CN115178267A - Catalyst for selective oligomerization of mixed butylene and preparation method thereof - Google Patents

Catalyst for selective oligomerization of mixed butylene and preparation method thereof Download PDF

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CN115178267A
CN115178267A CN202210848124.XA CN202210848124A CN115178267A CN 115178267 A CN115178267 A CN 115178267A CN 202210848124 A CN202210848124 A CN 202210848124A CN 115178267 A CN115178267 A CN 115178267A
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catalyst
metal
mixed
carrier
containing active
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刘璇
李寿丽
张川
崔勇
郭虎菲
赵德明
史会兵
王耀伟
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Shandong Chambroad Petrochemicals Co Ltd
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    • 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
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Abstract

The invention provides a catalyst for selective oligomerization of mixed butylene, which takes alumina and/or modified alumina as a carrier; the carrier is loaded with metal-containing active components; the metal-containing active component is one or more oxides of metals in a VIII group; the loading amount of the metal-containing active component in the catalyst is 5-50%. Compared with the prior art, the catalyst provided by the invention can regulate and control the distribution of the C eight and the C dodecene by changing the proportion of the metal-containing active component in the catalyst, so that the high conversion rate of the mixed butene and the high selectivity of the C eight and the C dodecene are realized, and the high added value utilization of the mixed butene is realized.

Description

Catalyst for selective oligomerization of mixed butylene and preparation method thereof
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a catalyst for selective oligomerization of mixed butylene and a preparation method thereof.
Background
With the rapid development of petrochemical industry, the carbon three and carbon four fractions have increasingly abundant capacity in China, and a large amount of carbon four olefins as byproducts in oil refineries and chemical plants have low chemical utilization rate of the carbon four fractions after butadiene and isobutene are extracted, wherein the carbon four fractions comprise 1-butene, cis-2-butene, trans-2-butene and the like. Therefore, how to improve the utilization value of the butenes has become one of the problems to be solved by petrochemical enterprises.
To date, researchers have developed a series of schemes for utilizing isobutene, mainly for producing high-octane gasoline, and in recent years, catalysts for preparing high-carbon olefins by oligomerization of high-concentration olefins and processes thereof have been developed.
At present, the olefin oligomerization process uses a lot of catalysts including solid phosphoric acid catalyst, zeolite molecular sieve catalyst, ziegler type homogeneous catalyst, supported heterogeneous acid catalyst, etc. The solid phosphoric acid catalyst is a widely used catalyst, is generally prepared by taking diatomite as a carrier to load phosphoric acid, can exert catalytic activity only by water participation, and cannot be regenerated after being easily slimed, easily caked and inactivated. The Shanghai petrochemical industry in China patent with publication number CN1318360C discloses a catalyst with MCM-56 molecular sieve as active main body, which solves the problems of easy argillization, low activity and high product selectivity of solid phosphoric acid catalystPoor, but the product is dominated by carbon eight, with an optimum selectivity of 81%, and the selectivity to carbon twelve is not mentioned. Chinese patent publication No. CN1087617A discloses a Ziegler-type homogeneous catalyst, in which the content of decadiene is increased by adjusting the ratio of nickel carboxylate and alkyl aluminum halide, although the reaction conditions are mild, the yields of carbon eight and carbon twelve only account for 60wt%, and the catalyst and the product are not easily separated, and the added alkali solution forms more waste water and waste residue, which increases the post-treatment cost. Chinese patent publication No. CN104324734A using Fe 2 O 3 -SO 4 2- As an active ingredient, gamma-Al 2 O 3 The supported heterogeneous acid catalyst is prepared by taking the supported heterogeneous acid as a carrier, has the characteristics of high reaction activity and simple preparation process, but has excessive acidity, so that the content of tetramer in oligomerization reaction is excessive, the selectivity of dimer and trimer is not high, and the regeneration performance of the catalyst is not mentioned.
