• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    A novel hydrocarbon alkylation catalyst is disclosed comprising a mineral acid and an ether component. A process for utilizing the novel catalyst is also disclosed.
    公开号:SU1598855A3
    申请号:SU874202335
    申请日:1987-04-10
    公开日:1990-10-07
    发明作者:Имаи Тамотсу；А.Кокал Джозеф
    申请人:Юоп Инк (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to catalysts, in particular catalysts for the alkylation of isobutane with C-olefins, as well as to a method for producing alkylate.
    The aim of the invention is to increase the selectivity of the catalyst in relation to trimethylpentane due to the content in its composition as a promoter of methyl tert-butyl ether at a certain content of components, as well as to obtain an alkylate with a high content of trimethylpentane, which is a high-octane component.
    Examples The process is carried out in a pilot plant equipped with an autoclave-type reactor made of a copper-nickel alloy, in which isoparaffin and the olefin activating agent are contacted with an acidic
    catalyst. After a sufficient time of contact, the hydrocarbon and acid phases are removed from the autoclave reactor and fed to a settling tank, in which the phases are separated. The acid phase is then withdrawn from the sump and recycled back to the autoclave reactor in order to contact the new batch of hydrocarbons. The hydrocarbon phase containing alkylate is removed from the settling tank and fed to the neutralization stage, which is carried out using special means. Next, the hydrocarbon phase is collected and subjected to analysis. Conducted two separate experiments on the specified pilot plant. In accordance with the first experiment, an acid catalyst containing 90% by weight of hydrofluoric acid and 10% by weight is used.
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    organic solvents. The organic solvent is oligomerized isobutylene with a carbon number range of 07-023 and is mainly a C8-Ci2 hydrocarbon. In accordance with the second experiment, a catalyst is used which is 90% by weight of hydrofluoric acid and 10% by weight of methyl tert-butyl ether.
    These experiments were carried out in an autoclave reactor under the following conditions: temperature 20 ° C, pressure 9.14 kgf / cm, residence time 10 minutes, the speed of the stirrer 1800 rpm. The volume ratio of the acid phase to the hydrocarbon in the autoclave is 1.5. The molar ratio between isobutane and C4 olefins is 7.9. The distribution parameters for C4-olefins are as follows,%: 2-butene 48.2; 1-butene 23.2; isobutene 28.6.
    In each experiment, the alkylate product is analyzed.
    The resulting products have the compositions and theoretical octane numbers given in table. one.
    As can be seen from the table. 1 in those cases when the acid catalyst contains an ether component, the theoretical octane number is 0.9 higher than in those cases when the acid catalyst contains hydrogen fluoride and an organic solvent. The higher octane number achieved in accordance with the invention is the direct result of the formation of more trimethylpentanes. than dimethylhexanes in alkylate. An increase in the content of trimethylpentane in the alkylate and a decrease in the content in the alkylate of dimethylhexane is a result of the presence of an ether compound.
    EXAMPLE 2 Two additional alkylation tests were conducted to determine the stability of the ether component of the acid catalyst. Two experiments on real alkylation were carried out on the pilot plant described in Example 1. The process conditions are the same as in Example 1.
    In the first experiment, the process lasts for 24 hours and the hydrocarbon supply to the pilot plant is carried out only for about 5 hours. The second experiment in the pilot plant is carried out for 16 days, but the hydrocarbon feed is carried out only for 54 hours However, acid catalysts are present at the plant for 24 hours and 16 days, respectively. At the end of each experiment, the acid phase is analyzed.
    The results obtained are presented in table. 2
    From the data of Table 2 it follows that only an insignificant amount of methyl tert-butyl ether decomposed to form methanol. A certain amount of methyl tert-butyl ether that dissociates into methanol is due to the presence of water, which is a contaminant. However, the vast majority of methyl tert-butyl ether remains unconverted to methanol. PRI me R 3 (comparative). In a pilot alkylation unit, 5 another experiment was conducted. The conditions of its conduct are similar to those. which are used when conducting experiments in examples 1 and 2. However, in this case, the acid catalyst contains 90 wt.% hydrogen fluoride and 0 10 wt.% methanol.
    The results of these experiments are presented in Table. 3. In table. 3 also includes the results obtained in the experiment of Example 1. Within which 5 the catalyst contains hydrofluoric acid and methyl tert-butyl ether.
