CN106946644A - A kind of oligomerization of isobutene - Google Patents
A kind of oligomerization of isobutene Download PDFInfo
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- CN106946644A CN106946644A CN201710158464.9A CN201710158464A CN106946644A CN 106946644 A CN106946644 A CN 106946644A CN 201710158464 A CN201710158464 A CN 201710158464A CN 106946644 A CN106946644 A CN 106946644A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
- C07C2/14—Catalytic processes with inorganic acids; with salts or anhydrides of acids
- C07C2/16—Acids of sulfur; Salts thereof; Sulfur oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
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Abstract
The invention discloses a kind of oligomerization of isobutene, using fixed bed reactors；The catalyst is ferric sulfate and nickel sulfate loaded catalyst, and its oligomerization process condition is：160 220 DEG C of reaction temperature, the 6.5MPa of reaction pressure 1.0, the 10.0h of volume space velocity 2.0‑1.Oligomerisation reaction process conditions are gentle, under conditions of isobutene conversion is higher, and dimer selectivity is high, and trimer is selectively low, and the activity stability of catalyst is good.
Description
Technical field
The present invention relates to a kind of oligomerization of isobutene, more specifically using a kind of with multiple containing zinc oxide-alumina
Condensation material is carrier isobutene oligomerisation catalyst, the oligomerisation reaction for isobutene.
Background technology
Low-carbon alkene oligomerisation is one of important chemical process, wherein the oligomerisation production of butylene in oil refining and Organic Chemical Industry
Thing is important chemical intermediate, can be used for production oligomerisation gasoline and diesel oil, be also used as production detergent, plasticizer,
The important intermediate of additive and agricultural chemicals.Butene oligomerization catalyst mainly has Ziggler types homogeneous catalyst, solid phosphoric acid catalysis
The multiple catalysts such as agent, zeolite molecular sieve catalyst and loaded catalyst.
The composite of zinc oxide and aluminum oxide is frequently as the carrier material of catalyst, and application field is extensive.Spinel-type
Composite oxides are the up-and-coming Inorganic Non-metallic Materials of a class, and height is widely used in a series of good characteristics
The fields such as adiabator, catalyst and catalyst carrier.The conventional preparation method of the domestic and international material includes infusion process, mechanical mixture
Method, coprecipitation and peptisation.Wherein, because infusion process and mechanical mixing use alumina material as predecessor, pass through
The specific surface area of alumina material is adjusted, both approaches can prepare the composite of high specific surface area, but be due to multiple
Aluminum oxide and zinc oxide interaction in condensation material is weaker, and the loss of zinc oxide is easily produced during use, is typically to adopt
The two is promoted to form spinelle to avoid the loss of zinc oxide with the method for high-temperature roasting；And coprecipitation and peptisation are used and contained
The compound of aluminum and zinc prepares zinc-aluminium precursor by precipitation or peptization, and aluminum and zinc is stronger by reacting generation in preparation process
Interaction the zinc oxide during use can be avoided to be lost in, but the specific surface area that peptisation prepares material is minimum, makes
It is restricted when it is used as catalysis material.
European patent EP 0371983 uses specific surface area 52m2/ g, the granular SiO that aperture is 60nm2Phosphorus is prepared for for carrier
Acid/SiO2Catalyst, for isobutene oligomerisation reaction gasoline.
United States Patent (USP) US4100220, US4463211 report anti-using cation exchange resin catalyst as butene oligomerization
The catalyst answered, but HMW oligomer easily block reaction duct, and resin matrix alkylation can cause its activity decrease compared with
It hurry up, the heat-resisting quantity of resin is poor in addition, constrain its application.Mobil companies exploitation MOGO techniques (US4150063 and
US4254298) use silica alumina ratio for 79 ZSM-5 molecular sieve catalyst, obtained by changing process conditions with gasoline and bavin
Product based on oil, but because oligomerisation in course of reaction, cracking copolyreaction are present, product carbon number distribution is too wide, selectivity compared with
Difference.
Chinese patent CN1721073A discloses a kind of catalyst of suitable butene oligomerization reaction, by using with YO2/
M2O3The hetero atom ZSM-5 molecular sieve that mol ratio is 50-200 is the active main body of catalyst, and M is triad, and Y is tetravalence member
The butene oligomerization catalyst of element.
Chinese patent CN104324734A discloses a kind of butene oligomerization reaction synthesis C8 and C12 catalyst preparation side
Method, using equi-volume impregnating by Fe (NO3)3First carry out dissolving and be impregnated into γ-Al2O3On, after drying, roasting, then will
(NH4)2SO4Dissolving is impregnated into Fe (NO3)3On/γ-Al2O3,1- butene oligomerization catalyst is obtained after drying and roasting.
The subject matter that above-mentioned catalyst is present is found during butene oligomerization is：Solid acid catalyst SPAC is current
Extensive catalyst is used in butene oligomerization reaction, but it can not regenerate after having argillization, caking, inactivation；Heterogeneous catalyst
Oligomerisation reaction activity and selectivity of product are high, but easily inactivation；Loaded catalyst and ionic-liquid catalyst are preferable due to its
Reactivity worth, it is wide in recent years concerned.
