CN111375433B - Method for oligomerization of isobutene - Google Patents

Method for oligomerization of isobutene Download PDF

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CN111375433B
CN111375433B CN201811624811.3A CN201811624811A CN111375433B CN 111375433 B CN111375433 B CN 111375433B CN 201811624811 A CN201811624811 A CN 201811624811A CN 111375433 B CN111375433 B CN 111375433B
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catalyst
isobutene
acid salt
oligomerization
reaction
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CN111375433A (en
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霍稳周
吕清林
姜睿
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Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
Sinopec Dalian Research Institute of Petroleum and Petrochemicals
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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
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/14—Phosphorus; Compounds thereof
    • C07C2527/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2527/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

A process for oligomerizing isobutene uses the supported cesium phosphotungstate as catalyst, in which the molecular formula of said cesium phosphotungstate is C S2.5 H 0.5 PW 12 O 40 . The supported cesium phosphotungstate acid salt catalyst takes silica gel as a carrier and acid salt of cesium phosphotungstate as an active component, and the load accounts for 20-50 percent of the total weight of the catalyst, preferably 30-40 percent. The invention realizes continuous production on the fixed bed reactor, has high reaction activity, is easy to recover and can be repeatedly used, and the reaction process is simple and convenient to operate, thereby being a novel environment-friendly chemical process.

