CN108299147A - The production technology of residue mixing four freshening high yield of isobutene of carbon - Google Patents

The production technology of residue mixing four freshening high yield of isobutene of carbon Download PDF

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CN108299147A
CN108299147A CN201711479679.7A CN201711479679A CN108299147A CN 108299147 A CN108299147 A CN 108299147A CN 201711479679 A CN201711479679 A CN 201711479679A CN 108299147 A CN108299147 A CN 108299147A
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magnesium
isobutene
production technology
butylene
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沈秋云
余伟
刘丰敏
胡敏达
王裕振
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Zhejiang Meifu Petrochemical LLC
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Zhejiang Meifu Petrochemical LLC
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    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
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    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
    • C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
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    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
    • C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
    • C07C5/2767—Changing the number of side-chains
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    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
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    • C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
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    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
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Abstract

The invention discloses the production technologies of four freshening high yield of isobutene of residual carbon, it is raw material with residue mixing carbon four, butadiene catalytic hydrogenation therein generates 1 butylene and 2 butylene, remove normal butane, iso-butane and first material are obtained, the former dehydrogenation is converted into isobutene, and the latter carries out isomerization reaction under phosphorus and the effect of magnesium oxide modified 22 molecular sieve catalytics of ZSM, 1 butylene and 2 isomerization of butene therein are isobutene, and two parts isobutene product is merged.The invention comprehensively utilizes the remaining each components mixed in carbon four, obtain the higher high-purity isobutylene of added value in high yield.

Description

The production technology of residue mixing four freshening high yield of isobutene of carbon
Technical field
The present invention relates to a kind of production technologies of isobutene, and in particular to a kind of remaining mixing four freshening high yield of isobutene of carbon Production technology, belong to technical field of petrochemical industry.
Background technology
Isobutene（2- metering systems）It is important one of basic organic, is mainly used in gasoline additive methyl- tert It is inflammable and explosive in the production of butyl ether, polyisobutene etc., it is easy to react with many chemicals, is that butyl rubber produces Primary raw material.Industrially, high concentration isobutene is usually used in producing polyisobutene and produces butyl rubber with isoprene copolymer Glue.Isobutene is widely used as medicine, pesticide, antioxidant, synthesis senior lubricant, gasoline additive and the production of other fine chemistry industries The raw material of product.With the high demand of downstream product, the demand of isobutene in the world also rises year by year therewith.Isobutyl Alkene is mainly derived from the by-product mixing carbon four of steam cracking device and refinery catalytic cracking device.
Residue mixing carbon four is a kind of important petrochemical industry resource, is the general name of alkane, monoolefine and alkadienes（Isobutyl Alkane, normal butane, isobutene, n-butene, butadiene etc.）.
China in Recent Years is constructed and put into operation and the refining capacity built is quickly grown, and is building or the steaming of planning construction Vapour cracker scale is also considerable, and therefore, future, which has a large amount of remaining mixing carbon four, to be occurred, and mixing carbon four how is improved Comprehensive utilization ratio and promoted chemical utilization value have very important significance.
Invention content
The purpose of the present invention is to overcome above-mentioned the deficiencies in the prior art, it is different to provide a kind of remaining mixing four freshening fecund of carbon The production technology of butylene.
To achieve the above object, the present invention uses following technical proposals：
The production technology of residue mixing four freshening high yield of isobutene of carbon, is as follows：
（1）It is raw material with residue mixing carbon four, butadiene catalytic hydrogenation therein generates 1- butylene and 2- butylene, isolates isobutyl Alkane, and normal butane is removed, iso-butane and first material are obtained, step is respectively enterd（2）And step（3）；
（2）Dehydrogenation of isobutane is converted into high-purity isobutylene；
（3）Under phosphorus and the effect of magnesium oxide modified ZSM-22 molecular sieve catalytics, first material carries out isomerization reaction, therein 1- butylene and 2- isomerization of butene are isobutene, and rectifying obtains high-purity isobutylene；
（4）Merge step（2）And step（3）Gained high-purity isobutylene to get.
Preferably, step（1）In, the remaining mixing carbon four is the mixing carbon four of catalytic cracking unit by-product, wherein wrapping Include normal butane, iso-butane, 1- butylene, 2- butylene, butadiene, isobutene.