In conclusion, the research on the selective oligomerization of low-concentration mixed butene at home and abroad is still in the stage of exploration and attempt, and particularly, the reports related to the catalyst for improving the yield of the carbon dodecene by customization are few.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a catalyst for selective oligomerization of mixed butene and a preparation method thereof, the prepared catalyst has the excellent characteristics of high activity, excellent stability, simple preparation process, renewable and reusable catalyst, low preparation cost of the catalyst, and the like, and the distribution of carbon eight and carbon dodecene can be regulated and controlled by changing the ratio of active components of the catalyst, so as to realize high value-added utilization of mixed butene.
The invention provides a catalyst for selective oligomerization of mixed butylene, which takes alumina and/or modified alumina as a carrier; the carrier is loaded with metal-containing active components; the metal-containing active component is one or more oxides of group VIII metals; the loading amount of the metal-containing active component in the catalyst is 5-50%.
Preferably, the alumina is gamma-Al 2 O 3 (ii) a The modified alumina is phosphorus modified alumina; the mass of the phosphorus-containing substance in the phosphorus-modified alumina is 0.1-10% of the mass of the phosphorus-modified alumina; the phosphorus-containing substance is selected from one or more of phosphoric acid, amine phosphate and metaphosphoric acid.
Preferably, the specific surface area of the carrier is 250 to 400m 2 (ii)/g; the pore volume of the carrier is 0.6-1.2 mL/g.
Preferably, the metal-containing active component comprises an oxide of iron and/or an oxide of nickel; the molar ratio of iron atoms to nickel atoms in the metal-containing active component is (0-10): (10-0).
Preferably, the molar ratio of iron atoms to nickel atoms in the metal-containing active component is (1-4): (4-1).
Preferably, the loading amount of the metal-containing active component in the catalyst is 16-24%.
The invention also provides a preparation method of the catalyst for selective oligomerization of mixed butylene, which comprises the following steps:
dipping the carrier in a solution containing VIII group metal salt, drying and roasting to obtain a catalyst for selective oligomerization of mixed butylene; the carrier is alumina and/or modified alumina.
Preferably, the group VIII metal salt is selected from one or more of nitrate, sulfate, acetate and chloride salts of group VIII metals;
the dipping time is 4-12 h; the drying temperature is 100-150 ℃; the drying time is 1-5 h; the roasting temperature is 500-600 ℃; the roasting time is 2-6 h.
The invention also provides a method for selectively oligomerizing the mixed butylene, which mixes the catalyst for selectively oligomerizing the mixed butylene with the mixed butylene to carry out oligomerization reaction.
Preferably, the mixed butene is a carbon four-cut fraction; the carbon four fraction comprises one or more of 1-butene, cis-2-butene and trans-2-butene; the content of olefin in the four-carbon fraction is more than or equal to 30wt%;
the describedThe temperature of oligomerization reaction is 40-190 ℃; the pressure of oligomerization reaction is 2-7 MPa; the liquid hourly space velocity during the oligomerization reaction is 0.3 to 3h -1 。
The invention provides a catalyst for selective oligomerization of mixed butylene, which takes alumina and/or modified alumina as a carrier; the carrier is loaded with metal-containing active components; the metal-containing active component is one or more oxides of group VIII metals; the loading amount of the metal-containing active component in the catalyst is 5-50%. Compared with the prior art, the catalyst provided by the invention can regulate and control the distribution of the C eight and the C dodecene by changing the proportion of the metal-containing active component in the catalyst, so that the high conversion rate of the mixed butene and the high selectivity of the C eight and the C dodecene are realized, and the high added value utilization of the mixed butene is realized.
Experiments show that the oligomerization method provided by the invention can realize the conversion rate of mixed butylene of 60-80%, the selectivity of octa-carbon olefin of 50-70% and the selectivity of deca-carbon diene of 32-48%.
Drawings
FIG. 1 is a photograph of catalyst F obtained in example 6 according to the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
The invention provides a catalyst for selective oligomerization of mixed butylene, which takes alumina and/or modified alumina as a carrier; the carrier is loaded with metal-containing active components; the metal-containing active component is one or more oxides of group VIII metals; the loading amount of the metal-containing active component in the catalyst is 5-50%.
