CN107159278A - A kind of method of olefin(e) oligomerization - Google Patents

Abstract

The invention discloses a kind of method of olefin(e) oligomerization, using fixed bed reactors；The catalyst is ferric sulfate and nickel sulfate loaded catalyst, and carrier is the aluminum oxide with macroporous structure, and its oligomerization process condition is：165 215 DEG C of reaction temperature, the 6.0MPa of reaction pressure 1.2, the 9.8h of volume space velocity 2.2^‑1.Oligomerisation reaction process conditions are gentle, under conditions of olefin conversion is higher, and dimer selectivity is high, and trimer is selectively low, and the activity stability of catalyst is good.

Description

A kind of method of olefin oligomerization

technical field

The invention relates to a method for olefin oligomerization, and more specifically uses an olefin oligomerization catalyst supported by alumina with a macroporous structure for the olefin oligomerization reaction.

Background technique

Oligomerization of low-carbon olefins is one of the important chemical processes in oil refining and organic chemical industry. The oligomerization product of butene is an important chemical intermediate, which can be used to produce oligomerized gasoline and diesel oil, as well as detergent, Important intermediates for plasticizers, additives and pesticides. Butene oligomerization catalysts mainly include Ziggler-type homogeneous catalysts, solid phosphoric acid catalysts, zeolite molecular sieve catalysts, and supported catalysts.

The composite material of zinc oxide and aluminum oxide is often used as the carrier material of the catalyst and has a wide range of applications. Spinel-type composite oxides are a kind of promising inorganic non-metallic materials, which have a series of good characteristics and are widely used in high-temperature materials, catalysts and catalyst supports and other fields. The common preparation methods of this material at home and abroad include impregnation method, mechanical mixing method, co-precipitation method and peptization method. Among them, since the impregnation method and the mechanical mixing method use alumina material as a precursor, by adjusting the specific surface area of the alumina material, these two methods can prepare a composite material with a higher specific surface area, but due to the alumina and oxide in the composite material The zinc interaction is weak, and the loss of zinc oxide is easy to occur during use. Usually, high-temperature roasting is used to promote the formation of spinel to avoid the loss of zinc oxide; while the co-precipitation method and peptization method use aluminum and zinc The compound prepared by precipitation or peptization is used to prepare zinc-aluminum precursors. During the preparation process, aluminum and zinc react to produce a strong interaction to avoid the loss of zinc oxide during use, but the specific surface area of the material prepared by the peptization method is the lowest, so that Its use as a catalytic material is restricted.

European patent EP0371983 uses granular SiO ₂ with a specific surface area of 52m ² /g and a pore size of 60nm as a carrier to prepare a phosphoric acid/SiO ₂ catalyst for olefin oligomerization to produce gasoline.

U.S. Patent No. 4100220, U.S. No. 4463211 have reported to use cationic exchange resin catalyst as the catalyzer of butene oligomerization reaction, but high molecular weight oligomer is easy to block reaction channel, and resin skeleton alkylation can cause its activity to decline faster, in addition the resistance of resin Poor high temperature performance restricts its application. The MOGO process developed by Mobil Company (US4150063 and US4254298) adopts the ZSM-5 molecular sieve catalyst with a silicon-aluminum ratio of 79, and obtains gasoline and diesel-based products by changing the process conditions, but due to oligomerization and cracking copolymerization reactions in the reaction process Existence, product carbon number distribution is too broad, selectivity is poor.

Chinese patent CN1721073A discloses a catalyst suitable for the oligomerization of butene, by using heteroatom ZSM _{- 5} molecular sieve with YO2/M2O3 molar ratio _of 50-200 as the active body of the catalyst, and M is a trivalent element , Y is a catalyst for butene oligomerization of tetravalent elements.

Chinese patent CN104324734A discloses a catalyst preparation method for synthesizing C8 and C12 by oligomerization of butene, using an equal-volume impregnation method to dissolve and impregnate Fe(NO ₃ ) ₃ onto γ-Al ₂ O ₃ , then dry and roast Afterwards, (NH ₄ ) ₂ SO ₄ is dissolved and impregnated on Fe(NO ₃ ) ₃ /γ-Al2O3, dried and calcined to obtain a 1-butene oligomerization catalyst.