Preferably, step（1）In, catalyst used in catalytic hydrogenation is Pd/Al2O3。
Preferably, step（1）Catalytic hydrogenation is first carried out in catalytic rectifying tower, is isolated iso-butane, is then transferred to extraction It takes and carries out separation of alkane and olefin in rectifying column, remove normal butane.
Preferably, step（1）The normal butane of middle removing can be used as steam cracking device raw material.
Preferably, step（2）In, dehydrogenation of isobutane, catalyst Pt/Al are carried out using fluidized-bed reactor2O3、Sn/ Al2O3Or Zn/Al2O3。
Preferably, step（3）Isomerization reaction is first carried out in flowing bed reactor, and essence is then carried out in rectifying column It evaporates.
Preferably, step（3）In, the phosphorus and magnesium oxide modified ZSM-22 molecular sieves, preparation method are as follows：It will ZSM-22 molecular sieves are impregnated in liquid containing phosphorus source, then soluble magnesium salting liquid is added in 80~90 DEG C of rotary evaporations 5~6 hours, It is added with stirring the precipitating reagent containing oxalate, obtains mixed solution, 30~40 DEG C are aged 10~12 hours, filter, and drying is forged Burn to get.
It is further preferred that the liquid containing phosphorus source is selected from any one of phosphoric acid, diammonium hydrogen phosphate or ammonium dihydrogen phosphate.
It is further preferred that the mass volume ratio of ZSM-22 molecular sieves and the liquid containing phosphorus source is 1g：15~20mL, it is described phosphorous P elements weight content is the 5~8% of ZSM-22 molecular sieves in the liquid of source.
It is further preferred that any of the soluble magnesium salt in magnesium acetate, magnesium chloride, magnesium nitrate or magnesium sulfate Kind.
It is further preferred that the mass volume ratio of ZSM-22 molecular sieves and soluble magnesium salting liquid is 1g：25~30mL, institute It states in soluble magnesium salting liquid, the weight content of magnesium elements is the 2~3% of ZSM-22 molecular sieves.
It is further preferred that the molar ratio of contained magnesium elements and oxalate is 1 in soluble magnesium salting liquid：1.5~2.
It is further preferred that the precipitating reagent containing oxalate is oxalic acid or ammonium oxalate.
Preferably, the process conditions of drying are：150~160 DEG C of dryings 18~22 hours.
Preferably, the process conditions of calcining are：700~800 DEG C are calcined 5~8 hours, first with the heating of 10~15 DEG C/min Rate is warming up to 500~550 DEG C, is then warming up to 700~800 DEG C with the heating rate of 2~3 DEG C/min.
Beneficial effects of the present invention：
1, the present invention is raw material with residue mixing carbon four, and butadiene catalytic hydrogenation therein generates 1- butylene and 2- butylene, removing Normal butane obtains iso-butane and first material, the former dehydrogenation is converted into isobutene, and the latter is in phosphorus and magnesium oxide modified ZSM-22 Molecular sieve catalytic effect is lower to carry out isomerization reaction, and 1- butylene and 2- isomerization of butene therein are isobutene, and two parts are different Butylene product merges.The invention comprehensively utilizes the remaining each component mixed in carbon four, obtain in high yield added value compared with High high-purity isobutylene.
2, the catalyst of isomerization reaction of the present invention is phosphorus and magnesium oxide modified ZSM-22 molecular sieves, is with ZSM-22 points Son sieve starting material, obtains after containing phosphorus source liquid and soluble magnesium salt solution treatment.ZSM-22 molecular sieves itself have micropore knot Structure, through phosphorus and it is magnesium oxide modified after, provide certain shape selectivity to be isomerized to isobutene, improve the selectivity of target product.
Specific implementation mode
With reference to embodiment, the present invention will be further elaborated, it should explanation, following the description merely to It explains the present invention, its content is not defined.