In the present invention, the sources of all raw materials are not particularly limited, and they may be commercially available.
The catalyst provided by the invention takes alumina and/or modified alumina as a carrier; the alumina is preferably gamma-Al 2 O 3 (ii) a The modified alumina is preferably phosphorus modified alumina; the mass of the phosphorus-containing substance in the phosphorus-modified alumina is preferably 0.1-10%, more preferably 0.1-5%, and even more preferably 0.2-3% of the mass of the phosphorus-modified alumina; the phosphorus-containing substance is preferably one or more of phosphoric acid, amine phosphate and metaphosphoric acid; the specific surface area of the carrier is preferably 250 to 400m 2 (ii) g, more preferably 280 to 350m 2 Per g, more preferably 300 to 350m 2 (iv) g, most preferably 300 to 320m 2 (iv) g; the pore volume of the carrier is preferably 0.6 to 1.2mL/g, more preferably 0.6 to 1mL/g, still more preferably 0.6 to 0.8mL/g, and most preferably 0.6 to 0.7mL/g.
The carrier is loaded with metal-containing active components; the metal-containing active component is one or more oxides of group VIII metals, preferably including iron oxide and/or nickel oxide; the molar ratio of iron atoms to nickel atoms in the metal-containing active component is preferably (0 to 10): (10-0), more preferably (1-4): (4-1); in the embodiment provided by the present invention, the molar ratio of the iron atom to the nickel atom in the metal-containing active component is specifically 2:1 or 1:2; in the present invention, the metal-containing active component preferably further includes an oxide of chromium; the molar ratio of iron atoms, nickel atoms and chromium atoms in the metal-containing active component is preferably (0-10): (10-0): (0 to 10), more preferably (1 to 8): (8-1): (1 to 8), more preferably (1 to 4): (4-1): (1-4); the loading amount of the metal-containing active component in the catalyst is preferably 5-50%, more preferably 15-30%, and most preferably 16-24%.
The invention also provides a preparation method of the catalyst for selective oligomerization of mixed butylene, which comprises the following steps: dipping the carrier in a solution containing VIII group metal salt, drying and roasting to obtain a catalyst for selective oligomerization of mixed butylene; the carrier is alumina and/or modified alumina.
Wherein, the carrier is the same as the above, and is not described in detail herein.
Impregnating the support in a solution containing a group VIII metal salt; the VIII group metal salt is preferably one or more of nitrate, sulfate, acetate and chloride of VIII group metal, more preferably one or more of nitrate, sulfate, acetate and chloride of iron and/or nickel, and further preferably one or more of ferric nitrate, ferrous sulfate, ferric chloride, nickel nitrate, nickel sulfate, nickel acetate and nickel acetate; the mass ratio of the iron salt to the nickel salt is preferably (0.3-1.5): 1, more preferably (0.4 to 1.3): 1, more preferably (0.49 to 1.26): 1; preferably, chromium salts are included in addition to the above salts of iron and/or nickel; the chromium salt is preferably chromium nitrate, chromium sulfate and chromium chloride; the weight of the chromium salt is preferably 15 to 30 percent of the mass of the VIII group metal salt, more preferably 18 to 28 percent, still more preferably 22 to 26 percent, and most preferably 24.8 percent; the mass concentration of the VIII group metal salt in the solution containing the VIII group metal salt is preferably 15-50%, more preferably 20-40%, and still more preferably 25-36%; the time for the impregnation is preferably 4 to 12 hours, more preferably 6 to 12 hours.
After dipping, drying and roasting to obtain a catalyst for selective oligomerization of the mixed butylene; the drying temperature is preferably 100-150 ℃, and more preferably 110-120 ℃; the drying time is preferably 1 to 5 hours, and more preferably 3 to 4 hours; the roasting temperature is preferably 400-600 ℃, and more preferably 500-550 ℃; the roasting time is preferably 2 to 6 hours, and more preferably 3 to 4 hours.
According to the invention, a series of supported heterogeneous catalysts with different metal component contents and different acidity are prepared by an impregnation method, and the prepared catalyst has the advantages of high activity, excellent stability, regeneration and reuse, simple preparation process and low cost.