In the process of butene oligomerization, it is found that the main problems of the above-mentioned catalysts are: solid acid catalyst SPAC is currently a widely used catalyst in butene oligomerization, but it has muddy, agglomerated, and cannot be regenerated after deactivation; heterogeneous Catalysts have high oligomerization activity and product selectivity, but are easy to deactivate; supported catalysts and ionic liquid catalysts have attracted widespread attention in recent years due to their good reactivity.

Contents of the invention

The invention provides an olefin oligomerization method, which is used for olefin oligomerization to produce dimers. Including the following steps:

Pack the treated ferric sulfate-nickel sulfate catalyst in the fixed bed reactor, start to feed the olefin-containing raw material after the airtight test is passed, carry out the oligomerization reaction under the reaction process conditions, and conduct the chromatographic analysis of the reaction product.

The fixed bed reactor of the present invention is a fixed bed adiabatic reactor or a fixed bed isothermal reactor, preferably a fixed bed adiabatic reactor.

The process conditions of the olefin oligomerization reaction are: reaction temperature 165-215°C, reaction pressure 1.2-6.0MPa, volume space velocity 2.2-9.8h ^-1 ;

Preferably, the reaction temperature is 182-198°C, the reaction pressure is 2.6-4.3MPa, and the volume space velocity is 4.2-6.8h ^-1 .

The catalyst described in the invention is an iron sulfate and nickel sulfate-based catalyst supported on an alumina carrier with a macroporous structure.

The composition of the catalyst includes the following components in terms of oxide mass: 81.0-96.0 wt% of an alumina support with a macroporous structure, 2.5-11.5 wt% of ferric sulfate and 1.5-7.5 wt% of nickel sulfate as active components;

Preferably, the alumina support with a macroporous structure accounts for 85.0-95.0 wt%, the active components include 3.5-11.0 wt% of iron sulfate and 2.5-5.5 wt% of nickel sulfate.

A kind of olefin oligomerization catalyst of the present invention and preparation method, comprise the steps:

Prepare ferric sulfate and nickel sulfate soluble salt as impregnation solution, impregnate alumina support with macroporous structure, dry at 110-130°C for 4-8 hours, and roast at 450°C-600°C for 4-8 hours to obtain olefin oligomerization catalyst;

The alumina carrier with macroporous structure of the present invention uses chitosan as a pore-enlarging agent to synthesize the alumina carrier with macroporous structure.

According to the alumina carrier with macroporous structure in the present invention, the carrier contains auxiliary components phosphorus, lanthanum and potassium, and the contents of the auxiliary components phosphorus, lanthanum and potassium in the mass of the carrier are respectively P ₂ O ₅ 0.1-2.0wt%, La ₂ O ₃ 0.2-2.4wt%; K ₂ O 0.1-2.5wt%, pore size distribution 60-180nm, preferably 65-150nm, macropore ratio 2-75%, preferably 5-65%, The pore volume is 0.8-2.0ml/g, preferably 0.8-1.3ml/g or preferably 1.6-2.0ml/g, the specific surface area is 250-300m ² /g, and the carrier uses chitosan as a pore-expanding agent.

The pore diameter of the alumina carrier with a macropore structure in the present invention can be adjusted by changing the amount of the pore-enlarging agent and the molecular weight of the pore-enlarging agent. The pore size distribution can vary between 60-180nm, such as 60-90nm, 100-160nm, 120-180nm and other ranges. The proportion of macropores is 2-75%, which can be adjusted to 5-30%, 35-50%, 55-75% and other ranges.

The preparation method of the alumina carrier with a macroporous structure of the present invention comprises the following steps: first, acidify chitosan with an acid solution, then add pseudo-boehmite and scallop powder to a kneader and mix evenly, then add phosphoric acid , a mixed solution of lanthanum nitrate and potassium nitrate, and finally add the chitosan-containing acid solution to the pseudo-boehmite powder and knead evenly, and the acid solution containing the pore-enlarging agent is added in an amount of 0.1- 8 wt%, preferably 0.2-5.0 wt%, through extruding-shaping-drying-calcining to obtain an alumina carrier with a macroporous structure.

