment 1, configuration The iron nitrate solution of 10L1.0mol/L, metal precursor are ground to the microspheroidal of 80 mesh, and the presoma of metal A is divided into 60% He 40% two part, the reaction time that two minor tick of metal precursor is added is respectively 60 minutes and 60 minutes, each metal precursor Dosage is：The presoma of metal A is Chromium nitrate (Cr(NO3)3),nonahydrate 2400g, the presoma of metal B is vanadic anhydride 5.5g, metal C Presoma is barium chloride 52g；Activated carbon 19.6g, methylcellulose 208g is added after 30 minutes in reaction；Stirring is after forty minutes to slurry The ammonium hydroxide that volumn concentration is 15% is added dropwise in material, the pH value for adjusting slurry is 8.5, and is carried out to slurry under 90 DEG C of constant temperature Heat modification 100 minutes；Simultaneously slurry is washed with deionized in filter slurry, and slurry pH value is made to reach 7.5；Filter slurry simultaneously squeezes 3mm It grows, the thick trifolium-shapeds of 1mm, modification by calcination 8 hours at 200 DEG C, then modification by calcination 4 hours at 300 DEG C, then at 360 DEG C Lower modification by calcination 3 hours, finally modification by calcination 2 hours at 450 DEG C；The wolframic acid of catalyst after roasting in 3L, 0.2mol/L It is impregnated 24 hours in ammonium salt solution, dipping temperature is 15 DEG C, takes out catalyst drying 12 hours at 120 DEG C, is activated at 450 DEG C 12 hours, obtaining mainly organizing became Cr₆V_0.06Ba_0.25W_0.1·Fe₁₀O_21.5Finished catalyst.

3) catalyst for etherification is the D005-II type resin catalysts of Dandong Mingzhu Special Type Resin Co., Ltd.'s production, grain Degree is 0.315-1.25mm, wet true density 1180-1200g/L, total exchange capacity >=5.2mmol/g [H⁺], mechanical strength >= 95% (H-type).

4) implementing process

Using raw material A；

1. in catalytic dehydrogenating reaction device, the molar ratio of hydrogen and raw material A is 0.15:1, reaction temperature is 650 DEG C, volume Air speed is 8.0h^-1, reaction pressure 2.4MPa, the content of alkene is 41.5% in catalytic dehydrogenation product obtained by the reaction；

2. catalytic dehydrogenation product passes through separative element I, it is separated into the hydro carbons of light dydrocarbon hydrocarbon material flow below and six or more carbon Logistics；

3. light dydrocarbon hydrocarbon material flow below, oxygenous 40% oxygen-enriched stream, water are mixed into oxidative dehydrogenation reactor (the alkene in light dydrocarbon hydrocarbon material flow below:Oxygen=1:0.55 (molar ratio), light dydrocarbon hydrocarbon material flow below:Water=1:30 (mass ratio)), at 280 DEG C, 10Kpa, volume space velocity 300h^-1Under conditions of carry out olefin oxidation dehydrogenation reaction, obtained oxygen Fluidized dehydrogenation product；

4. oxidative dehydrogenation product enters in separative element II, alkadienes (mass content 28.1%), alcohols (matter are isolated Measure yield be 0.68%), ketone (mass yield 0.35%)；

5. the hydrocarbon of the oxidative dehydrogenation product and six or more carbon isolated in separative element I after step 4. separating treatment Class logistics is mixed into methyltertiarvbutyl ether reactor, in methanol with all hydrocarbon materials into methyltertiarvbutyl ether reactor (by 4. dividing through step Hydrocarbon material flow from treated oxidative dehydrogenation product and six or more carbon isolated in separative element I is constituted) in tertiary carbon The molar ratio of alkene is 1.3:1, reaction temperature is 65 DEG C, volume space velocity 4h^-1, reaction pressure be 0.4MP under conditions of carry out Reaction, obtains etherification product；After reaction product is removed on-condensible gas, gasoline component (mass yield 77.6%) is obtained, Wherein the content of ether compound is 40.7%.

