Oligomerization method of isobutene
Technical Field
The invention relates to an oligomerization reaction method of isobutene, in particular to a process method for effectively improving isobutene conversion rate and dimer selectivity.
Background
Currently, isobutylene is mostly used in the synthesis of Methyl Tertiary Butyl Ether (MTBE) for blending components of high octane motor gasoline. However, this method of using isobutylene has become unreasonable due to the severe contaminating effect of methyl tertiary butyl ether on groundwater. Thus, is C 4 The isobutene in the fraction has very important practical significance in seeking a more reasonable utilization way.
The oligomerization of low-carbon olefin is one of important chemical processes in oil refining and organic chemistry industry, wherein the oligomerization product of butene 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.
Isobutene oligomerization is a typical acid-catalyzed reaction with catalysts mainly including liquid acid catalysts and solid acid catalysts. When liquid acid catalysts (sulfuric acid, toluene sulfonic 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, the catalysts have corrosion to equipment, and the continuous production process is difficult to realize. In recent years, solid acid catalysts are becoming hot spots for research on oligomerization of isobutene, and mainly include solid phosphoric acid catalysts, oxide and composite oxide catalysts, molecular sieve catalysts, ion exchange resin catalysts, supported sulfate catalysts, solid superacid catalysts, and the like.
At present, ion exchange resin is generally adopted as a catalyst for isobutene oligomerization, and in order to improve selectivity of isobutene dimers, a solvent is added into a reaction system to reduce production of isobutene dimers.
The kinetics of oligomerization of isobutylene by strongly acidic cation exchange resins in t-butanol was reported in petrochemical 2007, volume 36, phase 3, and the kinetics of oligomerization of isobutylene (m) was studied in strongly acidic cation exchange resins (catalysts) and t-butanol systems. The result shows that the isobutene oligomerization has the characteristic of first-stage serial connection irreversibility, and the tertiary butanol is added into the reaction system, so that the acidity of the catalyst can be reduced, but the adsorption capacity of isobutene on the surface of the catalyst is improved, and the selectivity of isobutene dimer (trimethylpentene) is obviously improved, but the conversion rate is reduced.
Disclosure of Invention
Aiming at the problems of low conversion rate or low dimer selectivity in an isobutene oligomerization reaction system in the prior art, the invention provides the oligomerization reaction method of isobutene, so that the selectivity of the dimer can be obviously improved on the basis of keeping higher isobutene conversion rate in the reaction, and the subsequent products are easier to separate and have lower energy consumption.
A process for oligomerization of isobutene includes such steps as loading the mixture of isobutene and phenolic reagent in reactor containing resin catalyst, and oligomerization of isobutene to obtain dimer.
In the above method, the phenolic reagent in the mixture of isobutene and phenolic reagent is 0.05 to 5% by weight of isobutene, preferably 0.5 to 3.0% by weight, and most preferably 0.5 to 1% by weight.
In the above method, the phenolic reagent is selected from at least one of phenol, hydroquinone and p-tert-butylcatechol.
In the above method, the specific operating conditions of the oligomerization of isobutene are: the liquid hourly space velocity of isobutene was 0.5h -1 ~20.0h -1 The reaction temperature is 100-200 ℃, and the reaction pressure is 1.0-6.0 MPa. Further, it is preferable that: the liquid hourly space velocity of isobutene was 0.5h -1 ~15.0h -1 The reaction temperature is 100-150 ℃, and the reaction pressure is 2.0-5.0 MPa. Further, more preferable is: liquid hourly space velocity of isobutene 1.0h -1 ~5.0h -1 The method comprises the steps of carrying out a first treatment on the surface of the The reaction temperature is 120-150 ℃, and the reaction pressure is 2.0-3.0 MPa.
In the above method, the catalyst used is a resin catalyst which is disclosed in the prior art and can be used for oligomerization of isobutene, in particular a strong acid cation exchange resin, more preferably a temperature-resistant strong acid cation exchange resin, which can be commercially available products or can be prepared according to the prior method, in particular a DNW-II type strong acid cation exchange resin catalyst produced by Dandonming special resin Co.
In the above method, as a further preferable mode, the strongly acidic cation exchange resin catalyst is modified by the following method and then catalyzes oligomerization: soaking the mixture for 8-24 h at 50-140 ℃ with low-carbon alcohol, then introducing inert gas or nitrogen in three stages, wherein the condition of introducing gas in the first stage is that the pressure is 0.3-0.6 MPa, the temperature is 40-60 ℃, and the flow rate is 1m 3 /h~2.5m 3 And/h, wherein the treatment time is 8-24 h; the condition of introducing gas in the second stage is that the pressure is 0.5-1.0 MPa, the temperature is 80-100 ℃ and the flow rate is 2m 3 /h~3m 3 And/h, wherein the treatment time is 10-32 h; the condition of introducing gas in the third stage is that the pressure is 1.0 MPa-1.5 MPa, the temperature is 90-120 ℃ and the flow rate is 3m 3 /h~5m 3 And/h, wherein the treatment time is 12-48 h; finally washing and drying are carried out.