The process of acidifying chitosan with the acid solution is as follows: first, the chitosan pore-enlarging agent is added to deionized water at 30-95° C., and then the acid is added dropwise until the chitosan is completely dissolved to obtain the acid containing pore-enlarging agent. solution. The acid may be an inorganic acid or an organic acid, preferably acetic acid, formic acid, malic acid, lactic acid and the like. The addition amount of acid is advisable with can dissolving chitosan completely. Water-soluble chitosan can also be selected, such as carboxylated chitosan, chitosan salts, chitosan sulfate and the like. The chitosan acid solution is preferably stirred by ultrasonic vibration or magnetic force. Ultrasonic vibration for more than 10min, magnetic stirring for 0.5-2h. Ultrasonic vibration or magnetic stirring is performed on the pore-enlarging agent, the pore-enlarging agent has good dispersibility, the alumina carrier is more likely to produce large pores, and the pore size distribution is more concentrated, and the pore size distribution is 70-180nm.

The added amount of the scallop powder is 0.1-7wt% of the pseudo-boehmite.

The kneading or extruding process is to add the prepared acid solution containing pore-enlarging agent to the safflower powder and pseudo-boehmite and mix evenly, then extrude, shape, and dry at 100-160°C for 3-9 hours , Calcined at 650-800°C for 4-8 hours, finally obtaining an alumina carrier with a macroporous structure.

The alumina carrier of the present invention uses chitosan as a pore-expanding agent, and the prepared alumina carrier contains a macroporous structure and a mesoporous structure, the mesopore range is 2-50nm, and the mesopore ratio is 15-75%, preferably 15-50%, is an alumina carrier containing meso-macropores, and the pore size is not uniform.

The alumina support with macroporous structure obtained by the above preparation method can also use lanthanum and potassium to modify the surface of the support. The concentration of lanthanum and potassium should not be too high, and it is best to configure the concentration lower than the lanthanum nitrate when preparing the support. Spray the surface of the carrier with potassium nitrate aqueous solution, preferably carry out the modification of the carrier surface by the following steps: configure the aqueous solution containing lanthanum nitrate and potassium nitrate to spray the alumina carrier with macroporous structure, dry and roast to obtain the auxiliary agent lanthanum and potassium A surface-modified alumina carrier, controlling the contents of La ₂ O ₅ and K ₂ O in the alumina carrier with a macroporous structure in the ranges of 0.2-2.4wt% and 0.1-2.5wt% respectively, and making the surface of the carrier The content of La ₂ O ₅ and K ₂ O is 1.2-1.4 times that of internal La ₂ O ₅ and K ₂ O.

Compared with the prior art, the present invention has the following advantages:

1. The alumina carrier of the present invention adopts chitosan as a pore-enlarging agent. The pore-enlarging agent chitosan is cheap, environmentally friendly and non-toxic, and is suitable for industrial production. The obtained alumina support has a macroporous structure, the pore size can be adjusted, and the macropore ratio can be effectively controlled. Moreover, the carrier also contains mesopores, which is a kind of meso-macroporous alumina carrier. The alumina carrier with this structure has better active center dispersion performance, impurity resistance performance and long-term stability in the reaction.

2. The present invention can also introduce phosphorus, lanthanum and potassium into the alumina carrier to obtain an alumina carrier with a macroporous structure. The carrier is prepared as an olefin oligomerization catalyst, which has better oligomerization activity, selectivity and stability sex.

3. The alumina support with macroporous structure obtained in the present invention uses lanthanum and potassium to modify the surface of the alumina support with macroporous structure, and makes the content of _La2O5 and K2O _on the surface of the support _equal to that of the internal La 1.2-1.4 times the content of ₂ O ₅ and K ₂ O. The surface of the carrier is modified by spraying, which can effectively peptize part of the micropores on the surface of the carrier, which is beneficial to reduce the proportion of micropores on the surface of the carrier, increase the ratio of meso-macropores on the surface of the carrier, and promote the generation of more pores on the surface of the carrier. The active site loading center can effectively improve the catalyst activity.