Embodiment 4

Present embodiments provide a kind of method of conversion plug oils lighter hydrocarbons comprising following steps：

1) dehydrogenation is prepared using the method for embodiment 4 in CN101940922A, and specific steps include：

The chromium oxide for first weighing 117.5 grams, is dissolved in deionized water and being sufficiently stirred, and it is 47% oxidation to be configured to weight concentration Chromium solution；It is reconfigured the potassium nitrate aqueous solution that weight concentration is 3.86%；Then by 55.0 grams of boehmites, 2.2 grams of swellings Soil is sufficiently mixed with 7.59 grams of prepared oxidation chromium solutions, mediates, is extruded into bead；Then 3 hours dry at 120 DEG C, so Afterwards in 500 DEG C of constant temperature 3 hours, in 620 DEG C of constant temperature 2 hours, finally under 20% water and 80% air 760 DEG C roast 4 hours.Again Prepared 11.39 grams of oxidation chromium solution is taken, roasting sample is impregnated 20 minutes, it is 3 hours dry at 120 DEG C, at 550 DEG C Constant temperature calcining 5 hours；Prepared potassium nitrate aqueous solution is taken to impregnate again, it is 3 hours dry at 120 DEG C, in 620 DEG C of constant temperature calcinings 6 Hour is spare.

2) preparation of olefin oxidation dehydrogenation

1. by the precursor ZnO 25g, metal C of presoma the cabaltous nitrate hexahydrate 1455g, metal B of metal A used The presoma tungstic acid 12g of presoma Magnesium dichloride hexahydrate 40g, metal D be ground to the microspheroidals of 60 mesh；It secondly, will be golden The presoma cabaltous nitrate hexahydrate for belonging to A is divided into two parts of 1164g and 291g in 80% and 20% ratio, by zinc oxide, six hydrations Magnesium chloride and nickel nitrate are uniformly mixed；

2. the iron nitrate solution of 20L 0.65mol/L is configured, it is under agitation, first that 873g cabaltous nitrate hexahydrates is gradual It is added in iron nitrate solution, reacts 70 minutes, be slow added into the mixing of zinc oxide, Magnesium dichloride hexahydrate and tungstic acid Object, reaction are slow added into the cabaltous nitrate hexahydrate of 582g after 80 minutes, sesbania powder 91.92g is added in reaction after sixty minutes；

3. stirring slurry is gradually added into the ammonium hydroxide that volumetric concentration is 20% for 60 minutes into slurry, the pH value for adjusting slurry is 9.0；

4. carrying out heat modification in the environment of slurry is placed in 85 DEG C, modification time is 90 minutes；

5. filter slurry makes the pH value of slurry reach 7.0 with tap water filtering stock；

6. filter slurry, extruded moulding is 3mm long, cylindrical type thick 1mm；

7. modification by calcination 11 hours at 160 DEG C of the catalyst after extrusion, then modification by calcination 7 hours at 240 DEG C, then Modification by calcination 3 hours at 310 DEG C, finally modification by calcination 4 hours at 440 DEG C；Obtaining main group becomes： Co₅W_0.05Mg_0.2Zn_0.3·Fe₁₃O₂₅Finished catalyst.

3) catalyst for etherification is urged using the macropore strong acid resin that Jiangsu AudioCodes petrochemistry Technology Co., Ltd. is produced Agent, granularity 0.315-1.25mm, bulk density 0.77-0.85g/mL, specific surface area are more than 20-70m²/ g, aperture More than 20-50nm, large pore volume is in 0.3-0.5cc/g.

4) implementing process

Using raw material B；

1. in catalytic dehydrogenating reaction device, the molar ratio of hydrogen and raw material B are 0.01:1, it is 550 DEG C in reaction temperature, body Product air speed is 10.0h^-1, reaction pressure is is reacted under conditions of 3.0MPa, alkene in catalytic dehydrogenation product obtained by the reaction Content be 50.1%；

2. catalytic dehydrogenation product passes through separative element I, it is separated into the hydro carbons of light dydrocarbon hydrocarbon material flow below and six or more carbon Logistics；

3. light dydrocarbon hydrocarbon material flow below, oxygenous 32% oxygen-enriched stream, water are through being mixed into oxidative dehydrogenation reactor In (the alkene in light dydrocarbon hydrocarbon material flow below:Oxygen=1:0.1 (molar ratio), light dydrocarbon hydrocarbon material flow below:Water=1: 0.5 (mass ratio)), at 340 DEG C, atmospheric pressure, volume space velocity 250h^-1Under conditions of carry out oxidative dehydrogenation, obtained oxygen Fluidized dehydrogenation product；

4. oxidative dehydrogenation product enters in separative element II, alkadienes (mass content 36.7%), alcohols (matter are isolated Measure yield be 0.69%), ketone (mass yield 0.33%)；