Embodiment 1：
The production technology of residue mixing four freshening high yield of isobutene of carbon, is as follows：
（1）It is raw material with residue mixing carbon four, butadiene therein is in Pd/Al2O3Under the action of catalytic hydrogenation generate 1- butylene With 2- butylene, iso-butane is isolated, and remove normal butane, obtain iso-butane and first material, respectively enter step（2）And step （3）；
（2）Dehydrogenation of isobutane is converted into high-purity isobutylene；
（3）Under phosphorus and the effect of magnesium oxide modified ZSM-22 molecular sieve catalytics, first material carries out isomerization reaction, therein 1- butylene and 2- isomerization of butene are isobutene, and rectifying obtains high-purity isobutylene；
（4）Merge step（2）And step（3）Gained high-purity isobutylene to get.
Wherein, step（2）In, dehydrogenation of isobutane, catalyst Pt/Al are carried out using fluidized-bed reactor2O3。
Step（3）In, phosphorus and magnesium oxide modified ZSM-22 molecular sieves, preparation method are as follows：By ZSM-22 molecular sieves It is impregnated in liquid containing phosphorus source, then 80 DEG C of rotary evaporations 5 hours are added soluble magnesium salting liquid, are added with stirring containing oxalate Precipitating reagent, obtain mixed solution, 30 DEG C are aged 10 hours, filter, drying, calcining to get.
Liquid containing phosphorus source is phosphoric acid.
The mass volume ratio of ZSM-22 molecular sieves and the liquid containing phosphorus source is 1g：15mL, P elements weight content in liquid containing phosphorus source It is the 5% of ZSM-22 molecular sieves.
Soluble magnesium salt is magnesium acetate.
The mass volume ratio of ZSM-22 molecular sieves and soluble magnesium salting liquid is 1g：25mL, in soluble magnesium salting liquid, magnesium The weight content of element is the 2% of ZSM-22 molecular sieves.
The molar ratio of contained magnesium elements and oxalate is 1 in soluble magnesium salting liquid：1.5.
Precipitating reagent containing oxalate is oxalic acid.
The process conditions of drying are：150 DEG C of dryings 18 hours.
The process conditions of calcining are：700 DEG C are calcined 5 hours, are first warming up to 500 DEG C with the heating rate of 10 DEG C/min, so Afterwards 700 DEG C are warming up to the heating rate of 2 DEG C/min.
Embodiment 2：
The production technology of residue mixing four freshening high yield of isobutene of carbon, is as follows：
（1）It is raw material with residue mixing carbon four, butadiene therein is in Pd/Al2O3Under the action of catalytic hydrogenation generate 1- butylene With 2- butylene, iso-butane is isolated, and remove normal butane, obtain iso-butane and first material, respectively enter step（2）And step （3）；
（2）Dehydrogenation of isobutane is converted into high-purity isobutylene；
（3）Under phosphorus and the effect of magnesium oxide modified ZSM-22 molecular sieve catalytics, first material carries out isomerization reaction, therein 1- butylene and 2- isomerization of butene are isobutene, and rectifying obtains high-purity isobutylene；
（4）Merge step（2）And step（3）Gained high-purity isobutylene to get.
Wherein, step（2）In, dehydrogenation of isobutane, catalyst Sn/Al are carried out using fluidized-bed reactor2O3。
Step（3）In, phosphorus and magnesium oxide modified ZSM-22 molecular sieves, preparation method are as follows：By ZSM-22 molecular sieves It is impregnated in liquid containing phosphorus source, then 90 DEG C of rotary evaporations 6 hours are added soluble magnesium salting liquid, are added with stirring containing oxalate Precipitating reagent, obtain mixed solution, 40 DEG C are aged 12 hours, filter, drying, calcining to get.
Liquid containing phosphorus source is diammonium hydrogen phosphate.
The mass volume ratio of ZSM-22 molecular sieves and the liquid containing phosphorus source is 1g：20mL, P elements weight content in liquid containing phosphorus source It is the 8% of ZSM-22 molecular sieves.
Soluble magnesium salt is magnesium chloride.
The mass volume ratio of ZSM-22 molecular sieves and soluble magnesium salting liquid is 1g：30mL, in soluble magnesium salting liquid, The weight content of magnesium elements is the 3% of ZSM-22 molecular sieves.
The molar ratio of contained magnesium elements and oxalate is 1 in soluble magnesium salting liquid： 2.