4. The olefin oligomerization catalyst carrier provided by the present invention is an alumina carrier with a meso-macroporous structure. The catalyst oligomerization reaction conditions are mild, the olefin conversion rate is high, the target dimer selectivity is good, the reaction stability is good, and the cycle time is long. Good responsiveness.

Description of drawings

Fig. 1 is the pore size distribution diagram of the alumina support with macroporous structure prepared in Example 3.

detailed description

A method for olefin oligomerization of the present invention will be further described in detail through examples and comparative examples below. However, these examples should not be construed as limiting the invention.

Analysis methods and standards:

Raw material and product composition analysis method: gas chromatography.

Sources of main raw materials used in the preparation of catalysts: the reagents of the present invention are all commercially available products.

The feed oil is an olefin raw material, and the olefin content is greater than 80%.

Example 1

First, 8.0 g of the water-soluble chitosan pore-enlarging agent was added to deionized water at 50° C., and then acetic acid was added dropwise until the chitosan was completely dissolved to obtain an acid solution containing the pore-enlarging agent. Weigh a certain amount of phosphoric acid and potassium nitrate respectively, completely dissolve the phosphoric acid and potassium nitrate in 70 g of distilled water to prepare an aqueous solution containing phosphorus and potassium. Weigh 350g of pseudo-boehmite powder and 20.0g of fennel powder into the kneader, and mix evenly, then add the mixed solution of phosphoric acid, lanthanum nitrate and potassium nitrate, and finally add the acid solution containing chitosan to the pseudo-boehmite The diaspore powder is evenly kneaded, and then kneaded-extruded into a clover shape. Dry at 120° C. for 8 hours, and calcined at 700° C. for 4 hours to obtain an alumina carrier 1 containing phosphorus, lanthanum and potassium. In carrier 1, P ₂ O ₅ is 0.5 wt%, La ₂ O ₃ is 1.2%, and K ₂ O is 1.8 wt%. The specific surface area and pore size distribution of alumina supports with macroporous structure are shown in Table 1.

Take 6.4g of ferric sulfate hexahydrate, 11.1g of nickel sulfate hexahydrate and add them into 30ml of distilled water, then dilute with deionized water, make an impregnating solution to impregnate 100g of alumina carrier with macroporous structure, and obtain the catalyst precursor at 120°C After drying for 6 hours, it was calcined at 450°C for 6 hours to obtain Enene Oligomerization Catalyst 1. The main composition of the catalyst 1 is: 5.0 wt% of iron sulfate, 2.5 wt% of nickel sulfate, and 92.5 wt% of alumina carrier with macroporous structure.

Mix catalyst 1 and φ1mm small ceramic balls 1:1 and put them into a 100ml fixed bed reactor. The filling sequence is φ1mm small ceramic balls, catalyst ceramic ball mixture, and φ1mm small ceramic balls. After the catalyst is filled, conduct an airtight test. After the airtightness is qualified, the olefin raw material is fed in, and the olefin oligomerization reaction is carried out under certain process conditions.

The technological conditions of the olefin oligomerization reaction are: reaction temperature 175°C, reaction pressure 3.0MPa, volume space velocity 5.0h ^-1 . After reacting for about 55 hours, sampling analysis showed that the properties of the reaction product of catalyst 1 were as follows: the conversion rate of olefin was 95.6%, the selectivity of dimer was 72.6%, and the selectivity of trimer was 27.4%. The catalyst has suitable reactivity, high dimer selectivity and mild reaction conditions. The reaction ran for 500 hours, the conversion rate of olefins was 93.4%, the selectivity of dimers was 73.4%, and the selectivity of trimers was 27.0%. The results of long-term operation show that the activity stability of the catalyst without surface modification is slightly reduced, and the overall performance is still good.