In the above treatment method, it is further preferable that the lower alcohol is selected from C 1 ~C 7 At least one of the normal and isomeric alcohols, preferably C 1 ~C 4 At least one of the normal and isomeric alcohols, more preferably C 1 ~C 3 At least one of normal and isomeric alcohols. Most preferably, the lower alcohol is at least one selected from methanol, ethanol and isopropanol。
In the above treatment method, the condition of soaking with a low carbon alcohol is preferably a soaking condition at 60 ℃ to 120 ℃ for 12 hours to 24 hours.
In the above treatment method, it is further preferable that when the strongly acidic cation exchange resin is immersed in the low-carbon alcohol, the volume ratio of the low-carbon alcohol to the strongly acidic cation exchange resin is (2 to 10): 1, preferably (2 to 5): 1, more preferably (2 to 3): 1.
compared with the prior art, phenols are added into the reaction system, under the condition of oligomerization of isobutene, the dispersibility of isobutene in reaction materials is improved due to the existence of the phenols, so that an isobutene molecular liquid film is rarely formed on the surface of a catalyst or the formed liquid film is thinned, the diffusion resistance of isobutene to the surface of the catalyst is reduced, the formation of carbonium ions is increased, the oligomerization speed is improved, and the generation speed of polymers is reduced.
Detailed Description
The invention is further described below by means of specific examples. The conversion of isobutylene and the selectivity of dimer alcohol in examples and comparative examples were calculated by the following formulas.
In examples 1 to 10, the oligomerization of isobutene was catalyzed by DNW-II type temperature-resistant strong acid cation exchange resin catalyst (manufacturer: dendong pearl specialty resin Co., ltd.):
examples 1 to 27
The oligomerization reaction adopts a stainless steel fixed bed reactor, the size of which is phi 18mm multiplied by 1200mm, and the material is a stainless steel single tube. The reactor is divided into three sections to be filled, a certain amount of quartz sand is filled at the bottom, 30mL DNW-II type temperature-resistant strong acid cation exchange resin catalyst (manufacturer: dandong pearl special resin Co., ltd.) is filled at the middle section, the catalyst properties are shown in Table 1, the quartz sand is filled at the top until the quartz sand is filled, and the diameter of the quartz sand is phi 0.5-1.2 mm. And (3) replacing air in the fixed bed reactor with nitrogen, after the air tightness is qualified, dissolving the phenolic reagent in isobutene, feeding the isobutene into a preheater by a metering pump according to the required proportion, preheating the reaction materials, feeding the preheated reaction materials into the fixed bed reactor for reaction, keeping the reaction temperature at 130 ℃, keeping the reaction pressure at 2.0MPa, and recycling unreacted materials. The reaction conditions of the types of the phenolic reagents, the mixing ratio of the isobutene and the phenolic reagents, the volume space velocity of the isobutene and the like in each example are shown in Table 2, and the reaction results of the isobutene conversion and the dimer selectivity are shown in Table 3.
TABLE 1
TABLE 2
TABLE 3 Table 3
Examples 28 to 39 used a low carbon alcohol modified DNW-II type temperature resistant strong acid cation exchange resin catalyst (manufacturer: dendong pearl specialty resin Co., ltd.) to catalyze the oligomerization of isobutylene:
examples 28 to 39
DNW-II type temperature-resistant strong acid cation exchange resin catalyst (manufacturer: dandong pearl special resin Co., ltd.) is firstly placed in isopropanol, and the volume ratio of isopropanol to catalyst is 3:1, soaking for 24 hours at 50 ℃, then introducing nitrogen in three stages, wherein the pressure of the first stage is 0.5MPa, the temperature of the first stage is 60 ℃, and the flow rate of the introduced nitrogen is 1m 3 Treating for 12h; the condition of introducing nitrogen in the second stage is that the pressure is 0.8MPa, the temperature is 80 ℃, and the flow rate of the nitrogen is 3m 3 Treating for 20h; the condition of introducing nitrogen in the third stage is that the pressure is 1.2MPa; the temperature is 100 ℃,the flow rate of nitrogen was 5m 3 Treating for 24 hours; after the treatment, a modified resin catalyst is obtained.
The modified catalyst was used for oligomerization of isobutene, the procedure was as in example 1, the types of phenolic reagents used and other specific reaction conditions are shown in Table 4, and the reaction results are shown in Table 5.
TABLE 4 Table 4
TABLE 5
Comparative examples 1 to 2
According to the method of example 1, only isobutylene was fed at the time of feeding, and other specific reaction conditions are shown in Table 6. The results are shown in Table 6.
Comparative examples 3 to 4
Following the procedure of example 1, isobutylene and t-butanol as organic solvents were added to the feed and other specific reaction conditions are shown in Table 6. The results are shown in Table 6.
TABLE 6