The content of the invention
The invention provides a kind of oligomerization of isobutene, dimer is produced for isobutene oligomerisation.Including following step
Suddenly：
By treated ferric sulfate-sulfuric acid ni-type Catalyst packing in fixed bed reactors, after airtight experiment is qualified
Start into the raw material containing isobutene, oligomerisation reaction is carried out under reaction process condition, reactor product carries out chromatography.
Catalyst of the present invention is the ferric sulfate and nickel sulfate being carried on the complex carrier containing zinc oxide-alumina
Base catalyst.
The composition of the catalyst is with oxidation material gauge, including following component：Complex carrier containing zinc oxide-alumina
80.0-97.0wt%, active component ferric sulfate 2.0-12.0wt%, nickel sulfate 1.0-8.0wt%.
The preparation method of described catalyst, comprises the following steps：
Ferric sulfate and nickel sulfate soluble-salt are made into maceration extract, the complex carrier containing zinc oxide-alumina is impregnated, done
Dry, roasting obtains catalyst；
The described complex carrier containing zinc oxide-alumina, including the zinc oxide containing gahnite, aluminum oxide, auxiliary agent
Component phosphorus, potassium and magnesium, the composition of complex carrier is with oxidation material gauge：Zinc oxide content containing gahnite is 5.0-
40.0wt%, alumina content is 60.0-95.0wt%, and the percentage that the content of adjuvant component phosphorus, potassium and magnesium accounts for carrier quality contains
Amount is respectively P2O50.2-1.2wt%, K2O0.2-2.0wt%, MgO 0.2-2.0wt%, complex carrier specific surface area 200-
300m2/g；
The described complex carrier containing zinc oxide-alumina, the method for being prepared by the following procedure is obtained：
Soluble salt solutions and zinc-containing solution containing aluminium are alternately titrated by non-constant pH, prepared containing gahnite
Zinc oxide stratified material；Zinc oxide and boehmite containing gahnite are well mixed, sesbania powder, nitric acid is added
The acid solution containing Sodium Polyacrylate after acidification, and phosphoric acid, potassium nitrate and magnesium nitrate the aqueous solution, kneading, after shaping,
Drying process, calcination process obtains containing zinc oxide-alumina composite carrier.
Fixed bed reactors of the present invention, are fixed bed adiabatic reactor or fixed bed isothermal reactor, preferably solid
Fixed bed isothermal reactor.
Described isobutene oligomerisation reaction, its process conditions is：160-220 DEG C of reaction temperature, reaction pressure 1.0-
6.5MPa, volume space velocity 2.0-10.0h-1；
180-200 DEG C of preferable reaction temperature, reaction pressure 2.5-4.5MPa, volume space velocity 4.0-7.0h-1。
It is preferred that catalyst composition with oxidation material gauge, the complex carrier 84.0- containing zinc oxide-alumina
95.0wt%, active component ferric sulfate 4.0-10.0wt%, nickel sulfate 1.0-6.0wt%；
It is preferred that, the composition of described complex carrier is with oxidation material gauge：Zinc oxide content containing gahnite is
10.0-35.0wt%, alumina content is 65.0-90.0wt%, and the content of adjuvant component phosphorus, potassium and magnesium accounts for the hundred of carrier quality
Point content is respectively P2O50.2-1.2wt%, K2O0.4-1.5wt%, MgO 0.4-1.5wt%, complex carrier specific surface area
200-300m2/g。
Drying of the present invention, roasting obtains catalyst, is roasted at being dried 6 hours, 400-600 DEG C preferably at 120 DEG C
Burn 6-8 hours.
The described zinc oxide stratified material prepared containing gahnite, is preferably prepared by the following preparation method：Will
Soluble Zn salting liquid is divided into 2-4 parts, under the conditions of 40-80 DEG C, and sodium metaaluminate and sodium carbonate are added in a zinc solution
Mixed solution containing aluminium, stops that mixed solution containing aluminium is added dropwise when pH value reaches 8.5-9.5；Be further continued for be added dropwise another zinc salt it is molten
Liquid；After zinc solution is dripped, continue that mixed solution containing aluminium is added dropwise, stop being added dropwise containing aluminium mixing when pH value reaches 8.5-9.5
Solution；It will contain aluminium mixed solution according to the above method and replace titration with zinc solution, until the whole completion of dropping of zinc solution, finally
Mixed solution containing aluminium is once added dropwise, when pH value reaches 8.5-9.5, the alternating titration process of non-constant pH value terminates, control drop
Determine process to complete in 1-6h；After 80-95 DEG C of aging 2-8h, cooling washing is to neutrality, in 80-140 DEG C of dry 4-10h,
450-550 DEG C of roasting 4-10h, obtains the dispersed zinc oxide stratified material containing gahnite.
The soluble zinc salt is zinc nitrate or zinc chloride.