Precipitating reagent containing oxalate is ammonium oxalate.
The process conditions of drying are：160 DEG C of dryings 22 hours.
The process conditions of calcining are：800 DEG C are calcined 8 hours, are first warming up to 550 DEG C with the heating rate of 15 DEG C/min, so Afterwards 800 DEG C are warming up to the heating rate of 3 DEG C/min.
Embodiment 3：
The production technology of residue mixing four freshening high yield of isobutene of carbon, is as follows：
（1）It is raw material with residue mixing carbon four, butadiene therein is in Pd/Al2O3Under the action of catalytic hydrogenation generate 1- butylene With 2- butylene, iso-butane is isolated, and remove normal butane, obtain iso-butane and first material, respectively enter step（2）And step （3）；
（2）Dehydrogenation of isobutane is converted into high-purity isobutylene；
（3）Under phosphorus and the effect of magnesium oxide modified ZSM-22 molecular sieve catalytics, first material carries out isomerization reaction, therein 1- butylene and 2- isomerization of butene are isobutene, and rectifying obtains high-purity isobutylene；
（4）Merge step（2）And step（3）Gained high-purity isobutylene to get.
Wherein, step（2）In, dehydrogenation of isobutane, catalyst Zn/Al are carried out using fluidized-bed reactor2O3。
Step（3）In, phosphorus and magnesium oxide modified ZSM-22 molecular sieves, preparation method are as follows：By ZSM-22 molecular sieves It is impregnated in liquid containing phosphorus source, then 80 DEG C of rotary evaporations 6 hours are added soluble magnesium salting liquid, are added with stirring containing oxalate Precipitating reagent, obtain mixed solution, 30 DEG C are aged 12 hours, filter, drying, calcining to get.
Liquid containing phosphorus source is ammonium dihydrogen phosphate.
The mass volume ratio of ZSM-22 molecular sieves and the liquid containing phosphorus source is 1g：15mL, P elements weight content in liquid containing phosphorus source It is the 8% of ZSM-22 molecular sieves.
Soluble magnesium salt is magnesium nitrate.
The mass volume ratio of ZSM-22 molecular sieves and soluble magnesium salting liquid is 1g：25mL, in soluble magnesium salting liquid, magnesium The weight content of element is the 3% of ZSM-22 molecular sieves.
The molar ratio of contained magnesium elements and oxalate is 1 in soluble magnesium salting liquid：1.5.
Precipitating reagent containing oxalate is oxalic acid.
The process conditions of drying are：160 DEG C of dryings 18 hours.
The process conditions of calcining are：800 DEG C are calcined 5 hours, are first warming up to 500 DEG C with the heating rate of 15 DEG C/min, so Afterwards 700 DEG C are warming up to the heating rate of 3 DEG C/min.
Embodiment 4：
The production technology of residue mixing four freshening high yield of isobutene of carbon, is as follows：
（1）It is raw material with residue mixing carbon four, butadiene therein is in Pd/Al2O3Under the action of catalytic hydrogenation generate 1- butylene With 2- butylene, iso-butane is isolated, and remove normal butane, obtain iso-butane and first material, respectively enter step（2）And step （3）；
（2）Dehydrogenation of isobutane is converted into high-purity isobutylene；
（3）Under phosphorus and the effect of magnesium oxide modified ZSM-22 molecular sieve catalytics, first material carries out isomerization reaction, therein 1- butylene and 2- isomerization of butene are isobutene, and rectifying obtains high-purity isobutylene；
（4）Merge step（2）And step（3）Gained high-purity isobutylene to get.
Wherein, step（2）In, dehydrogenation of isobutane, catalyst Pt/Al are carried out using fluidized-bed reactor2O3。
Step（3）In, phosphorus and magnesium oxide modified ZSM-22 molecular sieves, preparation method are as follows：By ZSM-22 molecular sieves It is impregnated in liquid containing phosphorus source, then 90 DEG C of rotary evaporations 5 hours are added soluble magnesium salting liquid, are added with stirring containing oxalate Precipitating reagent, obtain mixed solution, 40 DEG C are aged 10 hours, filter, drying, calcining to get.
Liquid containing phosphorus source is phosphoric acid.