    As can be seen from the data table. 3, the use of an acid catalyst containing a simple ether component provides results that are superior to those achieved with an acid catalyst containing an alcohol component. The use of the simple 5th ether component provides an increase in the octane number by 0.4 units. theoretical octane number compared to the case when using an acid catalyst containing methanol. This 40 increase in the octane number is due to an increase in the amount of trimethylpentane formed (75.7% by weight as opposed to 72.9% by weight and a corresponding decrease in the amount of di-45 methylhexane formed.
    PRI me R 4. The process is carried out in a pilot plant comprising an autoclave from Monel. in which isoparaffin and olefin are contacted with an acid catalyst. After a sufficient time, the hydrocarbon and acidic phases are removed from the autoclave and sent to a sump in which the phases are separated. After separation, the acidic phase is removed from the sump and returned to the autoclave, where it is again contacted with the hydrocarbon. The hydrocarbon phase, "containing alkylate. removed from the sump and sent to a device for neutralization, after which it is collected for analysis.
    In a pilot plant, 1-5 experiments according to the invention and comparative experiments 6-8 were carried out. In each experiment, an acid catalyst containing 85–98 wt.% Hydrofluoric acid and 2–15 wt.% Methyl tert-butyl ether (MTBE) is used. All experiments were carried out at 20 ° C and an autoclave pressure of 896 kPa, the residence time was 10 minutes, the rotation speed of the agitator was 1800 rpm. The volume ratio of the acid and hydrocarbon phases is 1.5. The molar ratio of isobutane and C4-olefin is 7.9. The composition of C4-olefins,%; 2-butene 48.2; 1-butene 23.2; isobutylene 28.6.
    After each experiment, the obtained alkylate is analyzed, and for the composition and octane numbers, the values given in Table 1 are obtained. four.
    EXAMPLE 5 Alkylate, a product of an alkylation process that uses a catalyst containing hydrofluoric acid and methyl tert-butyl ether, is compared with a product that uses only hydrofluoric acid as a catalyst. Process parameters: the temperature in the reaction zone is 32 ° C and the pressure is 1216 kP &.
    The feed rates of the raw materials in the process and the components are the same in both cases and are listed in the table below. 5 and 6.
    Additional operating parameters include a isobutane / olefin molar ratio of about 1.0.
    In the first experiment, a catalyst containing 97% by weight hydrofluoric acid and 3.0% by weight methyl tert-butyl ether was used. In the second experiment, a catalyst is used which contains only 100% by weight of hydrofluoric acid.
    The product of the alkylation process is subjected to a separation step to remove light non-reactive hydrocarbons from the alkylation product. The first separation takes place in a propane distillation column operating at a pressure of 260 kPa and at an overhead temperature of 50 ° C. The overhead product from the propane-distilling column is listed for the first and second experiments, respectively, in table. 5 and 6 as a propane product. The residue from the propane distillation column is fed to the second separation in a column for the distillation of isobutane. The residue product from the bottom of the isobutane distillation column is an alkylation product. The overhead product from the isobutane distillation section is named as butane product.
    and its composition for the first and second experiments are listed respectively in Table. 5 and 6.
    An additional important factor is the volume ratio of acid to carbon in the load, which is 10 in this polymer. The method, carried out under the specified conditions, is capable of producing approximately 51.3 m / h of alkylation product with an octane number of approximately 96.0.
    In tab. 5 and 6, for the first and second experiments, respectively, the composition and quantity of the raw materials of the obtained products are given. In tab. Figure 7 shows for comparison the composition of the alkylation product obtained in the first and second experiments of Example 5.
    A comparative analysis of the alkylation product from the first and second experiments shows that the product is alkylated and in the first experiment 1, obtained by using a catalyst for alkylation, containing hydrofluoric acid and methyl tert-butyl ether, has a higher content of trimethylpentane than the product obtained using catalyst containing only hydrofluoric acid, as in the second experiment. The additional content of trimethylpentane in the product from the first experiment provides a higher octane alkylate
    number (RON) than the product from the second experience. This is a convincing confirmation that the alkylation catalyst in accordance with the invention, containing 8598 wt.% Hydrofluoric acid and 15-2 wt.% Methyl tert-butyl ether, is superior to the known catalyst containing only hydrofluoric acid, giving an alkylate with more high
    octane number
    权利要求:
    Claims (2)
    [1]
    1. A catalyst for the alkylation of isobutane with C-olefins, containing hydrofluoric acid and a promoter characterized in that. that, in order to increase the selectivity of the catalyst with respect to trimethylpentane, as a promoter it
    contains methyl tert-butyl ether and is anhydrous, alcohol-free. homogenous mixture with the following content of components, wt.%:
    Hydrofluoric acid
    acid85-98
    Methyl tert-butyl ether 2-15.