The acid solution containing Sodium Polyacrylate after described nitric acid acidification, is preferably prepared by the following preparation method：
Deionized water is heated to 30-90 DEG C, then nitric acid is dissolved into deionized water, Sodium Polyacrylate is added, and dissolved
Entirely, the acid solution containing Sodium Polyacrylate is obtained.The addition of described Sodium Polyacrylate is preferably the 0.6- of boehmite
12.0wt%.The Sodium Polyacrylate of acidified processing, its is uniformly dispersed more preferably, and zinc oxide, alumina powder mixing are more
Uniformly.
The addition of the sesbania powder is preferably the 0.2-7.0wt% of boehmite.
Described drying process, calcination process is roasted at preferably 110-150 DEG C drying process 4-8 hours, 550 DEG C -700 DEG C
Burn processing 4.5-8 hours.
The complex carrier containing zinc oxide-alumina obtained using preparation method of the present invention, can also using potassium and
Magnesium is modified to the complex carrier surface containing zinc oxide-alumina, and the concentration of potassium and magnesium is unsuitable too high, preferably configuration concentration
Carrier surface is sprayed less than the potassium nitrate and magnesium nitrate aqueous solution when preparing complex carrier, carrier is preferably carried out as follows
Surface is modified：Complex carrier of the aqueous solution spray containing zinc oxide-alumina containing potassium nitrate and magnesium nitrate is configured, through drying, roasting
The zinc oxide-alumina complex carrier for obtaining used additives potassium and magnesium progress surface modification is burnt, control zinc oxide-alumina is compound to be carried
Potassium oxide and content of magnesia are respectively in the range of 0.2-2.0wt% and 0.2-2.0wt%, and aoxidize carrier surface in body
The content of potassium and magnesia is 1.4-1.5 times of internal oxidation potassium and content of magnesia.
Compared with prior art, the present invention has advantages below：
1st, the method for isobutene oligomerisation of the present invention, reaction condition is gentle, and isobutene conversion is high, the choosing of target dimer
Selecting property is good, and reaction stability is good, and long period reactivity worth is good.
2nd, the zinc oxide containing gahnite of the invention is that alternately prepared by titration by non-constant pH, i.e., in non-constant pH
Prepared by the alternating titration of sodium carbonate liquor and zinc-containing solution under the conditions of value, containing aluminium, accordingly, it would be desirable to which zinc-containing solution is divided into number
Part, the sodium carbonate liquor containing aluminium is strong alkali solution, and the strong acid weak base salting liquid containing zinc is between acid solution, aluminium zinc solution
Repeatedly alternately titration pH value is swung between soda acid, be conducive to aluminium zinc precursor thing can orderly accumulation be layer structure, through straight
Connect that low-temperature bake can be uniformly dispersed and specific surface area can be in 150-220m2The point containing zinc-aluminium regulated and controled between/g is brilliant
The zinc oxide material of stone, it is to avoid the precursor obtained using the step of alkaline solution one titration zinc-aluminium mixed solution needs high-temperature roasting
The problem of fixed zinc oxide, decrease hydrothermal treatment process.The material has larger specific surface area.
2nd, the present invention can also introduce phosphorus, potassium, magnesium and Sodium Polyacrylate, poly- third in zinc oxide-alumina complex carrier
Olefin(e) acid sodium can repair that to improve diffusion effect in catalytic inner pore passage structure, catalyst good.It is neat that the carrier is prepared into isobutene
Poly- catalyst, such as catalyst for oligomerization, are conducive to adjusting the acidity of catalyst for oligomerization, and catalytic inner duct knot is improved in finishing
Structure, suppresses catalytic inner carbon deposit, improves the stability of isobutene oligomerisation catalyst.
What the 3rd, the present invention was obtained contains zinc oxide-alumina composite carrier, and surface makes carrier table after potassium and magnesium modification
The content of the potassium in face and the concentration of magnesium and the concentration formation concentration difference of carrier inside potassium and magnesium, carrier surface potassium and magnesium is higher than carrier
The content of internal potassium and magnesium, i.e., the molar content or mass content of outside potassium and magnesium can be the 1.4- of the content of internal potassium and magnesium
1.5 times, it carrier surface is tended to equally distributed state, reduce the acidity of carrier surface, the carrier can be improved
The specific surface area of catalyst.Improvement to carrier surface should not use dipping method, and impregnated carrier surface can enter large quantity of moisture
Carrier, intensity is deteriorated, and does not reach the purpose for improving carrier surface Jie-macropore ratio.To complex carrier table by the way of spray
Face is modified, and is capable of the partial pore on effective peptization complex carrier surface, is so advantageously reduced the micro- of complex carrier surface
Boring ratio example, improves complex carrier surface Jie-macropore ratio, promotes complex carrier surface to produce in more active sites loads
The heart, effectively improves catalyst activity.
4th, carrier surface of the present invention is through potassium and magnesium modification, and the complex carrier containing zinc oxide-alumina can be made
To be used for isobutene oligomerisation reaction after the carrier loaded active component of isobutene oligomerisation catalyst.