Description

Method for oligomerization of isobutene
Technical Field
The invention relates to an oligomerization method of isobutene, in particular to an acid salt (C) of load type cesium phosphotungstate S2.5 H 0.5 PW 12 O 40 ) A method for catalyzing isobutene oligomerization reaction by using the catalyst.
Background
At present, isobutene is mostly used for synthesizing methyl tert-butyl ether (MTBE) and is used as a blending component of high-octane motor gasoline. However, this method of using isobutylene has become unreasonable due to the serious pollution effect of methyl t-butyl ether on groundwater. Thus, is C 4 The isobutene in the fraction has very important practical significance for seeking a more reasonable utilization way.
The oligomerization of low-carbon olefin is one of the important chemical processes in the oil refining and organic chemical industry, wherein the oligomerization product of butylene is an important chemical intermediate, can be used for producing oligomerization gasoline and diesel oil, and can also be used as an important intermediate for producing detergents, plasticizers, additives and pesticides.
The oligomerization of isobutene is a typical acid-catalyzed reaction, and the catalyst mainly comprises a liquid acid catalyst and a solid acid catalyst. When liquid acid catalysts (sulfuric acid, methyl benzenesulfonic acid and the like) are adopted in the early stage, the reaction selectivity is poor, the purity of the product isobutene dimer is low, the catalysts are not easy to separate and corrode equipment, and the production process is difficult to realize continuously. In recent years, solid acid catalysts have gradually become hot spots for research on oligomerization of isobutene, and mainly include solid phosphoric acid catalysts, oxides and composite oxide catalysts, molecular sieve catalysts, ion exchange resin catalysts, supported sulfate catalysts, solid super acidic catalysts and the like.
The traditional solid phosphoric acid catalyst is generally prepared by taking diatomite as a carrier and loading strong phosphoric acid (or called polyphosphoric acid), has been applied to petrochemical aspects such as olefin oligomerization for decades, and has exposed a plurality of problems in the long-term application process, such as poor water resistance, low mechanical strength, easy argillization and the like.
Multiple metal oxides and composite oxides can catalyze oligomerization of isobutene, and binary composite oxide A1 with strong acidity 2 O 3 -SiO 2 , TiO 2 -SiO 2 , ZrO 2 -SiO: has both B acid center and L acid center, wherein A1 with high acidity 2 O 3 -SiO: has good catalytic activity in isobutene oligomerization reaction.
The molecular sieve is aluminosilicate with high crystallinity, has a regular pore structure, uniform distribution of surface acid centers, moderate acidity and good activity in oligomerization reaction of isobutene. The types, the silicon-aluminum ratio, the contained metal ions, the pore structure, the reaction conditions and the like of the molecular sieve have influence on the activity and the selectivity of the isobutene oligomerization reaction.
The supported sulfate is a solid acid with wider application, and a plurality of metal sulfates can generate a considerable amount of acid centers with medium strength after being calcined, so that the conversion rate of isobutene is high and the selectivity of dimers is lowest when the supported sulfate is used for isobutene oligomerization.
The solid super acidic catalyst catalyzes the oligomerization reaction of isobutene, the reaction is carried out in liquid phase, isobutene can be completely converted at low space velocity, and products mainly comprise di-trimer and trimer, but still contain tetramer with a certain proportion.
The ion exchange resin is a novel solid acid catalyst, and has the advantages of stable catalytic effect, no corrosion, no pollution, low price and the like, so that the ion exchange resin is widely applied to reactions such as etherification, esterification, superposition, hydration, alkylation and the like.
U.S. Pat. No. 4,300,022,211 reports a cation exchange resin catalyst as a catalyst for butene oligomerization, but the high molecular weight oligomers easily block reaction channels, and alkylation of the resin skeleton causes rapid activity reduction, and the resin has poor high temperature resistance, which limits the application. The CA2435590A1 patent describes a process for obtaining high purity diisobutylene by reducing the acid capacity of the catalyst using NaOH, using a macroporous sulfonic acid resin as the catalyst and pure isobutylene as the starting material. Chinese patent CN107754852A provides a method for modifying a strong acid cation exchange resin catalyst by a silicophosphoric acid solution.
2017, volume 3 of volume 33 reports that sodium exchange Amberlyst-15 catalyzes isobutene to prepare diisobutylene by means of superposition, and the results show that the conversion rate of isobutene is gradually reduced along with the increase of the sodium exchange rate, the selectivity of a dimerization product is rapidly increased, and the conversion rate of isobutene and the number of acid centers on a catalyst are in a linear relationship. The reaction temperature is increased, the conversion rate of isobutene on resin catalysts with different sodium exchange rates is increased, the dimerization selectivity is reduced, and the higher sodium exchange rate enables the selectivity of dimerization products on the resin to be reduced along with the change range of the temperature. The space velocity is increased, the selectivity of dimerization products is increased, and the conversion rate of isobutene is reduced.
Petrochemical 2007, volume 36, phase 3, reports that strong-acid cation exchange resin in tertiary butanol catalyzes oligomerization kinetics of isobutylene, and in a system of strong-acid cation exchange resin (catalyst) and tertiary butanol, the oligomerization kinetics of isobutylene (m) was studied. The results show that isobutylene oligomerization has the feature of first order series irreversible. The tertiary butanol is added into the reaction system, although the acidity of the catalyst can be reduced, the adsorption capacity of isobutene on the surface of the catalyst is improved, so that the selectivity of a dimer (trimethylpentene) of isobutene is obviously improved, and the conversion rate is reduced to some extent.
Disclosure of Invention
Aiming at the defects that the typical heteropolyacid catalyst is mostly adopted in the isobutene oligomerization reaction in the prior art, the dimer selectivity is low when the catalyst catalyzes the isobutene oligomerization reaction, the dimer is easy to lose in the using process, the particles are too small to cause difficult separation, and the catalyst is difficult to use on a fixed bed reactor, the invention provides the isobutene oligomerization method.
The technical purpose of the invention is realized by the following technical means:
a process for oligomerizing isobutene uses the supported cesium phosphotungstate as catalyst, in which the molecular formula of said cesium phosphotungstate is C S2.5 H 0.5 PW 12 O 40 。
In the method, the supported cesium phosphotungstate acid salt catalyst takes silica gel as a carrier and takes acid salt of cesium phosphotungstate as an active component. The particle size of the catalyst is phi 2 x 2 mm-phi 5 x 5mm, preferably phi 2 x 2 mm-phi 3 x 3mm.
In the method, in the supported cesium phosphotungstate acid salt catalyst, the supported amount of cesium phosphotungstate acid salt accounts for 20-50%, preferably 30-40% of the total weight of the catalyst.