5. oxidative dehydrogenation product of the oxygen after step 4. separating treatment and six or more carbon isolated in separative element I Enter in methyltertiarvbutyl ether reactor after hydrocarbon material flow mixing, in methanol with all hydrocarbon materials into methyltertiarvbutyl ether reactor (by through step 4. the oxidative dehydrogenation product and the hydrocarbon material flow of six or more carbon isolated in separative element I after separating treatment are constituted) in The molar ratio of Tertiary olefin is 1.5:1,75 DEG C of reaction temperature, volume space velocity 5h^-1, reaction pressure be 3MPa under conditions of carry out Reaction, obtains etherification product；After reaction product is removed on-condensible gas, gasoline component (mass yield 83.5%) is obtained, Wherein the content of ether compound is 36.7%.

Embodiment 5

Present embodiments provide a kind of method of conversion plug oils lighter hydrocarbons comprising following steps：

1) catalytic dehydrogenation catalyst is prepared using the method for embodiment 9 in patent CN96121452.X, specific steps packet It includes：

Weigh 17 grams of Cr (NO₃)₃·9H₂O, 1.1 grams of Cu (NO₃)₂·3H₂O, 80.8 grams of Al (NO₃)₃·9H₂O, with co-precipitation Method prepares catalyst, and it is 10% KOH (or NaOH) solution that precipitating reagent, which selects mass concentration, and nitrate is dissolved in distilled water, Precipitating reagent is added while stirring, so that it is formed gel completely, and pH value is 8.5-9, aging 3 hours is filtered, and at 110 DEG C, is done It dry 20 hours, is roasted at 650 DEG C 7 hours, it is rear spare after crushing and screening.

2) preparation of olefin oxidation dehydrogenation

The catalyst is prepared according to the preparation method of the olefin oxidation dehydrogenation in embodiment 4, configuration The iron nitrate solution of 10L2.0mol/L, metal precursor are ground to the microspheroidal of 100 mesh, and the presoma of metal A is divided into 55% He 45% two part, the reaction time that two minor tick of metal precursor is added is respectively 30 minutes and 90 minutes, each metal precursor Dosage is：The presoma that the presoma of metal A is Salzburg vitriol 498g, the presoma of metal B is potassium oxide 47g, metal C For the presoma tungstic acid 23.2g of six calcium chloride hydrate 2.2g, metal D；Sesbania powder 17.7g is added after 80 minutes in reaction.It stirs The ammonium hydroxide for being added dropwise that volumn concentration is 25% in 25 minutes backward slurries is mixed, the pH value for adjusting slurry is 10, and in 95 DEG C of perseverances Heat modification is carried out 60 minutes to slurry under temperature；It is washed with distilled water slurry, slurry pH value is made to reach 7.5.Filter slurry is simultaneously extruded into The thick cylindrical type of 3mm long, 1mm, modification by calcination 12 hours at 180 DEG C；Modification by calcination 6 hours at 260 DEG C, roast at 300 DEG C It is 4 hours modified, modification by calcination 2.5 hours at 400 DEG C；Obtaining main group becomes：Cu₂W_0.1Ca_0.01K_0.5·Fe₂₀O_32.6Urge Agent finished product.

3) preparation process of olefin oxidation dehydrogenation is with reference to embodiment 1, but is not added in catalyst preparation process Tungsten.

4) catalyst for etherification uses the etherified resin catalyst of Kai Rui Chemical Co., Ltd.s production, granularity 0.335- 1.25mm, wet true density 0.75-0.85g/mL, total exchange capacity >=5.2mmol/g, mechanical strength >=95%.

5) implementing process

Using raw material A；

1. in catalytic dehydrogenating reaction device, the molar ratio of hydrogen and raw material A is 0.25:1, reaction temperature is 480 DEG C, volume Air speed is 0.1h^-1, reaction pressure 0.01MPa, the content of alkene is 40.3% in catalytic dehydrogenation product obtained by the reaction；

2. catalytic dehydrogenation product passes through separative element I, it is separated into the hydro carbons of light dydrocarbon hydrocarbon material flow below and six or more carbon Logistics；