Embodiment
Carried out by the following examples with the comparative example oligomerization for isobutene a kind of to the present invention further detailed
Describe in detail bright.But these embodiments are not regarded as limiting of the invention.
Analysis method and standard：
Raw material and product form analysis method：Gas chromatography.
Primary raw material used by catalyst is prepared to originate：Reagent of the present invention is commercially available prod.
Feedstock oil is isobutene raw material, and isobutene content is more than 80%.
Embodiment 1
1.2kg zinc nitrates are dissolved in 6L water and are made into zinc-containing solution, by 0.24kg sodium metaaluminates and 0.30kg sodium carbonate
It is dissolved in 4L water and is made into containing aluminum solutions.Zinc-containing solution is divided into 3 parts, every part of 2L.2L zinc-containing solutions are taken, temperature keeps 80
DEG C, mixed solution containing aluminium to pH value is added dropwise thereto and reaches 9.0；Stop that mixed solution containing aluminium is added dropwise, then 2L zinc-containing solutions are added dropwise
Into hybrid system, continue dropwise addition mixed solution containing aluminium to pH value and reach 9.0；Mixed solution containing aluminium and zinc-containing solution alternately drip
Fixed, until zinc-containing solution is all added, last time is added dropwise mixed solution containing aluminium and reaches 9.0 to pH, and titration time amounts to 3h.
The mixture arrived is after 80 DEG C of aging 4h, and cooling washing dries 3h to neutrality in 135 DEG C of air atmospheres, in 500 DEG C of roastings
9h, obtains the dispersed zinc oxide stratified material containing gahnite, in terms of oxide, the content 65% of zinc oxide；Than
Surface area is 196m2/g。
Phosphatase 11 .04g, potassium nitrate 1.03g are weighed respectively, and magnesium nitrate 8.88g, which is dissolved completely in be made into 60g distilled water, to be contained
Phosphorus, potassium, the aqueous solution of magnesium.6.0g Sodium Polyacrylates are dissolved in 70g distilled water, add the nitre that 3.8g mass concentrations are 65%
Acid.Zinc oxide of the 40g containing gahnite and 164.3g boehmites ground and mixed is uniform, 6.0g sesbania powders are added,
Sodium Polyacrylate acid solution, phosphorous, potassium, the aqueous solution of magnesium, kneading after shaping, is roasted at 125 DEG C of drying process 7 hours, 580 DEG C
Burn processing and obtain the complex carrier containing zinc oxide-alumina in 7 hours.Complex carrier specific surface area 276m2/g.Complex carrier includes
Zinc oxide 25.0wt% containing gahnite, aluminum oxide is 71.9wt%, and adjuvant component phosphorus, potassium, content of magnesium are respectively P2O5
0.4wt%, K2O 1.2wt%, MgO1.5wt%.
The water ferric sulfate of 12.7g six is taken, 11.1g nickel sulfate hexahydrates are added in 30ml distilled water, then diluted with deionized water,
Maceration extract complex carrier 100g of the dipping containing zinc oxide-alumina is made into, obtained catalyst precursor is after 120 DEG C dry 6h
6h is calcined at 450 DEG C, isobutene oligomerisation catalyst 1 is obtained.Catalyst 1 is mainly constituted：Ferric sulfate 10.0wt%, nickel sulfate
2.5wt%, the complex carrier 87.5wt% containing zinc oxide-alumina.
By catalyst 1 and the small porcelain balls 1 of φ 1mm:It is fitted into after 1 mixing in 100ml fixed bed reactors, filling order is φ
The small porcelain balls of 1mm, catalyst porcelain ball mixture, the small porcelain balls of φ 1mm, after Catalyst packing is finished, carry out airtight experiment, airtight qualified
After start into isobutene raw material, and carry out under certain process conditions isobutene oligomerisation reaction.
The process conditions of isobutene oligomerisation reaction are：175 DEG C of reaction temperature, reaction pressure 3.0MPa, volume space velocity 5.0h-1.Sampling analysis after about 55h is reacted, the reactor product property of catalyst 1 is as follows：The conversion ratio of isobutene is 97.6%, dimer
Selectivity is 71.3%, and the selectivity of trimer is 28.4%.The reactivity of catalyst is suitable, and dimer selectivity is high, instead
Answer mild condition.Reaction operation 500h, the conversion ratio of isobutene is 95.4%, and the selectivity of dimer is 72.4%, trimer
Selectivity be 27.0%.Long-term operation result shows：The activity stability of the catalyst reaction of non-surface modification slightly has
Decline, overall performance is still good.
Comparative example 1
Zinc nitrate solution, sodium metaaluminate and the sodium carbonate liquor of amount same as Example 1 are well mixed by blending method, with reality
Apply the zinc-aluminium mol ratio of example 1 identical, similarity condition aging, washing, drying, roasting obtain the oxide material containing zinc-aluminium.Zinc oxide
Content be 65%；Specific surface area is 141m2/g.Compared with comparative example 1, embodiment 1 is using pH swing methods zinc, the friendship of aluminum solutions
For titration, zinc-aluminium stratified material can be obtained, in two kinds of material zinc-aluminium mol ratios under the same conditions, embodiment 1 is containing zinc-aluminium point
The specific surface area of the zinc oxide stratified material of spar is higher.