Example 2

8.0 g of water-soluble chitosan pore-enlarging agent was added to deionized water at 50° C., and then acetic acid was added dropwise until the chitosan was completely dissolved to obtain an acid solution containing the pore-enlarging agent. Weigh a certain amount of phosphoric acid and potassium nitrate respectively, completely dissolve phosphoric acid, lanthanum nitrate and potassium nitrate in 70 g of distilled water to prepare an aqueous solution containing phosphorus and potassium. Weigh 350g of pseudo-boehmite powder and 20.0g of fenugreek powder into the kneader, and mix evenly, then add the mixed solution of phosphoric acid, lanthanum nitrate and potassium nitrate, and finally add the acid solution containing chitosan to the pseudo-boehmite The boehmite powder is evenly kneaded, and then kneaded-extruded into a clover shape. Dry at 120° C. for 8 hours, and calcined at 700° C. for 4 hours to obtain an alumina carrier 2 containing phosphorus, lanthanum and potassium. In carrier 2, P ₂ O ₅ is 1.5 wt%, La ₂ O ₃ is 0.5%, and K ₂ O is 0.6 wt%.

Then use lanthanum and potassium to modify the surface of the carrier, configure an aqueous solution containing lanthanum nitrate and potassium nitrate to spray the alumina carrier with a macroporous structure, dry at 120°C for 8 hours, and calcinate at 700°C for 4 hours to obtain phosphorus and Potassium surface modified alumina carrier 2, the content of P ₂ O ₅ and K ₂ O on the surface of the carrier is 1.2 times the content of P ₂ O ₅ and K ₂ O inside. The specific surface area and pore size distribution of alumina supports with macroporous structure are shown in Table 1.

Add ferric sulfate hexahydrate and nickel sulfate hexahydrate into 30ml of distilled water, then dilute with deionized water, make an impregnation solution to impregnate 100g of alumina carrier with macroporous structure, and dry the obtained catalyst precursor at 130°C for 6h Calcined at 500°C for 6h to obtain enene oligomerization catalyst 2. Catalyst 2 mainly consists of 8.0 wt% iron sulfate, 3.0 wt% nickel sulfate, and 89.0 wt% alumina carrier with macroporous structure.

Mix catalyst 2 and φ1mm small ceramic balls 1:1 and put them into a 100ml fixed-bed reactor. The filling order is φ1mm small ceramic balls, catalyst ceramic ball mixture, and φ1mm small ceramic balls. After the catalyst is filled, conduct an airtight test. After the airtightness is qualified, the olefin raw material is fed in, and the olefin oligomerization reaction is carried out under certain process conditions.

The technological conditions of the olefin oligomerization reaction are: reaction temperature 190°C, reaction pressure 3.0MPa, volume space velocity 6.0h ^-1 . After reacting for about 55 hours, sampling analysis showed that the properties of the reaction product of catalyst 2 were as follows: the conversion rate of olefin was 99.6%, the selectivity of dimer was 71.3%, and the selectivity of trimer was 28.5%. The catalyst has suitable reactivity, high dimer selectivity and mild reaction conditions. The reaction ran for 500 hours, the conversion rate of olefin was 98.8%, the selectivity of dimer was 72.8%, and the selectivity of trimer was 27.8%. The results of long-term operation show that the catalytic activity is stable, the operation period is long, and the performance is excellent.

Example 3

The preparation method of the carrier was carried out according to Example 1. The difference is that the water-soluble chitosan pore-enlarging agent is replaced by the non-water-soluble chitosan pore-enlarging agent, and the chitosan formic acid solution is stirred with a magnetic stirrer for 30 minutes to obtain the alumina carrier 3 with a macroporous structure. The contents of the additive components phosphorus, lanthanum and potassium in the carrier are respectively _1.2wt % for _P2O5 , _1.5 % for _La2O3 and 1.4wt% for K2O in the weight _of the carrier. Its specific surface area and pore size distribution are shown in Table 1.

Ferric sulfate hexahydrate and nickel sulfate hexahydrate were prepared as an impregnating solution, and 100 g of alumina carrier with a macroporous structure was impregnated. The specific steps were the same as in Example 1. The catalyst was dried at 130°C for 7h and then calcined at 550°C for 7.0h to obtain olefin oligomerization catalyst 3. The main composition of the catalyst 3 is: 6.0 wt% of iron sulfate, 4.5 wt% of nickel sulfate, and 89.5 wt% of alumina carrier with macroporous structure.

Mix the catalyst 3 with φ1mm small ceramic balls 1:1 and put them into a 100ml fixed bed reactor. The filling sequence is φ1mm small ceramic balls, the mixture of catalyst ceramic balls, and φ1mm small ceramic balls. After the catalyst is filled, conduct an airtight test. After the airtightness is qualified, the olefin raw material is fed in, and the olefin oligomerization reaction is carried out under certain process conditions.