3. light dydrocarbon hydrocarbon material flow below, pure oxygen gas and water enter by preheating in oxidative dehydrogenation reactor, (light dydrocarbon is below Alkene in hydrocarbon material flow:Oxygen=1:0.68 (molar ratio), light dydrocarbon hydrocarbon material flow below:Water=1:30 (mass ratioes)), 300 DEG C, 75KPa, volume space velocity 10h^-1Under conditions of carry out oxidative dehydrogenation, obtained oxidative dehydrogenation product；

4. oxidative dehydrogenation product enters in separative element II, alkadienes (mass yield 17.5%), alcohols (matter are isolated It is 1.23%) ketone (mass yield 0.91%) to measure yield；

5. the hydro carbons of the oxidative dehydrogenation product and six or more isolated separative element I carbon after step 4. separating treatment Logistics is mixed into methyltertiarvbutyl ether reactor, in ethyl alcohol with all hydrocarbon materials into methyltertiarvbutyl ether reactor (by 4. being detached through step The hydrocarbon material flow of treated oxidative dehydrogenation product and six or more carbon isolated in separative element I is constituted) in tertiary carbon alkene The molar ratio of hydrocarbon is 0.8:1, reaction temperature is 55 DEG C, volume space velocity 0.1h^-1, reaction pressure be 2.0MPa under conditions of carry out Reaction, obtains etherification product；After reaction product is removed on-condensible gas, gasoline component (mass yield 96.8%) is obtained, Wherein the content of ether compound is 43.6%.

Embodiment 6

Present embodiments provide a kind of method of conversion plug oils lighter hydrocarbons comprising following steps：

1) catalytic dehydrogenation catalyst is used in patent CN 101623633A and is prepared the step of catalyst preparation in embodiment 1, Its specific steps includes：

ZSM-5 molecular sieve original powder is placed in the SnCl of 0.16M₂·2H₂10h is impregnated in 80 DEG C so that catalyst in O solution In the load capacity of Sn reach 4wt%, the then dry 6h at 120 DEG C；Sample after drying roasts under 550 DEG C of air atmospheres 4h；The H of powder after roasting in 0.03M₂PtCl₆·6H₂Impregnating 4h at 80 DEG C in O solution (makes final Pt in the catalyst Content is 20wt%), 6h is then dried at 120 DEG C, then 4h is roasted at 550 DEG C, it is finally standby in 550 DEG C of hydrogen reducing 12h With.

2) preparation of olefin oxidation dehydrogenation

The catalyst is prepared according to the preparation method of the olefin oxidation dehydrogenation in embodiment 4, configuration The iron nitrate solution of 60L0.1mol/L, metal precursor are ground to the microspheroidal of 40 mesh, and the presoma of metal A is divided into 65% He 35% two part, the reaction time that two minor tick of metal precursor is added is respectively 90 minutes and 30 minutes, each metal precursor Dosage is：The presoma of metal A is Chromium nitrate (Cr(NO3)3),nonahydrate 4000g, the presoma of metal B is vanadic anhydride 0.9g, metal C Presoma is Strontium dichloride hexahydrate 133g, the presoma of metal D is tungstic acid 2.32g；Sesbania powder is added in reaction after twenty minutes 66.2g；The ammonium hydroxide for being added dropwise that volumn concentration is 10% in 30 minutes backward slurries is stirred, the pH value for adjusting slurry is 7.5, and Heat modification is carried out 180 minutes to slurry under 80 DEG C of constant temperature；With desalted water filtering stock, slurry pH value is made to reach 7.0.Cross filter pulp Expect and squeeze 3mm long, the thick trifolium-shapeds of 1mm, modification by calcination 6 hours at 190 DEG C.Modification by calcination 4 hours at 230 DEG C, at 380 DEG C Lower modification by calcination 2 hours, modification by calcination 3.5 hours at 420 DEG C；Obtaining main group becomes：Cr₁₀W_0.01Sr_0.5V_0.01· Fe₆O_19.6Finished catalyst.

3) it is spherical (straight that catalyst for etherification, which uses the RZE-3 zeolite catalyst for etherification of petrochemical industry academy of sciences research and development, shape, Diameter is 8mm), bulk density 0.71g/cm³, specific surface area 487m²/ g, Kong Rongwei 0.464mL/g, average pore size are 175nm, intensity>20N.