In the above method, the supported cesium phosphotungstate acid salt catalyst is prepared by the following method: and (3) taking a silica gel carrier, firstly soaking the silica gel carrier in a cesium carbonate solution, drying and roasting, then soaking the silica gel carrier in a phosphotungstic acid solution, and then drying and roasting to obtain the catalyst.
Furthermore, in the preparation process of the catalyst, the temperature of the two-step drying is 80-200 ℃, and the time of the two-step drying is 5-20 hours; soaking in cesium carbonate solution, and then roasting at the temperature of 300-400 ℃ for 3-10 hours; the temperature for baking after dipping in the phosphotungstic acid solution is 350 to 550 ℃, and the baking time is 2 to 14 hours.
Further, in the preparation process of the catalyst, the impregnation is selected from one of equal-volume impregnation, spray impregnation or supersaturated impregnation.
In the method, the specific reaction conditions of the isobutene oligomerization are as follows: isobutene is used as a reaction raw material, supported cesium phosphotungstate acid salt is used as a catalyst, and the liquid hourly volume space velocity of the isobutene is 0.5h -1 ～5.0h -1 Preferably 1.0h -1 ～4.0h -1 More preferably 1.0h -1 ～2.5h -1 (ii) a The reaction temperature is 90-160 ℃, preferably 90-130 ℃, and more preferably 90-100 ℃; the reaction pressure is 2.0 to 6.0MPa, preferably 3.0 to 5.0MPa, and more preferably 4.0 to 5.0MPa.
In the above process, the feedstock is a mixed C4 feedstock containing isobutene or pure isobutene. Wherein the mixed C4 feedstock has an isobutylene content of at least 5% by weight, more preferably at least 10% by weight, and even more preferably at least 15% by weight.
The invention adopts supported cesium phosphotungstate acid salt (C) S2.5 H 0.5 PW 12 O 40 ) As a catalyst for the oligomerization of isobutene, can catalyze the reaction at relatively low temperature and has high dimer selectivity and isobutene conversion. The catalyst such as heteropoly acid phosphotungstic acid catalyst which is typical for isobutene oligomerization reaction is easy to lose in the using process due to small particles, difficult to separate and difficult to use on a fixed bed reactor.
Detailed Description
The invention is described in detail below with reference to specific examples, which are provided to understand and explain the invention, but not to limit the invention.
Example 1
Acid salt (C) of supported cesium phosphotungstate S2.5 H 0.5 PW 12 O 40 ) Preparation of the catalyst:
by two-step equivoluminal impregnation, 5g of cesium carbonate (C) was taken S2 CO 3 ) Dissolved in 200mL of deionized water. 50g of carrier silica gel were immersed in the above solution, and the sample was dried at 120 ℃ and calcined at 350 ℃ for 5 hours.
10g of phosphotungstic acid (H) 3 PW 12 O 40 ) Dissolving in 300mL of deionized water, immersing the roasted sample in phosphotungstic acid solution, drying at 120 ℃, and roasting at 450 ℃ for 4 hours to obtain the catalyst A.
By XRD analysis shows that the active component of the catalyst A is an acid salt of cesium phosphotungstate (C) S2.5 H 0.5 PW 12 O 40 ) The content of active component in the catalyst was 15% by weight.
The prepared catalyst is used for the oligomerization of isobutene, the reaction is carried out in a stainless steel fixed bed reactor with phi 18mm multiplied by 1200mm, 30mL of the catalyst is filled in the reactor, quartz sand with the diameter of phi 0.5 mm-1.2 mm is respectively filled in the top and the bottom of the reactor, after the reactor is installed, nitrogen is used for replacing three times, and the airtight test is qualified, and isobutene, ethanol or ethanol water solution is sent into a preheater by a metering pump. The reaction conditions and the reaction results are shown in Table 1.
Example 2
When a catalyst was prepared, catalyst B, in which the mass content of the acid salt of cesium phosphotungstate as an active component in the catalyst was 25%, was obtained under the same conditions as in example 1 except that the mass of cesium carbonate was changed to 10g and the mass of phosphotungstic acid was changed to 15 g.
The prepared catalyst was used for the oligomerization of isobutylene, and the reaction conditions and the reaction results are shown in Table 1, the same as in example 1.
Example 3
When the catalyst was prepared, catalyst B, in which the mass content of the acid salt of cesium phosphotungstate as an active component in the catalyst was 35%, was obtained under the same conditions as in example 1 except that the mass of cesium carbonate was changed to 15g and the mass of phosphotungstic acid was changed to 20 g.
The prepared catalyst was used for the oligomerization of isobutylene, and the reaction conditions and the reaction results are shown in Table 1, the same as in example 1.
Example 4
When the catalyst was prepared, catalyst B, in which the mass content of the acid salt of cesium phosphotungstate as an active component in the catalyst was 45%, was obtained under the same conditions as in example 1 except that the mass of cesium carbonate was changed to 20g and the mass of phosphotungstic acid was changed to 10 g.
The prepared catalyst was used for the oligomerization of isobutylene, and the reaction conditions and the reaction results are shown in Table 1, the same as in example 1.
Example 5
The catalyst prepared in example 1 was used for the oligomerization of isobutylene under the same conditions as in example 1 except that the reaction temperature was changed to 100 ℃.
Example 6
The catalyst prepared in example 1 was used for the oligomerization of isobutylene under the same conditions as in example 1 except that the reaction temperature was changed to 110 ℃.
Example 7
The catalyst prepared in example 1 was used for the oligomerization of isobutylene under the same conditions as in example 1 except that the reaction temperature was changed to 120 ℃.
Example 8
The catalyst prepared in example 1 was used for the oligomerization of isobutylene under the same conditions as in example 1 except that the reaction temperature was changed to 130 ℃.
Example 9
The catalyst prepared in example 1 was used for the oligomerization of isobutylene under the same conditions as in example 1 except that the reaction temperature was changed to 140 ℃.
Example 10
The catalyst prepared in example 1 was used for oligomerization of isobutylene under the same conditions as in example 1 except that the reaction temperature was changed to 150 ℃.
Example 11
The catalyst prepared in example 1 was used for the oligomerization of isobutylene under the same conditions as in example 1 except that the reaction temperature was changed to 160 ℃.
Comparative example 1
Preparing a supported phosphotungstic acid catalyst: loading phosphotungstic acid on a silica gel carrier by an isometric impregnation method, wherein the weight content of the phosphotungstic acid is 20 percent. The reaction was carried out under the same conditions as in example 1, and the results are shown in Table 1, and the conversion and dimer selectivity data in Table 1 are the average values of three replicates.
Comparative example 2
Preparing a supported phosphotungstic acid catalyst: loading phosphotungstic acid on a silica gel carrier by an isometric impregnation method, wherein the weight content of the phosphotungstic acid is 20 percent. The reaction was carried out under the same conditions as in example 5, and the results are shown in Table 1, and the conversion and dimer selectivity data in Table 1 are the average values of three replicates.
TABLE 1
Figure DEST_PATH_IMAGE001