The technological conditions of the olefin oligomerization reaction are: reaction temperature 195°C, reaction pressure 4.0MPa, volume space velocity 4.0h ^-1 . After reacting for about 55 hours, sampling and analysis showed that the properties of the reaction product of catalyst 3 were as follows: the conversion rate of olefin was 97.7%, the selectivity of dimer was 72.3%, and the selectivity of trimer was 28.2%. The catalyst has suitable reactivity, high dimer selectivity and mild reaction conditions. The reaction ran for 500 hours, the conversion rate of olefin was 94.2%, the selectivity of dimer was 72.7%, and the selectivity of trimer was 28.1%. The results of long-term operation show that the activity stability of the catalyst without surface modification is slightly reduced, and the overall performance is good.

Example 4

The preparation method of the carrier was carried out according to Example 1. The difference is that the water-soluble chitosan pore-enlarging agent is replaced by a non-water-soluble chitosan pore-enlarging agent, and the chitosan acetic acid solution is ultrasonically oscillated for 15 minutes. An alumina support with a macroporous structure is obtained. _The contents of the auxiliary components phosphorus, lanthanum and potassium in the carrier are respectively 1.0wt% _{of P2O5} , 0.4 _% of _La2O3 and 0.6wt% of K2O in the weight of the carrier. The surface of the support was modified with lanthanum and potassium to obtain a support 4, the content of La ₂ O ₃ and K ₂ O on the surface of the support 4 was 1.4 times the content of La ₂ O ₃ and K ₂ O inside. The specific surface area and pore size distribution of alumina support 4 with macroporous structure are shown in Table 1.

Ferric sulfate hexahydrate and nickel sulfate hexahydrate were prepared as an impregnating solution, and 100 g of alumina carrier with a macroporous structure was impregnated. The specific steps were the same as in Example 1. The catalyst was dried at 130°C for 4h and then calcined at 550°C for 8.0h to obtain olefin oligomerization catalyst 4. The main composition of the catalyst is: 7.0 wt% of iron sulfate, 3.5 wt% of nickel sulfate, and 89.5 wt% of alumina carrier with macroporous structure.

Mix catalyst 4 with φ1mm small ceramic balls 1:1 and put them into a 100ml fixed-bed reactor. The filling sequence is φ1mm small ceramic balls, catalyst ceramic ball mixture, and φ1mm small ceramic balls. After the catalyst is filled, conduct an airtight test. After the airtightness is qualified, the olefin raw material is fed in, and the olefin oligomerization reaction is carried out under certain process conditions.

The technological conditions of olefin oligomerization reaction are: reaction temperature 200°C, reaction pressure 4.0MPa, volume space velocity 7.0h ^-1 . After reacting for about 55 hours, sampling and analysis showed that the properties of the reaction product of catalyst 4 were as follows: the conversion rate of olefin was 99.4%, the selectivity of dimer was 78.4%, and the selectivity of trimer was 27.5%. The catalyst has suitable reactivity, high dimer selectivity and mild reaction conditions. The reaction ran for 500 hours, the conversion rate of olefin was 97.8%, the selectivity of dimer was 78.8%, and the selectivity of trimer was 26.8%. The results of long-term operation show that the activity stability of the catalyst without surface modification is slightly reduced, and the overall performance is still good.

Table 1 Specific surface area and pore size distribution of alumina supports with macroporous structure

Certainly, the present invention also can have other various embodiments, without departing from the spirit and essence of the present invention, those skilled in the art can make various corresponding changes and deformations according to the present invention, but these corresponding changes And deformation should belong to the protection scope of the present invention.