4) implementing process

Using raw material B；

1. in catalytic dehydrogenating reaction device, the molar ratio of hydrogen and raw material B are 0.1:1, reaction temperature is 700 DEG C, volume Air speed is 1.0h^-1, reaction pressure 0.15MPa, the content of alkene is 59.6% in catalytic dehydrogenation product obtained by the reaction；

2. catalytic dehydrogenation product passes through separative element I, it is separated into the hydro carbons of light dydrocarbon hydrocarbon material flow below and six or more carbon Logistics；

3. it is anti-that light dydrocarbon hydrocarbon material flow below, oxygenous 45% oxygen-enriched stream, water enter oxidative dehydrogenation after preheating (the alkene in light dydrocarbon hydrocarbon material flow below is answered in device:Oxygen=1:0.3 (molar ratio), light dydrocarbon hydrocarbon material flow below:Water= 20 (mass ratioes)), at 350 DEG C, pressure 100KPa, volume space velocity 350h^-1Under conditions of carry out olefin oxidation dehydrogenation reaction, Obtain oxidative dehydrogenation product；

4. oxidative dehydrogenation product enters in separative element II, alkadienes (mass yield 38.0%), alcohols (matter are isolated Measure yield be 0.88%), ketone (mass yield 0.53%)；

5. the hydro carbons of the oxidative dehydrogenation product and six or more isolated separative element I carbon after step 4. separating treatment Logistics is mixed into methyltertiarvbutyl ether reactor, in methanol with all hydrocarbon materials into methyltertiarvbutyl ether reactor (by 4. being detached through step The hydrocarbon material flow of treated oxidative dehydrogenation product and six or more carbon isolated in separative element I is constituted) in tertiary carbon alkene The molar ratio of hydrocarbon is 0.95:1, reaction temperature is 90 DEG C, volume space velocity 1.4h^-1, reaction pressure be 3.0MPa under conditions of into Row reaction, obtains etherification product；After reaction product is isolated on-condensible gas, obtaining gasoline component, (mass yield is 82.5%), wherein the content of ether compound is 44.2%.

Embodiment 7

Present embodiments provide a kind of method of conversion plug oils lighter hydrocarbons, the operating procedure sky embodiment 1 of this method In it is consistent.

The preparation process of olefin oxidation dehydrogenation is with consistent in embodiment 1 in the present embodiment, but in preparation process Metal precursor is not ground, the presoma cabaltous nitrate hexahydrate of metal A is not drawn to be divided to two parts, potassium oxide, six water Calcium chloride is closed not to be pre-mixed.The presoma of each metal is added sequentially in configured iron nitrate solution.

Using the specific steps in process example 1, the content by alkene in the present embodiment catalytic dehydrogenating reaction product is 56.3%；The content of alkadienes is 20.4% in oxidative dehydrogenation product, and the mass yield of alcohols is 0.55%, and the quality of ketone is received Rate is 0.38%；It is etherified after unit abjection on-condensible gas, obtains gasoline component component (mass yield 114.5%), wherein The content of ether compound is 53.5%.

Comparative example 1

This comparative example provides a kind of conventional method of conversion plug oils lighter hydrocarbons comprising following steps：

1) catalytic dehydrogenation catalyst is prepared using the method for embodiment 4 in CN101940922A, and specific steps include：

The chromium oxide for first weighing 117.5 grams, is dissolved in deionized water and being sufficiently stirred, and it is 47% oxidation to be configured to weight concentration Chromium solution.The potassium nitrate aqueous solution for being 3.86% in configuration weight concentration；Then by 55.0 grams of boehmites, 2.2 grams of swellings Soil is sufficiently mixed with 7.59 grams of prepared oxidation chromium solutions, mediates, is extruded into bead；Then 3 hours dry at 120 DEG C again, so 500 DEG C of constant temperature 3 hours again afterwards, in 620 DEG C of constant temperature 2 hours, finally under 20% water and 80% air 760 DEG C roast 4 hours, obtain To roasting sample；Prepared 11.39 grams of oxidation chromium solution is taken, roasting sample is impregnated 20 minutes, is done at 120 DEG C Dry 3 hours, in 550 DEG C of constant temperature calcinings 5 hours, prepared potassium nitrate aqueous solution is then taken to impregnate again, dry 3 is small at 120 DEG C When, it is spare in 620 DEG C of constant temperature calcinings 6 hours.