The invention also provides a method for selectively oligomerizing the mixed butylene, which mixes the catalyst for selectively oligomerizing the mixed butylene with the mixed butylene to carry out oligomerization reaction.
Wherein, the mixed butene is the mixed butene well known to those skilled in the art, and is not particularly limited, and is preferably a carbon four-cut fraction in the present invention; the carbon four fraction preferably comprises one or more of 1-butene, cis-2-butene and trans-2-butene; the content of olefins in the carbon four fraction is preferably equal to or greater than 30wt%; the content of impurities containing oxygen, sulfur, nitrogen, diene and the like in the four-carbon fraction is preferably less than or equal to 0.1 percent.
Mixing a catalyst for selective oligomerization of mixed butylene with the mixed butylene for oligomerization reaction; the temperature of the oligomerization reaction is preferably 40-190 ℃, more preferably 60-140 ℃, and further preferably 80-120 ℃; the pressure of the oligomerization reaction is preferably 1 to 9MPa, more preferably 2 to 7MPa, and still more preferably 3 to 5MPa; the liquid hourly space velocity during the oligomerization reaction is preferably 0.3 to 3h -1 More preferably 0.5 to 2 hours -1 More preferably 0.8 to 1.2 hours -1 。
The method for selectively oligomerizing the mixed butene can realize the oligomerization of the butene to generate high-carbon olefin under the temperature and the condition, and can realize different selectivity of the C eight and C dodecene by regulating and controlling the acid amount and the metal content of the catalyst.
In order to further illustrate the present invention, the following will describe in detail a catalyst for selective oligomerization of mixed butenes and a preparation method thereof, which are provided by the present invention, with reference to examples.
The reagents used in the following examples are all commercially available.
The components of the mixed butenes used in the examples include: 1.2% by weight of isobutene, 11.3% by weight of 1-butene, 14% by weight of cis-2-butene, 12.1% by weight of trans-2-butene, 0.01% by weight of 1, 3-butadiene, a sulfur content of 9ppmw, the remainder being mixed butanes.
Example 1
4.50g Fe were weighed 2 (SO 4 ) 3 ·9H 2 O, adding 13ml of deionized water, dissolving to prepare a metal salt solution, and roasting 16.8g of formed Al 2 O 3 The carrier (clover with the appearance of 2-5 mm, the strength of 106N/cm and the specific surface area of 320m 2 Per g, pore volume 0.67 ml/g) was poured into a metal salt bathThe solution is evenly mixed and then dipped for 6h, and then dried at 110 ℃ for 3h and roasted at 520 ℃ for 4h to prepare the catalyst A.
The catalyst is used for mixed butylene oligomerization at the reaction temperature of 90 ℃, the reaction pressure of 3.0MPa and the liquid hourly space velocity of 1.0h -1 The conversion rate of the mixed butene can reach 70.94 percent, the selectivity of the carbon octaolefin is 50.65 percent, and the selectivity of the carbon dodecene is 43.27 percent.
Example 2
5.43g of NiSO are weighed out 4 ·6H 2 O, adding 13ml of deionized water, and dissolving to prepare a metal salt solution; 16.8g of calcined formed Al 2 O 3 The carrier (clover with the appearance of 2-5 mm, the strength of 106N/cm and the specific surface area of 320m 2 /g, the pore volume is 0.67 ml/g) is poured into a metal salt solution, the mixture is evenly mixed and then is soaked for 8 hours, then the mixture is dried for 3 hours at the temperature of 110 ℃, and is roasted for 4 hours at the temperature of 520 ℃, thus obtaining the catalyst B.
The catalyst is used for mixed butylene oligomerization at the reaction temperature of 90 ℃, the reaction pressure of 3.0MPa and the liquid hourly space velocity of 1.0h -1 The conversion rate of mixed butene is 62.53 percent, the selectivity of the carbon octaolefin is 67.19 percent, and the selectivity of the carbon dodecene is 31.78 percent.