Phosphatase 11 .04g, potassium nitrate 1.03g are weighed respectively, and magnesium nitrate 8.88g, which is dissolved completely in be made into 60g distilled water, to be contained
Phosphorus, potassium, the aqueous solution of magnesium.6.0g Sodium Polyacrylates are dissolved in 70g distilled water, add the nitre that 3.8g mass concentrations are 65%
Acid.Oxide materials of the 40g containing zinc-aluminium and 164.3g boehmites ground and mixed is uniform, 6.0g sesbania powders are added, are gathered
PAA acid solution, phosphorous, potassium, the aqueous solution of magnesium, kneading after shaping, is calcined at 125 DEG C of drying process 7 hours, 580 DEG C
Processing obtains carrier in 7 hours.The water ferric sulfate of 12.7g six is taken, 11.1g nickel sulfate hexahydrates are added in 30ml distilled water, then are spent
Ionized water dilutes, and is made into maceration extract complex carrier 100g of the dipping containing zinc oxide-alumina, and obtained catalyst precursor exists
6h is calcined at 450 DEG C after 120 DEG C of drying 6h, comparative catalyst 1 is obtained.
By comparative catalyst 1 and the small porcelain balls 1 of φ 1mm:It is fitted into after 1 mixing in 100ml fixed bed reactors, filling order is
The small porcelain balls of φ 1mm, catalyst porcelain ball mixture, the small porcelain balls of φ 1mm, after Catalyst packing is finished, carry out airtight experiment, airtight to close
Start after lattice into isobutene raw material, and carry out under certain process conditions isobutene oligomerisation reaction.
The process conditions of isobutene oligomerisation reaction are：175 DEG C of reaction temperature, reaction pressure 3.0MPa, volume space velocity 5.0h-1.Sampling analysis after about 55h is reacted, the reactor product property of comparative catalyst 1 is as follows：The conversion ratio of isobutene is 88.6%, dimerization
The selectivity of thing is 62.5%, and the selectivity of trimer is 34.2%.The reactivity of catalyst is relatively low, dimer selectivity
It is low.Reaction operation 500h, the conversion ratio of isobutene is 78.4%, and the selectivity of dimer is 64.4%, the selectivity of trimer
For 33.7%.
Embodiment 2
The preparation method and step be the same as Example 1 of complex carrier containing zinc oxide-alumina, are prepared containing gahnite
Zinc oxide, pH value is adjusted to 8.7.In terms of oxide, the content of zinc oxide is 70%；Specific surface area is 191m2/g。
Complex carrier includes the zinc oxide 30wt% containing gahnite, and aluminum oxide is 68wt%, adjuvant component phosphorus, potassium,
Content of magnesium is respectively P2O50.6wt%, K2O 0.8wt%, MgO 0.6wt%.
Except that obtaining after complex carrier, table is carried out to the complex carrier containing zinc oxide-alumina using potassium and magnesium
Face is modified, and detailed process comprises the following steps：Configuration, as maceration extract, weighs nitric acid respectively containing potassium nitrate and magnesium nitrate aqueous solution
Potassium 1.2g, magnesium nitrate 10.7g, are dissolved completely in 30ml distilled water, then with deionized water dilution wiring solution-forming spray zinc oxide-
The complex carrier of aluminum oxide, obtains used additives potassium through drying, roasting and magnesium carries out the compound load of zinc oxide-alumina of surface modification
Body.Complex carrier specific surface area 238m2/g。
Six water ferric sulfate are taken, nickel sulfate hexahydrate is added in 30ml distilled water, then diluted with deionized water, is made into maceration extract
The complex carrier 100g containing zinc oxide-alumina is impregnated, obtained catalyst precursor is roasted after drying 6h at 130 DEG C at 500 DEG C
6h is burnt, isobutene oligomerisation catalyst 1 is obtained.Catalyst 1 is mainly constituted：Ferric sulfate 8.0wt%, nickel sulfate 3.0wt%, containing oxidation
The complex carrier 93.0wt% of zinc-aluminum oxide.
By catalyst 2 and the small porcelain balls 1 of φ 1mm:It is fitted into after 1 mixing in 100ml fixed bed reactors, filling order is φ
The small porcelain balls of 1mm, catalyst porcelain ball mixture, the small porcelain balls of φ 1mm, after Catalyst packing is finished, carry out airtight experiment, airtight qualified
After start into isobutene raw material, and carry out under certain process conditions isobutene oligomerisation reaction.