The mass volume ratio of ZSM-22 molecular sieves and the liquid containing phosphorus source is 1g：15mL, P elements weight content in liquid containing phosphorus source It is the 8% of ZSM-22 molecular sieves.
Soluble magnesium salt is magnesium sulfate.
The mass volume ratio of ZSM-22 molecular sieves and soluble magnesium salting liquid is 1g：25mL, in soluble magnesium salting liquid, magnesium The weight content of element is the 3% of ZSM-22 molecular sieves.
The molar ratio of contained magnesium elements and oxalate is 1 in soluble magnesium salting liquid：1.5.
Precipitating reagent containing oxalate is ammonium oxalate.
The process conditions of drying are：150 DEG C of dryings 22 hours.
The process conditions of calcining are：700 DEG C are calcined 8 hours, are first warming up to 550 DEG C with the heating rate of 10 DEG C/min, so Afterwards 800 DEG C are warming up to the heating rate of 2 DEG C/min.
Embodiment 5：
The production technology of residue mixing four freshening high yield of isobutene of carbon, is as follows：
（1）It is raw material with residue mixing carbon four, butadiene therein is in Pd/Al2O3Under the action of catalytic hydrogenation generate 1- butylene With 2- butylene, iso-butane is isolated, and remove normal butane, obtain iso-butane and first material, respectively enter step（2）And step （3）；
（2）Dehydrogenation of isobutane is converted into high-purity isobutylene；
（3）Under phosphorus and the effect of magnesium oxide modified ZSM-22 molecular sieve catalytics, first material carries out isomerization reaction, therein 1- butylene and 2- isomerization of butene are isobutene, and rectifying obtains high-purity isobutylene；
（4）Merge step（2）And step（3）Gained high-purity isobutylene to get.
Wherein, step（2）In, dehydrogenation of isobutane, catalyst Zn/Al are carried out using fluidized-bed reactor2O3。
Step（3）In, phosphorus and magnesium oxide modified ZSM-22 molecular sieves, preparation method are as follows：By ZSM-22 molecular sieves It is impregnated in liquid containing phosphorus source, then 85 DEG C of rotary evaporations 5 hours are added soluble magnesium salting liquid, are added with stirring containing oxalate Precipitating reagent, obtain mixed solution, 35 DEG C are aged 11 hours, filter, drying, calcining to get.
Liquid containing phosphorus source is ammonium dihydrogen phosphate.
The mass volume ratio of ZSM-22 molecular sieves and the liquid containing phosphorus source is 1g：18mL, P elements weight content in liquid containing phosphorus source It is the 7% of ZSM-22 molecular sieves.
Soluble magnesium salt is magnesium chloride.
The mass volume ratio of ZSM-22 molecular sieves and soluble magnesium salting liquid is 1g：28mL, in soluble magnesium salting liquid, magnesium The weight content of element is the 2% of ZSM-22 molecular sieves.
The molar ratio of contained magnesium elements and oxalate is 1 in soluble magnesium salting liquid：1.8.
Precipitating reagent containing oxalate is ammonium oxalate.
The process conditions of drying are：155 DEG C of dryings 20 hours.
The process conditions of calcining are：750 DEG C are calcined 6 hours, are first warming up to 520 DEG C with the heating rate of 12 DEG C/min, so Afterwards 750 DEG C are warming up to the heating rate of 2 DEG C/min.
Comparative example 1
The production technology of residue mixing four freshening high yield of isobutene of carbon, is as follows：
（1）It is raw material with residue mixing carbon four, butadiene therein is in Pd/Al2O3Under the action of catalytic hydrogenation generate 1- butylene With 2- butylene, iso-butane is isolated, and remove normal butane, obtain iso-butane and first material, respectively enter step（2）And step （3）；
（2）Dehydrogenation of isobutane is converted into high-purity isobutylene；
（3）P Modification ZSM-22 molecular sieve catalytics effect under, first material carry out isomerization reaction, 1- butylene therein and 2- isomerization of butene is isobutene, and rectifying obtains high-purity isobutylene；
（4）Merge step（2）And step（3）Gained high-purity isobutylene to get.