Claims (8)

1. The method for oligomerization of isobutene is characterized in that supported cesium phosphotungstate acid salt is used as a catalyst, silica gel is used as a carrier, and acid salt of cesium phosphotungstate is used as an active component, wherein the molecular formula of the cesium phosphotungstate acid salt is C S2.5 H 0.5 PW 12 O 40 (ii) a The loading amount of the cesium phosphotungstate acid salt accounts for 20-50% of the total weight of the catalyst; the specific reaction conditions for the isobutene oligomerization are as follows: isobutene is used as a reaction raw material, supported cesium phosphotungstate acid salt is used as a catalyst, and the liquid hourly volume space velocity of the isobutene is 0.5h -1 ～5.0h -1 The reaction temperature is 90-160 ℃, and the reaction pressure is 2.0-6.0 MPa.
2. The method of claim 1, wherein the catalyst has a particle size of Φ 2 x 2mm to Φ 5 x 5mm.
3. The method of claim 2, wherein the catalyst has a particle size of Φ 2 x 2mm to Φ 3 x 3mm.
4. The method as claimed in claim 1, wherein the supported cesium phosphotungstate acid salt catalyst has a cesium phosphotungstate acid salt loading of 30-40% based on the total weight of the catalyst.
5. The process of claim 1, wherein the supported cesium phosphotungstate acid salt catalyst is prepared by the following method: and (3) taking a silica gel carrier, firstly soaking the silica gel carrier in a cesium carbonate solution, drying and roasting, then soaking the silica gel carrier in a phosphotungstic acid solution, and then drying and roasting to obtain the catalyst.
6. The method according to claim 1, wherein the specific reaction conditions for the oligomerization of isobutene are as follows: the liquid hourly space velocity of isobutene is 1.0h -1 ～4.0h -1 The reaction temperature is 90-130 ℃, and the reaction pressure is 3.0-5.0 MPa.
7. The method according to claim 1, wherein the specific reaction conditions for the oligomerization of isobutene are as follows: the liquid hourly space velocity of isobutene is 1.0h -1 ～2.5h -1 The reaction temperature is 90-100 ℃, and the reaction pressure is 4.0-5.0 MPa.
8. The process of claim 1 wherein the feedstock is a mixed C4 feedstock containing isobutylene or pure isobutylene, wherein the mixed C4 feedstock has an isobutylene content of at least 5% by weight.
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CN85102831B (en) * 1985-04-01 1988-03-16 大连工学院 Eliminating minute iso-butane in butane mixture
CN1208130C (en) * 2002-12-11 2005-06-29 中国石油化工股份有限公司 Prepn of solid phosphoric acid catalyst for oligomerization of low-carbon olefine
JP4524427B2 (en) * 2004-09-24 2010-08-18 国立大学法人北海道大学 Composition comprising heteropolyacid salt and inorganic oxide and method for producing the same
CN100402518C (en) * 2004-12-30 2008-07-16 浙江工业大学 Application of cesium phosphotungstic acid as catalyst for synthesizing acetyl thiophene
CN103044214B (en) * 2011-10-17 2015-07-22 中国石油化工股份有限公司 Preparation method of ethyl tert butyl ether
CN106000463B (en) * 2016-05-30 2018-12-28 河南工业大学 The preparation method and application of immobilized Tricesium dodecatungstophosphate salt catalyst

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