Example 3
3.17g of Ni (NO) are weighed 3 ) 2 ·6H 2 O and 4.01g Fe 2 (SO 4 ) 3 ·9H 2 O, adding 13ml of deionized water, heating and dissolving at 75 ℃ to prepare a metal salt solution, and roasting 16.8g of formed Al 2 O 3 The carrier (clover with the appearance of 2-5 mm, the strength of 106N/cm and the specific surface area of 320m 2 /g, the pore volume is 0.67 ml/g) is poured into a metal salt solution, the mixture is evenly mixed and then is soaked for 6 hours, then the mixture is dried for 3 hours at the temperature of 110 ℃, and is roasted for 4 hours at the temperature of 500 ℃, thus obtaining the catalyst C.
The catalyst is used for mixed butylene oligomerization at the reaction temperature of 90 ℃, the reaction pressure of 3.0MPa and the liquid hourly space velocity of 1.0h -1 The conversion rate of the mixed butene can reach 75.33 percent, the selectivity of the carbon octaolefin is 56.21 percent, and the selectivity of the carbon dodecene is 38.71 percent.
Example 4
3.62g of NiSO are weighed out 4 ·6H 2 O and 1.79g Fe (NO) 3 ) 3 ·9H 2 O, adding 13ml of deionized water, heating at 75 ℃ to dissolve the mixture to prepare a metal salt solution, and roasting 16.8g of formed Al 2 O 3 The carrier (clover with the appearance of 2-5 mm, the strength of 106N/cm and the specific surface area of 320m 2 /g, pore volume of 0.67 ml/g) into a metal salt solution, uniformly mixing, then soaking for 8 hours, then drying at 110 ℃ for 3hours, and roasting at 500 ℃ for 4 hours to obtain a catalyst D.
The catalyst is used for mixed butylene oligomerization at the reaction temperature of 90 ℃, the reaction pressure of 3.0MPa and the liquid hourly space velocity of 1.0h -1 The conversion rate of mixed butene can reach 76.62%, the selectivity of octa-olefin is 63.93%, and the selectivity of dodecene is 35.48% by gas chromatography on-line analysis.
Example 5
3.62g of NiSO are weighed out 4 ·6H 2 O and 1.79g Fe (NO) 3 ) 3 ·9H 2 O, adding 13ml of deionized water to dissolve the mixture to prepare a metal salt solution, and roasting 16.8g of formed P 2 O 5 -Al 2 O 3 Carrier (cylindrical shape with appearance of 2-5 mm, P) 2 O 5 The content is 1.0wt%, and the specific surface area is 307m 2 /g, pore volume of 0.65 ml/g) into a metal salt solution, uniformly mixing, soaking overnight, drying at 120 ℃ for 3h, and roasting at 550 ℃ for 4h to obtain the catalyst E.
The catalyst is used for mixed butylene oligomerization reaction at the reaction temperature of 90 ℃, the reaction pressure of 3.0MPa and the liquid hourly space velocity of 1.0h -1 The conversion rate of the mixed butene can reach 77.23 percent, the selectivity of the carbon octaolefin is 66.54 percent, and the selectivity of the carbon dodecene is 32.73 percent.
Example 6
2.72g of NiSO are weighed in turn 4 ·6H 2 O、1.34g Fe(NO 3 ) 3 ·9H 2 O and 1.34g Cr (NO) 3 ) 3 ·9H 2 O, adding 13ml of deionized water, heating at 75 ℃ to dissolve to prepare metal salt solutionLiquid, 16.8g of P formed by baking 2 O 5 -Al 2 O 3 Carrier (cylindrical shape with appearance of 2-5 mm, P) 2 O 5 The content is 1.0wt%, and the specific surface area is 307m 2 /g, pore volume of 0.65 ml/g) into a metal salt solution, uniformly mixing, soaking overnight, drying at 120 ℃ for 3h, and roasting at 550 ℃ for 4h to obtain the catalyst F. FIG. 1 is a photograph showing the appearance of the catalyst F obtained in example 6.