2) catalyst for etherification uses the D005-II type resin catalysts that Dandong Mingzhu Special Type Resin Co., Ltd. produces, Granularity is 0.315-1.25mm, wet true density 1180-1200g/L, total exchange capacity >=5.2mmol/g [H⁺], mechanical strength >=95% (H-type)；

3) implementing process

Select raw material B；

1. in catalytic dehydrogenating reaction device, the molar ratio of hydrogen and hydro carbons (raw material B) is 0.3:1, reaction temperature 600 DEG C, volume space velocity 5.0h^-1, reaction pressure 1.1MPa, the content of alkene is in catalytic dehydrogenation product obtained by the reaction 66.7%；

Catalytic dehydrogenation product is mixed into methanol in methyltertiarvbutyl ether reactor, and the reaction condition of etherificate is：80 DEG C of reaction temperature, Volume space velocity 3.0h^-1, reaction pressure 1.0MPa, wherein methanol and the Tertiary olefin in the hydrocarbon material for entering methyltertiarvbutyl ether reactor Molar ratio is 1.1:1.After reaction product removes on-condensible gas, the content of yield 96.1%, wherein ether compound is 36.7%；

2. catalytic dehydrogenation product is mixed into methanol in methyltertiarvbutyl ether reactor, in methanol and owning into methyltertiarvbutyl ether reactor The molar ratio of Tertiary olefin in hydrocarbon material is 1.1:1, reaction temperature is 80 DEG C, volume space velocity 3.0h^-1, reaction pressure is It is reacted under conditions of 1.0MPa, obtains etherification product；After etherification product is removed on-condensible gas, gasoline component is obtained (mass yield 96.1%), the wherein content of ether compound are 36.7%.

Comparative example 2

This comparative example provides a kind of conventional method of conversion plug oils lighter hydrocarbons, specific as follows：

The operating procedure of this comparative example is consistent with embodiment 1；

Olefin oxidation dehydrogenation used in this comparative example is according to olefin oxidation dehydrogenation in embodiment 1 Prepared by preparation method, but without dipping ammonium tungstate solution in preparation process；

Olefin(e) centent is 58.8% in this comparative example catalytic dehydrogenating reaction product；The content of alkadienes in oxidative dehydrogenation product It is 18.0%, the mass yield of alcohols is 0.50%, and the mass yield of ketone is 0.33%；Etherification product deviate from on-condensible gas with Afterwards, gasoline component (mass yield 118.6%) is obtained, the wherein content of ether compound is 40.9%.

Claims (32)

1. a kind of method of conversion plug oils lighter hydrocarbons, this approach includes the following steps：

The first step, the raw material that will be enriched in C4-C6 alkane and hydrogen are sent into catalytic dehydrogenation unit and carry out catalytic dehydrogenating reaction, obtain Logistics a rich in alkene；

Second step, the logistics a for obtaining the first step are sent into separative element I, the hydrocarbon material flow b and C5 of isolated C6 or more with Under hydrocarbon material flow c；

Third step will carry out oxidative dehydrogenation in logistics c, the logistics containing oxidant and water feeding oxidative dehydrogenation unit, obtain To the logistics d containing alkadienes；

Logistics d is sent into separative element II by the 4th step, and logistics e is obtained after alkadienes is detached；

5th step will carry out etherification reaction in logistics e, logistics b and alcohols feeding etherificate unit, obtain gasoline component；Wherein,

In the third step, the composition of the Oxydehydrogenation catalyst used in oxidative dehydrogenation unit is shown in formula I：

A_aB_bC_cD_d·Fe_xO_eFormulas I

In Formulas I：A is 2-10, and b 0.01-0.5, c 0.01-0.5, d 0.01-0.2, x 4-20, e, which takes, meets chemical valence It is required that numerical value；

A is Cu, Co or Cr；B is K, Zn or V；C is Ca, Sr, Ba or Mg；D is W.

2. according to the method described in claim 1, it is characterized in that：Raw material rich in C4-C6 alkane meets the following conditions：Raw material In account for 95% part boiling range at 75 DEG C or less.

3. according to the method described in claim 1, it is characterized in that：In the first step, the reaction condition of catalytic dehydrogenation unit is：

Temperature is 480-700 DEG C, pressure 0.01-3MPa, and liquid volume air speed is 0.1-10h^-1。

4. according to the method described in claim 3, it is characterized in that：In the first step, the reaction condition of catalytic dehydrogenation unit is：

Temperature is 560-650 DEG C, pressure 0.4-1.2MPa, and liquid volume air speed is 2-7h^-1。

5. according to the method described in claim 1, it is characterized in that：In the first step, in hydrogen and entrance catalytic dehydrogenation unit All hydrocarbon materials molar ratio be (0.01-1):1.