The process conditions of isobutene oligomerisation reaction are：190 DEG C of reaction temperature, reaction pressure 3.0MPa, volume space velocity 6.0h-1.Sampling analysis after about 55h is reacted, the reactor product property of catalyst 2 is as follows：The conversion ratio of isobutene is 99.4%, dimer
Selectivity is 71.6%, and the selectivity of trimer is 28.7%.The reactivity of catalyst is suitable, and dimer selectivity is high, instead
Answer mild condition.Reaction operation 500h, the conversion ratio of isobutene is 98.5%, and the selectivity of dimer is 72.8%, trimer
Selectivity be 27.9%.Long-term operation result shows：The activity stability of catalyst reaction is good, and service cycle is long.
Embodiment 3
The preparation method and step be the same as Example 1 of complex carrier containing zinc oxide-alumina.Prepare containing gahnite
Zinc oxide, pH value is adjusted to 9.3.Zinc oxide containing gahnite, in terms of oxide, the content of zinc oxide is 63%；Compare table
Area is 214m2/g。
Complex carrier includes the zinc oxide 18.3wt% containing gahnite, and aluminum oxide is 79wt%, adjuvant component phosphorus,
Potassium, content of magnesium are respectively P2O50.9wt%, K2O 0.8wt%, MgO 1.0wt%.Complex carrier specific surface area 242m2/g。
Six water ferric sulfate are taken, nickel sulfate hexahydrate is configured to maceration extract, impregnates the complex carrier containing zinc oxide-alumina
100g, specific steps are with embodiment 1.Catalyst is calcined 7.0h after 130 DEG C of drying 7h at 550 DEG C, obtains isobutene oligomerisation
Catalyst 3.Catalyst 3 is mainly constituted：Ferric sulfate 6.0wt%, nickel sulfate 1.5wt%, the complex carrier containing zinc oxide-alumina
92.5wt%.
By catalyst 3 and the small porcelain balls 1 of φ 1mm:It is fitted into after 1 mixing in 100ml fixed bed reactors, filling order is φ
The small porcelain balls of 1mm, catalyst porcelain ball mixture, the small porcelain balls of φ 1mm, after Catalyst packing is finished, carry out airtight experiment, airtight qualified
After start into isobutene raw material, and carry out under certain process conditions isobutene oligomerisation reaction.
The process conditions of isobutene oligomerisation reaction are：195 DEG C of reaction temperature, reaction pressure 4.0MPa, volume space velocity 4.0h-1.Sampling analysis after about 55h is reacted, the reactor product property of catalyst 3 is as follows：The conversion ratio of isobutene is 97.9%, dimer
Selectivity is 72.0%, and the selectivity of trimer is 28.5%.The reactivity of catalyst is suitable, and dimer selectivity is high, instead
Answer mild condition.Reaction operation 500h, the conversion ratio of isobutene is 95.2%, and the selectivity of dimer is 72.6%, trimer
Selectivity be 28.1%.Long-term operation result shows：The activity stability of the catalyst reaction of non-surface modification slightly has
Decline, overall performance is still good.
Embodiment 4
The preparation method and step be the same as Example 1 of complex carrier containing zinc oxide-alumina, are prepared containing gahnite
Zinc oxide, pH value is adjusted to 8.6.Zinc oxide containing gahnite, in terms of oxide, the content of zinc oxide is 75%；Compare table
Area is 213m2/g。
Complex carrier includes the zinc oxide 22.9wt% containing gahnite, and aluminum oxide is 74.5wt%, adjuvant component phosphorus,
Potassium, content of magnesium are respectively P2O51.1wt%, K2O 0.5wt%, MgO 1.0wt%.Complex carrier specific surface area 256m2/g。
Six water ferric sulfate are taken, nickel sulfate hexahydrate is configured to maceration extract, impregnates the complex carrier containing zinc oxide-alumina
100g, specific steps are with embodiment 1.Catalyst is calcined 8.0h after 130 DEG C of drying 4h at 550 DEG C, obtains isobutene oligomerisation
Catalyst 3.Catalyst 3 is mainly constituted：Ferric sulfate 7.0wt%, nickel sulfate 3.5wt%, the complex carrier containing zinc oxide-alumina
89.5wt%.
By catalyst 4 and the small porcelain balls 1 of φ 1mm:It is fitted into after 1 mixing in 100ml fixed bed reactors, filling order is φ
The small porcelain balls of 1mm, catalyst porcelain ball mixture, the small porcelain balls of φ 1mm, after Catalyst packing is finished, carry out airtight experiment, airtight qualified
After start into isobutene raw material, and carry out under certain process conditions isobutene oligomerisation reaction.
The process conditions of isobutene oligomerisation reaction are：200 DEG C of reaction temperature, reaction pressure 4.0MPa, volume space velocity 7.0h-1.Sampling analysis after about 55h is reacted, the reactor product property of catalyst 4 is as follows：The conversion ratio of isobutene is 99.3%, dimer
Selectivity is 68.4%, and the selectivity of trimer is 31.5%.The reactivity of catalyst is suitable, and dimer selectivity is high, instead
Answer mild condition.Reaction operation 500h, the conversion ratio of isobutene is 95.7%, and the selectivity of dimer is 70.2%, trimer
Selectivity be 31.1%.Long-term operation result shows：The activity stability of the catalyst reaction of non-surface modification slightly has
Decline, overall performance is still good.