The catalyst is used for mixed butylene oligomerization reaction at the reaction temperature of 90 ℃, the reaction pressure of 5.0MPa and the liquid hourly space velocity of 1.0h -1 The conversion rate of mixed butene can reach 75.56%, the selectivity of carbon octaolefin is 65.37%, and the selectivity of carbon dodecene is 39.29% as measured by gas chromatography on-line analysis.
TABLE 1 evaluation results of catalyst Properties
Catalyst and process for preparing same Metal component Carrier Conversion of butene% C8 Selectivity% C12 Selectivity%
Example 1 Fe Al 2 O 3 70.94 50.65 43.27
Example 2 Ni Al 2 O 3 62.53 67.19 31.78
Example 3 Fe:Ni＝2:1 Al 2 O 3 75.33 56.21 38.71
Example 4 Fe:Ni＝1:2 Al 2 O 3 76.62 63.93 35.48
Example 5 Fe:Ni＝1:2 P 2 O 5 -Al 2 O 3 77.23 66.54 32.73
Example 6 Fe:Ni:Cr＝1:2:1 P 2 O 5 -Al 2 O 3 75.56 65.37 39.29

Claims (10)

1. The catalyst for selective oligomerization of mixed butylene is characterized in that the catalyst takes alumina and/or modified alumina as a carrier; the carrier is loaded with metal-containing active components; the metal-containing active component is one or more oxides of metals in a VIII group; the loading amount of the metal-containing active component in the catalyst is 5-50%.
2. The catalyst of claim 1, wherein the alumina is γ -Al 2 O 3 (ii) a The modified alumina is phosphorus modified alumina; the mass of the phosphorus-containing substance in the phosphorus-modified alumina is 0.1-10% of the mass of the phosphorus-modified alumina; the phosphorus-containing substance is selected from one or more of phosphoric acid, amine phosphate and metaphosphoric acid.
3. The catalyst according to claim 1, wherein the specific surface area of the carrier is 250 to 400m 2 (iv) g; the pore volume of the carrier is 0.6-1.2 mL/g.
4. The catalyst of claim 1, wherein the metal-containing active component comprises an oxide of iron and/or an oxide of nickel; the molar ratio of iron atoms to nickel atoms in the metal-containing active component is (0-10): (10-0).
5. The catalyst of claim 4, wherein the molar ratio of iron atoms to nickel atoms in the metal-containing active component is (1-4): (4-1).
6. The catalyst according to claim 1, wherein the loading of the metal-containing active component in the catalyst is 16-24%.
7. A process for the preparation of a catalyst for the selective oligomerization of mixed butenes according to claim 1, comprising:
dipping the carrier in a solution containing VIII group metal salt, drying and roasting to obtain a catalyst for selective oligomerization of mixed butylene; the carrier is alumina and/or modified alumina.
8. The preparation method according to claim 7, wherein the group VIII metal salt is selected from one or more of nitrate, sulfate, acetate and chloride salts of group VIII metal;
the dipping time is 4-12 h; the drying temperature is 100-150 ℃; the drying time is 1-5 h; the roasting temperature is 500-600 ℃; the roasting time is 2-6 h.
9. A method for selective oligomerization of mixed butylene is characterized in that the catalyst for selective oligomerization of mixed butylene according to any one of claims 1 to 6 or the catalyst for selective oligomerization of mixed butylene prepared by the preparation method according to claim 7 or 8 is mixed with mixed butylene to carry out oligomerization reaction.
10. The method of claim 9, wherein the mixed butenes are carbon four cuts; the carbon four fraction comprises one or more of 1-butene, cis-2-butene and trans-2-butene; the content of olefin in the four-carbon fraction is more than or equal to 30wt%;
the temperature of the oligomerization reaction is 40-190 ℃; the pressure of oligomerization reaction is 2-7 MPa; the liquid hourly space velocity during the oligomerization reaction is 0.3 to 3h -1 。
CN202210848124.XA 2022-07-19 2022-07-19 Catalyst for selective oligomerization of mixed butylene and preparation method thereof Pending CN115178267A (en)

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