Wherein, step（2）In, dehydrogenation of isobutane, catalyst Zn/Al are carried out using fluidized-bed reactor2O3。
Step（3）In, the ZSM-22 molecular sieves of P Modification, preparation method is as follows：ZSM-22 molecular sieves are impregnated in and are contained In phosphorus source liquid, 85 DEG C of rotary evaporations 5 hours, drying, calcining to get.
Liquid containing phosphorus source is ammonium dihydrogen phosphate.
The mass volume ratio of ZSM-22 molecular sieves and the liquid containing phosphorus source is 1g：18mL, P elements weight content in liquid containing phosphorus source It is the 7% of ZSM-22 molecular sieves.
The process conditions of drying are：155 DEG C of dryings 20 hours.
The process conditions of calcining are：750 DEG C are calcined 6 hours, are first warming up to 520 DEG C with the heating rate of 12 DEG C/min, so Afterwards 750 DEG C are warming up to the heating rate of 2 DEG C/min.
Comparative example 2
The production technology of residue mixing four freshening high yield of isobutene of carbon, is as follows：
（1）It is raw material with residue mixing carbon four, butadiene therein is in Pd/Al2O3Under the action of catalytic hydrogenation generate 1- butylene With 2- butylene, iso-butane is isolated, and remove normal butane, obtain iso-butane and first material, respectively enter step（2）And step （3）；
（2）Dehydrogenation of isobutane is converted into high-purity isobutylene；
（3）Under magnesium oxide modified ZSM-22 molecular sieve catalytics effect, first material carries out isomerization reaction, 1- fourths therein Alkene and 2- isomerization of butene are isobutene, and rectifying obtains high-purity isobutylene；
（4）Merge step（2）And step（3）Gained high-purity isobutylene to get.
Wherein, step（2）In, dehydrogenation of isobutane, catalyst Zn/Al are carried out using fluidized-bed reactor2O3。
Step（3）In, magnesium oxide modified ZSM-22 molecular sieves, preparation method is as follows：ZSM-22 molecular sieves are impregnated In soluble magnesium salting liquid, it is added with stirring the precipitating reagent containing oxalate, obtains mixed solution, 35 DEG C are aged 11 hours, mistake Filter, drying, calcining to get.
Soluble magnesium salt is magnesium chloride.
The mass volume ratio of ZSM-22 molecular sieves and soluble magnesium salting liquid is 1g：28mL, in soluble magnesium salting liquid, magnesium The weight content of element is the 2% of ZSM-22 molecular sieves.
The molar ratio of contained magnesium elements and oxalate is 1 in soluble magnesium salting liquid：1.8.
Precipitating reagent containing oxalate is ammonium oxalate.
The process conditions of drying are：155 DEG C of dryings 20 hours.
The process conditions of calcining are：750 DEG C are calcined 6 hours, are first warming up to 520 DEG C with the heating rate of 12 DEG C/min, so Afterwards 750 DEG C are warming up to the heating rate of 2 DEG C/min.
Comparative example 3
The production technology of residue mixing four freshening high yield of isobutene of carbon, is as follows：
（1）It is raw material with residue mixing carbon four, butadiene therein is in Pd/Al2O3Under the action of catalytic hydrogenation generate 1- butylene With 2- butylene, iso-butane is isolated, and remove normal butane, obtain iso-butane and first material, respectively enter step（2）And step （3）；
（2）Dehydrogenation of isobutane is converted into high-purity isobutylene；
（3）Under phosphorus and magnesium oxide modified ZSM-5 molecular sieve catalytic action, first material carries out isomerization reaction, therein 1- butylene and 2- isomerization of butene are isobutene, and rectifying obtains high-purity isobutylene；
（4）Merge step（2）And step（3）Gained high-purity isobutylene to get.
Wherein, step（2）In, dehydrogenation of isobutane, catalyst Zn/Al are carried out using fluidized-bed reactor2O3。
Step（3）In, phosphorus and magnesium oxide modified ZSM-5 molecular sieve, preparation method are as follows：ZSM-5 molecular sieve is soaked In liquid containing phosphorus source, then 85 DEG C of rotary evaporations 5 hours are added soluble magnesium salting liquid, are added with stirring containing oxalate stain Precipitating reagent, obtains mixed solution, and 35 DEG C are aged 11 hours, filter, drying, calcining to get.