Embodiment 5
The preparation method and step be the same as Example 1 of complex carrier containing zinc oxide-alumina, are prepared containing gahnite
Zinc oxide, pH value is adjusted to 8.7.Zinc oxide containing gahnite, in terms of oxide, the content of zinc oxide is 67%；Compare table
Area is 191m2/g。
Complex carrier includes the zinc oxide 30wt% containing gahnite, and aluminum oxide is 68wt%, adjuvant component phosphorus, potassium,
Content of magnesium is respectively P2O50.5wt%, K2O 1.0wt%, MgO 0.5wt%.
Except that obtaining after complex carrier, table is carried out to the complex carrier containing zinc oxide-alumina using potassium and magnesium
Face is modified, and detailed process comprises the following steps：Configuration is containing potassium nitrate and the compound load of magnesium nitrate aqueous solution spray zinc oxide-alumina
Body so that the content of carrier outside potassium and magnesium is 1.5 times of the content of internal potassium and magnesium.Used additives potassium is obtained through drying, roasting
The zinc oxide-alumina complex carrier of surface modification, complex carrier specific surface area 279m are carried out with magnesium2/g。
Six water ferric sulfate are taken, nickel sulfate hexahydrate is configured to maceration extract, impregnates the complex carrier containing zinc oxide-alumina
100g, specific steps are with embodiment 1.Catalyst is calcined 4.0h after 130 DEG C of drying 8h at 600 DEG C, obtains isobutene oligomerisation
Catalyst 5.Catalyst 5 is mainly constituted：Ferric sulfate 5.0wt%, nickel sulfate 5.5wt%, the complex carrier containing zinc oxide-alumina
89.5wt%.
By catalyst 5 and the small porcelain balls 1 of φ 1mm:It is fitted into after 1 mixing in 100ml fixed bed reactors, filling order is φ
The small porcelain balls of 1mm, catalyst porcelain ball mixture, the small porcelain balls of φ 1mm, after Catalyst packing is finished, carry out airtight experiment, airtight qualified
After start into isobutene raw material, and carry out under certain process conditions isobutene oligomerisation reaction.
The process conditions of isobutene oligomerisation reaction are：190 DEG C of reaction temperature, reaction pressure 4.0MPa, volume space velocity 4.0h-1.Sampling analysis after about 55h is reacted, the reactor product property of catalyst 5 is as follows：The conversion ratio of isobutene is 98.8%, dimer
Selectivity is 71.4%, and the selectivity of trimer is 29.0%.The reactivity of catalyst is suitable, and dimer selectivity is high, instead
Answer mild condition.Reaction operation 500h, the conversion ratio of isobutene is 97.2%, and the selectivity of dimer is 72.0%, trimer
Selectivity be 28.3%.Long-term operation result shows：The activity stability of catalyst reaction is good, and service cycle is long.
Certainly, the present invention can also have other various embodiments, ripe in the case of without departing substantially from spirit of the invention and its essence
Various corresponding changes and deformation, but these corresponding changes and deformation can be made according to the present invention by knowing those skilled in the art
Protection scope of the present invention should all be belonged to.
Claims (10)
1. a kind of oligomerization of isobutene, it is characterised in that comprise the following steps：
By treated ferric sulfate-sulfuric acid ni-type Catalyst packing in fixed bed reactors, start after airtight experiment is qualified
Enter the raw material containing isobutene, oligomerisation reaction is carried out under reaction process condition, reactor product carries out chromatography；
Described catalyst active center is ferric sulfate and nickel sulfate, and catalyst carrier is the compound load containing zinc oxide-alumina
Body, the composition of catalyst is with oxidation material gauge, including following component：Complex carrier 80.0- containing zinc oxide-alumina
97.0wt%, active component ferric sulfate 2.0-12.0wt%, nickel sulfate 1.0-8.0wt%；
The preparation method of described catalyst, comprises the following steps：
Ferric sulfate and nickel sulfate soluble-salt are made into maceration extract, the complex carrier containing zinc oxide-alumina is impregnated, dried, roasting
Burning obtains catalyst；
The described complex carrier containing zinc oxide-alumina, including the zinc oxide containing gahnite, aluminum oxide, adjuvant component
Phosphorus, potassium and magnesium, the composition of complex carrier is with oxidation material gauge：Zinc oxide content containing gahnite is 5.0-
40.0wt%, alumina content is 60.0-95.0wt%, and the percentage that the content of adjuvant component phosphorus, potassium and magnesium accounts for carrier quality contains
Amount is respectively P2O50.2-1.2wt%, K2O 0.2-2.0wt%, MgO 0.2-2.0wt%, complex carrier specific surface area 200-
300m2/g；
The described complex carrier containing zinc oxide-alumina, the method for being prepared by the following procedure is obtained：
Soluble salt solutions and zinc-containing solution containing aluminium are alternately titrated by non-constant pH, the oxygen containing gahnite is prepared
Change zinc stratified material；Zinc oxide and boehmite containing gahnite are well mixed, sesbania powder, nitric acid acidifying is added
The acid solution containing Sodium Polyacrylate after processing, and phosphoric acid, potassium nitrate and magnesium nitrate the aqueous solution, kneading, after shaping, dry
Processing, calcination process obtains containing zinc oxide-alumina composite carrier.