6. according to the method described in claim 5, it is characterized in that：In the first step, in hydrogen and entrance catalytic dehydrogenation unit All hydrocarbon materials molar ratio be (0.1-0.5):1.

7. according to the method described in claim 1, it is characterized in that：In the third step, n-butene is converted with n-pentene in logistics c It is not less than 70% for the conversion ratio of alkadienes.

8. according to the method described in claim 7, it is characterized in that：In the third step, n-butene is converted with n-pentene in logistics c It is not less than 75% for the conversion ratio of alkadienes.

9. according to the method described in claim 1, it is characterized in that：In the third step, the reaction condition of oxidative dehydrogenation unit is：

Temperature is 280 DEG C -410 DEG C, pressure 0-100KPa, volume space velocity 10-500h^-1。

10. according to the method described in claim 9, it is characterized in that：In the third step, the reaction condition of oxidative dehydrogenation unit For：

Temperature is 310 DEG C -390 DEG C, pressure 0-40KPa, volume space velocity 60-400h^-1。

11. according to the method described in claim 1, it is characterized in that：In the third step, the logistics containing oxidant is oxygen-containing original The material stream of son.

12. according to the method for claim 11, it is characterised in that：In the third step, the logistics containing oxidant be air, Oxygen rich air or purity oxygen.

13. according to the method described in claim 1, it is characterized in that：In the third step, the oxidation in the logistics containing oxidant Agent is (0.1- with the molar ratio for entering the alkene in all hydrocarbon materials in oxidative dehydrogenation unit with oxymeter, the oxygen 1.0):1。

14. according to the method for claim 13, it is characterised in that：In the third step, the oxygen in the logistics containing oxidant With oxymeter, the molar ratio of the oxygen and the alkene in all hydrocarbon materials entered in oxidative dehydrogenation unit is agent (0.3-0.85):1。

15. according to the method described in claim 1, it is characterized in that：In the third step, the water and entrance oxidative dehydrogenation unit In all hydrocarbon materials mass ratio be (0.5-30):1.

16. according to the method for claim 15, it is characterised in that：In the third step, the water and entrance oxidative dehydrogenation list The mass ratio of all hydrocarbon materials in member is (5-20):1.

17. according to the method described in claim 1, it is characterized in that：In the 4th step, alkadienes in isolated logistics e Mass content be not higher than 0.3%.

18. according to the method described in claim 1, it is characterized in that：In the 5th step, the alcohols refer to carbon atom number not Low-carbon alcohols more than four.

19. according to the method for claim 18, it is characterised in that：In the 5th step, the alcohols is methanol and/or second Alcohol.

20. according to the method described in claim 1, it is characterized in that：In the 5th step, in the alcohols and entrance etherificate unit All hydrocarbon materials in Tertiary olefin molar ratio be (0.8-1.5):1.

21. according to the method for claim 20, it is characterised in that：In the 5th step, the alcohols and entrance etherificate unit In all hydrocarbon materials in Tertiary olefin molar ratio be (0.95-1.3):1.

22. according to the method described in claim 1, it is characterized in that：In the 5th step, the reaction condition of the etherificate unit For：

Temperature is 45-90 DEG C, pressure 0.4-3.0MPa, volume space velocity 0.1-5h^-1。

23. according to the method for claim 22, it is characterised in that：In the 5th step, the reaction condition of the etherificate unit For：Temperature is 55-75 DEG C, pressure 0.5-2MPa, volume space velocity 1-2h^-1。

24. according to the method described in claim 1, it is characterized in that：In the 5th step, the reactor of the etherificate unit is solid One or several kinds of combinations in fixed bed, moving bed, suspension bed and catalytic distillation reactor.

25. according to the method for claim 24, it is characterised in that：In the 5th step, the reactor of the etherificate unit is Catalytic distillation reactor.