Liquid containing phosphorus source is ammonium dihydrogen phosphate.
The mass volume ratio of ZSM-5 molecular sieve and the liquid containing phosphorus source is 1g：18mL, P elements weight content is in liquid containing phosphorus source The 7% of ZSM-5 molecular sieve.
Soluble magnesium salt is magnesium chloride.
The mass volume ratio of ZSM-5 molecular sieve and soluble magnesium salting liquid is 1g：28mL, in soluble magnesium salting liquid, magnesium The weight content of element is the 2% of ZSM-5 molecular sieve.
The molar ratio of contained magnesium elements and oxalate is 1 in soluble magnesium salting liquid：1.8.
Precipitating reagent containing oxalate is ammonium oxalate.
The process conditions of drying are：155 DEG C of dryings 20 hours.
The process conditions of calcining are：750 DEG C are calcined 6 hours, are first warming up to 520 DEG C with the heating rate of 12 DEG C/min, so Afterwards 750 DEG C are warming up to the heating rate of 2 DEG C/min.
Comparative example 4
The production technology of residue mixing four freshening high yield of isobutene of carbon, is as follows：
（1）It is raw material with residue mixing carbon four, butadiene therein is in Pd/Al2O3Under the action of catalytic hydrogenation generate 1- butylene With 2- butylene, iso-butane is isolated, and remove normal butane, obtain iso-butane and first material, respectively enter step（2）And step （3）；
（2）Dehydrogenation of isobutane is converted into high-purity isobutylene；
（3）Under phosphorus and the effect of magnesium oxide modified SAPO-34 molecular sieve catalytics, first material carries out isomerization reaction, wherein 1- butylene and 2- isomerization of butene be isobutene, rectifying obtains high-purity isobutylene；
（4）Merge step（2）And step（3）Gained high-purity isobutylene to get.
Wherein, step（2）In, dehydrogenation of isobutane, catalyst Zn/Al are carried out using fluidized-bed reactor2O3。
Step（3）In, phosphorus and magnesium oxide modified SAPO-34 molecular sieves, preparation method are as follows：By SAPO-34 molecules Sieve is impregnated in liquid containing phosphorus source, then 85 DEG C of rotary evaporations 5 hours are added soluble magnesium salting liquid, are added with stirring containing oxalic acid The precipitating reagent of root, obtains mixed solution, and 35 DEG C are aged 11 hours, filter, drying, calcining to get.
Liquid containing phosphorus source is ammonium dihydrogen phosphate.
The mass volume ratio of SAPO-34 molecular sieves and the liquid containing phosphorus source is 1g：18mL, P elements weight content in liquid containing phosphorus source It is the 7% of SAPO-34 molecular sieves.
Soluble magnesium salt is magnesium chloride.
The mass volume ratio of SAPO-34 molecular sieves and soluble magnesium salting liquid is 1g：28mL, in soluble magnesium salting liquid, The weight content of magnesium elements is the 2% of SAPO-34 molecular sieves.
The molar ratio of contained magnesium elements and oxalate is 1 in soluble magnesium salting liquid：1.8.
Precipitating reagent containing oxalate is ammonium oxalate.
The process conditions of drying are：155 DEG C of dryings 20 hours.
The process conditions of calcining are：750 DEG C are calcined 6 hours, are first warming up to 520 DEG C with the heating rate of 12 DEG C/min, so Afterwards 750 DEG C are warming up to the heating rate of 2 DEG C/min.
Test example
The isobutene yield of Statistics Implementation example 1~5 and comparative example 1~4（The quality of the quality of isobutene/residue mixing carbon four × 100%）And purity, it the results are shown in Table 1.