2. a kind of oligomerization of isobutene according to claim 1, it is characterised in that：Described fixed bed reactors,
For fixed bed adiabatic reactor or fixed bed isothermal reactor.
3. a kind of oligomerization of isobutene according to claim 1, it is characterised in that：Described isobutene oligomerisation is anti-
Should, its process conditions is：160-220 DEG C of reaction temperature, reaction pressure 1.0-6.5MPa, volume space velocity 2.0-10.0h-1。
4. a kind of oligomerization of isobutene according to claim 3, it is characterised in that：Described isobutene oligomerisation is anti-
Should, its process conditions is：180-200 DEG C of reaction temperature, reaction pressure 2.5-4.5MPa, volume space velocity 4.0-7.0h-1。
5. a kind of oligomerization of isobutene according to claim 1, it is characterised in that：Described catalyst, including such as
Lower component：Complex carrier 84.0-95.0wt% containing zinc oxide-alumina, active component ferric sulfate 4.0-10.0wt%, sulfuric acid
Nickel 1.0-6.0wt%；Described complex carrier, is constituted with oxidation material gauge：Zinc oxide content containing gahnite is
10.0-35.0wt%, alumina content is 65.0-90.0wt%, and the content of adjuvant component phosphorus, potassium and magnesium accounts for the hundred of carrier quality
Point content is respectively P2O50.2-1.2wt%, K2O 0.4-1.5wt%, MgO 0.4-1.5wt%, complex carrier specific surface area
200-300m2/g。
6. a kind of oligomerization of isobutene according to claim 1, it is characterised in that：Described prepares containing zinc-aluminium point
The zinc oxide stratified material of spar, is to be prepared by the following preparation method：Soluble Zn salting liquid is divided into 2-4 parts, 40-80 DEG C
Under the conditions of, the mixed solution containing aluminium of sodium metaaluminate and sodium carbonate is added in a zinc solution, when pH value reaches 8.5-9.5
Stop that mixed solution containing aluminium is added dropwise；It is further continued for that another zinc solution is added dropwise；After zinc solution is dripped, continue to be added dropwise and mixed containing aluminium
Solution is closed, stops that mixed solution containing aluminium is added dropwise when pH value reaches 8.5-9.5；It will contain aluminium mixed solution and zinc salt according to the above method
Solution is alternately titrated, until the whole completion of dropping of zinc solution, mixed solution containing aluminium is added dropwise in last time, when pH value reaches 8.5-
When 9.5, the alternating titration process of non-constant pH value terminates, and control titration process is completed in 1-6h；In 80-95 DEG C of aging 2-8h
Afterwards, cooling washing is to neutrality, in 80-140 DEG C of drys 4-10h, 450-550 DEG C of roasting 4-10h, obtains dispersed containing zinc-aluminium
The zinc oxide stratified material of spinelle；The soluble zinc salt is zinc nitrate or zinc chloride.
7. a kind of oligomerization of isobutene according to claim 1, it is characterised in that：After described nitric acid acidification
The acid solution containing Sodium Polyacrylate, be to be prepared by the following preparation method：Deionized water is heated to 30-90 DEG C, then will
Nitric acid is dissolved into deionized water, adds Sodium Polyacrylate, and dissolves complete, obtains the acid solution containing Sodium Polyacrylate.
8. a kind of oligomerization of isobutene according to claim 1, it is characterised in that：Described Sodium Polyacrylate plus
Enter the 0.6-12wt% that amount is boehmite；The addition of the sesbania powder is the 0.2-7wt% of boehmite.
9. a kind of oligomerization of isobutene according to claim 1, it is characterised in that：Described drying, roasting is obtained
Catalyst, is that roasting obtains catalyst for oligomerization in 6-8 hours at being dried 6 hours, 400-600 DEG C at 120 DEG C；At described drying
Reason, calcination process is calcination process 4.5-8 hours at 110-150 DEG C of drying process 4-8 hours, 550 DEG C -700 DEG C.
10. a kind of oligomerization of isobutene according to claim 1, it is characterised in that：Described contains zinc oxide-oxidation
The complex carrier of aluminium, is modified to the complex carrier surface containing zinc oxide-alumina using potassium and magnesium, entered as follows
Row carrier surface modification：Complex carrier of the aqueous solution spray containing zinc oxide-alumina containing potassium nitrate and magnesium nitrate is configured, through dry
Dry, roasting obtains used additives potassium and magnesium carries out the zinc oxide-alumina complex carrier of surface modification, controls zinc oxide-alumina
Potassium oxide and content of magnesia are respectively in the range of 0.2-2.0wt% and 0.2-2.0wt%, and make carrier table in complex carrier
The content of face potassium oxide and magnesia is 1.4-1.5 times of internal oxidation potassium and content of magnesia.
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