26. according to the method described in claim 1, it is characterized in that：The preparation of the Oxydehydrogenation catalyst includes following step Suddenly：

Step 1: first, the presoma of metal A, B, C, D to be ground to the microspheroidal of 40-100 mesh respectively；It secondly, will be ground The presoma parts by weights of metal A be two parts, the weight percent of the presoma of first part of metal A is 55-80%, second part The weight percent of the presoma of metal A is 20-45%；The presoma of metal B, C and D are uniformly mixed；

Step 2: the presoma of first part of metal A is added under agitation for the iron nitrate solution of configuration 0.1-2mol/L It into iron nitrate solution, reacts 30-90 minutes, adds the presoma of mixed metal B, C and D, after reacting 30-90 minutes The presoma of second part of metal A is added, the binder for accounting for metal precursor gross mass 0.5-6% is added after 20-80 minutes in reaction, Obtain the slurry of presoma sediment；

Step 3: stirring slurry is gradually added into the ammonium hydroxide that mass percent concentration is 10-25% for 20-60 minutes into slurry, adjust The pH value for saving slurry is 7.5-10；

Step 4: carrying out heat modification in the environment of slurry is placed in 80-95 DEG C, modification time is 60-180 minutes；

Step 5: filter slurry makes the pH value of slurry reach 7-7.5 with washings filtering stock；

Step 6: filter slurry, molding, obtain catalyst after molding；

Step 7: by catalyst after molding modification by calcination 6-12 hours at 100-200 DEG C, roasts and change at 200-300 DEG C Property 4-8 hours, modification by calcination 1-4 hours at 300-400 DEG C, modification by calcination 1-4 hours at 400-500 DEG C, obtains finished product Catalyst.

27. according to the method described in claim 1, it is characterized in that：The preparation of the Oxydehydrogenation catalyst includes following step Suddenly：

Step 1: the presoma of metal A, B, C to be ground to the microspheroidal of 40-100 mesh respectively；Before ground metal A Two parts of body parts by weights is driven, the weight percent of the presoma of first part of metal A is 55-80%, the presoma of second part of metal A Weight percent be 20-45%；The presoma of metal B and C are uniformly mixed；

Step 2: the presoma of first part of metal A is added under agitation for the iron nitrate solution of configuration 0.1-2mol/L It into iron nitrate solution, reacts 30-90 minutes, adds the presoma of mixed metal B and C, reaction adds after 30-90 minutes Enter the presoma of second part of metal A, reaction is added binder and activated carbon after 20-80 minutes, obtains the slurry of presoma sediment Material；The additive amount of binder is the 0.5-6% of metal precursor gross mass, and the additive amount of activated carbon is metal precursor gross mass 0.5-4%；

Step 3: stirring slurry is gradually added into the ammonium hydroxide that mass percent concentration is 10-25% for 20-60 minutes into slurry, adjust The pH value for saving slurry is 7.5-10；

Step 4: carrying out heat modification in the environment of slurry is placed in 80-95 DEG C, modification time is 60-180 minutes；

Step 5: filter slurry makes the pH value of slurry reach 7-7.5 with washings filtering stock；

Step 6: filter slurry, molding, obtain catalyst after molding；

Step 7: by catalyst after molding modification by calcination 6-12 hours at 100-200 DEG C, roasts and change at 200-300 DEG C Property 4-8 hours, modification by calcination 1-4 hours at 300-400 DEG C, modification by calcination 1-4 hours at 400-500 DEG C；

Step 8: by being impregnated in the solution of the presoma of the catalyst input metal D after modification by calcination, metal D is tungsten, and tungsten source is WO₃, the precursor solution of metal D is the ammonium tungstate solution of a concentration of 0.01-0.6mol/L；Dipping temperature is 15-95 DEG C, dipping Time is 1-24 hours, takes out catalyst drying 6-24 hours at 80-160 DEG C, is activated 8-24 hours at 400-550 DEG C, Obtain finished catalyst.

28. the method according to claim 26 or 27, it is characterised in that：A concentration of 0.4- of the iron nitrate solution 1.2mol/L。

29. the method according to claim 26 or 27, it is characterised in that：The presoma of described metal A, B, C are respectively selected from The combination of one or more of their nitrate, chloride, sulfate and oxide.

30. according to the method for claim 26, it is characterised in that：In step 2, reaction is added after 40-60 minutes and bonds Agent；The binder is the combination of one or more of sesbania powder, polyacrylamide, methylcellulose and polyvinyl alcohol.

31. according to the method for claim 26, it is characterised in that：In step 2, reaction is added after 40-60 minutes and bonds Agent and activated carbon；The binder is one or more of sesbania powder, polyacrylamide, methylcellulose and polyvinyl alcohol Combination.

32. the method according to claim 27 or 31, it is characterised in that：In step 2, the addition of the activated carbon For the 1.0-3.0% of metal precursor gross mass.