1. isobutene yield of table and purity compare
Isobutene yield（%） Purity（%）
Embodiment 1 89.6 ≥99.9
Embodiment 2 89.7 ≥99.9
Embodiment 3 90.1 ≥99.9
Embodiment 4 90.1 ≥99.9
Embodiment 5 91.2 ≥99.9
Comparative example 1 62.3 97.3
Comparative example 2 60.1 96.5
Comparative example 3 71.8 92.1
Comparative example 4 68.5 91.2
As shown in Table 1, the production technology of Examples 1 to 5 can obtain the high-purity isobutylene of higher yields, far superior to compare Example 1~4.Phosphorus and magnesium oxide modified ZSM-22 molecular sieves are replaced with the ZSM-22 molecular sieves of P Modification, comparative example by comparative example 1 Phosphorus and magnesium oxide modified ZSM-22 molecular sieves are replaced with magnesium oxide modified ZSM-22 molecular sieves by 2, and comparative example 3 is by phosphorus and oxygen Change magnesium-modified ZSM-22 molecular sieves and replace with phosphorus and magnesium oxide modified ZSM-5 molecular sieve, comparative example 4 changes phosphorus and magnesia The ZSM-22 molecular sieves of property replace with phosphorus and magnesium oxide modified SAPO-34 molecular sieves, and isobutene yield is substantially reduced, and And product purity decrease to some degree.
Although the above-mentioned specific implementation mode to the present invention is described, not to the limit of the scope of the present invention System, based on the technical solutions of the present invention, those skilled in the art need not make the creative labor can make it is each Kind modification or deformation are still within protection scope of the present invention.

Claims (10)

1. the production technology of residue mixing four freshening high yield of isobutene of carbon, which is characterized in that be as follows：
（1）It is raw material with residue mixing carbon four, butadiene catalytic hydrogenation therein generates 1- butylene and 2- butylene, isolates isobutyl Alkane, and normal butane is removed, iso-butane and first material are obtained, step is respectively enterd（2）And step（3）；
（2）Dehydrogenation of isobutane is converted into high-purity isobutylene；
（3）Under phosphorus and the effect of magnesium oxide modified ZSM-22 molecular sieve catalytics, first material carries out isomerization reaction, therein 1- butylene and 2- isomerization of butene are isobutene, and rectifying obtains high-purity isobutylene；
（4）Merge step（2）And step（3）Gained high-purity isobutylene to get.
2. production technology according to claim 1, which is characterized in that step（1）In, the remaining mixing carbon four is catalysis The mixing carbon four of cracking unit by-product, including normal butane, iso-butane, 1- butylene, 2- butylene, butadiene, isobutene.
3. production technology according to claim 1, which is characterized in that step（1）In, catalyst used in catalytic hydrogenation For Pd/Al2O3。
4. production technology according to claim 1, which is characterized in that step（1）First it is catalyzed in catalytic rectifying tower Add hydrogen, isolate iso-butane, be then transferred in extractive distillation column and carry out separation of alkane and olefin, removes normal butane.
5. production technology according to claim 1, which is characterized in that step（2）In, it is carried out using fluidized-bed reactor different Butane dehydrogenation, catalyst Pt/Al2O3、Sn/Al2O3Or Zn/Al2O3。
6. production technology according to claim 1, which is characterized in that step（3）In, the phosphorus and magnesium oxide modified ZSM-22 molecular sieves, preparation method are as follows：ZSM-22 molecular sieves are impregnated in liquid containing phosphorus source, 80~90 DEG C of rotary evaporations 5 ~6 hours, soluble magnesium salting liquid is then added, is added with stirring the precipitating reagent containing oxalate, obtains mixed solution, 30~40 DEG C ageing 10~12 hours, filter, drying, calcining to get.
7. production technology according to claim 6, which is characterized in that the liquid containing phosphorus source is selected from phosphoric acid, diammonium hydrogen phosphate Or any one of ammonium dihydrogen phosphate.
8. production technology according to claim 6, which is characterized in that the quality volume of ZSM-22 molecular sieves and the liquid containing phosphorus source Than for 1g：15~20mL, P elements weight content is the 5~8% of ZSM-22 molecular sieves in the liquid containing phosphorus source.
9. production technology according to claim 6, which is characterized in that the soluble magnesium salt be selected from magnesium acetate, magnesium chloride, Any one of magnesium nitrate or magnesium sulfate.
10. production technology according to claim 6, which is characterized in that ZSM-22 molecular sieves and soluble magnesium salting liquid Mass volume ratio is 1g：25~30mL, in the soluble magnesium salting liquid, the weight content of magnesium elements is ZSM-22 molecular sieves 2~3%.
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