Claims (9)

1. a kind of method of olefin(e) oligomerization, 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 of olefin-containing, 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 carrying alumina with macroporous structure Body, the composition of catalyst is with oxidation material gauge, including following component：Alumina support 81.0- with macroporous structure 96.0wt%, carrier uses chitosan as expanding agent, active component ferric sulfate 2.5-11.5wt%, nickel sulfate 1.5- 7.5wt%；

The preparation method of described catalyst, comprises the following steps：

Ferric sulfate and nickel sulfate soluble-salt are made into maceration extract, alumina support of the dipping with macroporous structure, 110-130 DEG C Calcination process obtains olefin oligomerization catalyst in 4-8 hours at drying process 4-8 hours, 450 DEG C -600 DEG C；

The described alumina support with macroporous structure, the method for being prepared by the following procedure is obtained：

First, acid solution acidified chitosan is used, then boehmite and sesbania powder are added in kneader and are well mixed, then The mixed solution of phosphoric acid, lanthanum nitrate and potassium nitrate is added, the acid solution of chitosan-containing is finally added to boehmite powder Middle to mediate uniform, the addition of the acid solution containing expanding agent is the 0.1-8wt% of boehmite, by extrusion-shaping-dry Dry-roasting, obtains the alumina support with macroporous structure；

Described olefin oligomerization, its process conditions is：165-215 DEG C of reaction temperature, reaction pressure 1.2-6.0MPa, volume Air speed 2.2-9.8h^-1。

2. a kind of method of olefin(e) oligomerization according to claim 1, it is characterised in that：

Described fixed bed reactors, are fixed bed adiabatic reactor or fixed bed isothermal reactor；

Described olefin oligomerization, its process conditions is：182-198 DEG C of reaction temperature, reaction pressure 2.6-4.3MPa, volume Air speed 4.2-6.8h^-1。

3. a kind of method of olefin(e) oligomerization according to claim 1, it is characterised in that：

The composition of described olefin oligomerization catalyst is with oxidation material gauge, including following component, the oxidation with macroporous structure Alumina supporter accounts for 85.0-95.0wt%, active component ferric sulfate 3.5-11.0wt%, nickel sulfate 2.5-5.5wt%；

Described to have containing adjuvant component phosphorus, lanthanum and potassium in macropore alumina supporter, the content of adjuvant component phosphorus, lanthanum and potassium accounts for load The percentage composition of weight is respectively P₂O₅0.1-2.0wt%, La₂O₃0.2-2.4wt% and K₂O 0.1-2.5wt%；

The pore-size distribution 60-180nm of the catalyst, macropore ratio 2-75%, pore volume 0.8-2.0ml/g, specific surface area 250- 300m²/g。

4. a kind of method of olefin(e) oligomerization according to claim 3, it is characterised in that：The oxidation with macroporous structure Alumina supporter, the alumina support with macroporous structure obtained to claim 3, is changed using lanthanum and potassium to carrier surface Property：Alumina support of the aqueous solution spray with macroporous structure containing lanthanum nitrate and potassium nitrate is configured, is used through drying, roasting Auxiliary agent lanthanum and potassium carry out La in the alumina support of surface modification, alumina support of the control with macroporous structure₂O₃And K₂O contains Amount is respectively in the range of 0.2-2.4wt% and 0.1-2.5wt%, and make carrier surface La₂O₃And K₂O content is internal La₂O₃And K₂1.2-1.4 times of O content.

5. a kind of method of olefin(e) oligomerization according to claim 3, it is characterised in that：The aperture of the alumina support point Cloth is in 65-150nm, macropore ratio 5-65%, pore volume 0.8-1.3ml/g.

6. a kind of method of olefin(e) oligomerization according to claim 3, it is characterised in that：；Alumina support also contains simultaneously Meso-hole structure, macropore range is in 2-50nm, mesoporous ratio 15-75%.

7. a kind of method of olefin(e) oligomerization according to claim 1, it is characterised in that：The acid solution acidified chitosan Process is as follows：Chitosan expanding agent is added in 30-95 DEG C of deionized water first, acid is added dropwise afterwards, until chitosan is molten Solution is complete, obtains the acid solution containing expanding agent.

8. a kind of method of olefin(e) oligomerization according to claim 7, it is characterised in that：The acid is acetic acid, formic acid, apple One or more in acid or lactic acid, chitosan acid solution ultrasonic oscillation or magnetic agitation.

9. a kind of method of olefin(e) oligomerization according to claim 2, it is characterised in that：Described fixed bed reactors are solid Fixed bed adiabatic reactor.