    [2]
    2. A method for producing alkylate by alkylation of isobutane with C-olefins in the liquid phase in the presence of a catalyst.
    containing hydrofluoric acid and promoter, at a temperature of 20-32 ° C, pressure 896-1216 kPa, characterized in that, in order to increase the content of trimethylpentane in the alkylate, a catalyst is used that is an anhydrous, alcohol-free homogeneous mixture containing as a promoter methyl tert-butyl ether, with the following
    0
    the ratio of components in the catalyst, wt.%:
    Hydrofluoric acid
    acid85-98
    Methyl tert-butyl
    ether2-15
    and the process is carried out at a volume ratio of hydrofluoric acid to raw hydrocarbons 1.5-10.0.
    Table 1
    table 2
    Table 3
    Table 4
    Table 5
    eleven
    1598855
    12 Table 6
    Table
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    同族专利:
    公开号 | 公开日
    HU198636B|1989-11-28|
    DE3676995D1|1991-02-21|
    FI871590A|1987-04-10|
    NO168930C|1992-04-22|
    NO871509D0|1987-04-10|
    EP0232385A1|1987-08-19|
    AU6222486A|1987-03-10|
    CA1275402C|1990-10-23|
    US4636488A|1987-01-13|
    FI871590A0|1987-04-10|
    KR920009119B1|1992-10-13|
    BR8606815A|1987-10-13|
    IN166667B|1990-06-30|
    AU582463B2|1989-03-23|
    EP0232385B1|1991-01-16|
    NO168930B|1992-01-13|
    HUT42350A|1987-07-28|
    KR870700406A|1987-12-29|
    EP0232385A4|1987-11-09|
    AR241072A1|1991-10-31|
    JPS63500647A|1988-03-10|
    AR241072A2|1991-10-31|
    WO1987001053A1|1987-02-26|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US2090905A|1936-11-17|1937-08-24|Gulf Research Development Co|Polymerization of olefins|
    US2431715A|1944-01-14|1947-12-02|Shell Dev|Prevention of corrosion in hydrogen fluoride catalytic organic reactions|
    US2956095A|1958-06-17|1960-10-11|Exxon Research Engineering Co|Light naphtha isomerization process|
    US3531546A|1967-11-29|1970-09-29|Universal Oil Prod Co|Alkylation of organic compounds|
    US3761540A|1971-04-30|1973-09-25|Phillips Petroleum Co|Alkylation of isoparaffin with ethylene and a higher olefin|
    US3778489A|1971-12-16|1973-12-11|Exxon Research Engineering Co|Alkylation with separate olefin streams including isobutylene|US5196628A|1991-06-21|1993-03-23|Mobil Oil Corporation|Liquid acid alkylation catalyst and isoparaffin:olefin alkylation process|
    US5220096A|1991-06-21|1993-06-15|Mobil Oil Corporation|Liquid acid alkylation catalyst composition and isoparaffin:olefin alkylation process|
    US5292982A|1991-06-21|1994-03-08|Mobil Oil Corporation|Liquid acid alkylation catalyst and isoparaffin-olefin alkylation process|
    US5534657A|1991-06-21|1996-07-09|Phillips Petroleum Company|Isoparaffin-olefin alkylation|
    US5202518A|1991-09-18|1993-04-13|Mobil Oil Corporation|Liquid acid alkylation catalyst and isoparaffin:olefin alkylation process|
    US5569807A|1992-05-01|1996-10-29|Phillips Petroleum Company|Isoparaffin-olefin alkylation|
    US5324397A|1992-07-09|1994-06-28|Mobil Oil Corporation|Method for inhibiting corrosion of carbon steel in contact with hydrofluoric acid and tetrahydrothiophene-1, 1-dioxide|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US06/764,707|US4636488A|1985-08-12|1985-08-12|Novel motor fuel alkylation catalyst and process for the use thereof|
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