• 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 process for the separation of butene-1 from other C4 mono-olefins. A feed stream containing butene-1 is contacted with a K-X zeolite which selectively adsorbs butene-1. The butene-1 is desorbed using a mixture of hexene-1 and cyclohexene or cyclohexane.
    公开号:SU912042A3
    申请号:SU782637200
    申请日:1978-07-12
    公开日:1982-03-07
    发明作者:Вильям Ниузил Ричард；Лестер Ферджин Ричард
    申请人:Юоп Инк (Фирма)；
    IPC主号:
    专利说明:

    I
    This invention relates to a process for isolating butene-1 from a mixture of hydrocarbons containing other C mono-lefins using zeolite.
    The closest to the technical essence and the achieved result to the proposed method is the separation of butene-1 from raw materials containing butene-1, other CA hydrocarbons, by adsorbing butene-1 with zeolite type X adsorbent, containing potassium cations, followed by desorbing the desorbed butene -1 desorbent - a mixture containing olefins. Octen-1 or low molecular weight olefins, which can be easily separated from butene-1, can be used as desorbents. For paOoTjsi, a mixture of normal olefins and iso-paraffins is used in the liquid phase, for example, a mixture containing 20% octene-1 and 80% nzo-octane ClJ.
    However, the adsorbent base of pzooctane has a large volume
    retention that does not allow us to accept it in the industry.
    The purpose of the invention is to increase the se-: complexity of the process.
    The goal is achieved by the fact that in the process of isolating butene-1 from raw materials containing butene-1, other hydrocarbons Ci, by adsorbing butene-1 with an adsorbent, a type X zeolite, containing cations
    10 potassium, followed by desorption of adsorbed butene-1 with a desorbent - a mixture containing olefin, as a desorbent, use a mixture containing 25-75 vol. % hex- &
    on and 25-75 about. % cyclohexane or cyclohexene.
    Distinctive features are the use of the above.
    20 desorbent. The composition of the desorbent has a significant effect on the process. The use of cyclo-paraffin or cyclo-olefin as a diluent together with the preferred
    25 sorbent, hexene-1, allows 39 to obtain a desorbent having HAe properties for industrial use. The proposed method includes the following stages of contacting the feedstock with a type X zeolite containing potassium cations for the selective adsorption of butene-1, contacting the adsorbent containing the adsorbed butene-1 with desorbent. The adsorbent used in the proposed method is a type X zeolite ion-exchangeable for potassium cations. Desorbent may displace adsorbed moieties from the molecular sieve. The desorbent itself is quite easily replaced by the adsorbent, with the result that the molecular sieve can be reused in the process. The process of isolating butene-1 proceeds over an artificially moving layer of adsorbent. The desorbent itself cannot easily displace adsorbed | 1st butene-1 from the adsorbent, so it must be used in large quantities. This is undesirable because it requires the use of a large amount of energy to separate the desorbent butenes from the desorbent, which allows the desorbent to be reused in the process. It is also undesirable for the desorbent to be held too tightly by the adsorbent, since in this case it is difficult to fill the adsorbent with butene-.I. This can be compensated for by providing a large number of zones in the artificially moving layer or by significantly increasing the contact time between the raw material and the adsorbent that gets wet in the desorbent in order to adsorb butene. Raw streams can be streams of any refinery process. Raw materials mainly contain monoolefinic hydrocarbons C, such as butene-1, isobutylene, trans butene-2 and cis-butene-2. The term butene-2 includes both cis and trans isomeric configurations of this hydrocarbon. Other substances, for example, large quantities of paraffinic and naphthenic substances, may also be present in such raw materials - and in some cases low concentrations of aromatic hydrocarbons and other impurities such as combined sulfur-nitrogen compounds. However, 24 it is preferred to significantly reduce the number of components capable of deactivating the adsorbent by blocking the adsorption passages for the components of the feedstock. During the experiment, three different types of raw materials are used, which reflect the availability of different raw materials at various tests, Raw materials A consist of% by volume: 2.3t, - С; , 9 L- 35.1 butene-1; 46.4 iso-, butylene; 10.3 tert-butene-2. Raw material is supplied from a standard pipeline with a volume of 3 cm, displaced. its adsorbent and injected into the layer of adsorbent containing 70 cm of adsorbent located in a stainless steel tube with dimensions of 152.4 cm x 9.5 mm. Raw B consists of% vol .:, 26 butene-1, 19 isobutylene, 22 cis and trans-butene-2. This raw material is diluted with 75 cm of desorbent per 25 cm of raw material and 10 cm of jaKoA mixture is fed to an adsorbent layer containing 70 cm of adsorbent contained in a stainless steel tube with dimensions of 152.4 cm x 9.5 mm. Raw material C consists of% vol: 44 C, 42 butene-1, 4 isobutylene. This raw material is displaced from a 3 cm pipeline with a desorbent and injected into an adsorbent layer containing 70 cm of adsorbent contained in a stainless steel tube with dimensions of 152.4 cm X 9.5 mm. Use several adsorbents. All adsorbents are type X zeolites ion-exchanged for K ions. Such zeolites are initially N-X-type substances, then they are ion exchanged with K ions using conventional techniques. Almost complete ion exchange with more than 95% Na per K is carried out. For testing, one of the adsorbents is subjected to double ion exchange processing, however, there is no significant difference in performance. When testing various types of raw materials, I note T difference 6 mode of operation. It is established that the composition of the desorbent has a significant impact on the process. The active desorption ingredient is an olefin of various boiling points {hexene-1 being the preferred desorbent. This substance is diluted with normal vapor of fin, which is regarded as an inert substance. Testing two different adsorbents leads to unexpected results in that one of them works well and the other does not, while both are K-X adsorbents. Thus, adsorbents are equivalent, and desorbents are not. The test results are presented in tables. All experiments were carried out at 50 ° C. All adsorbents used are compounds of the type KX, although they are obtained from various sources. Example 1. The test was carried out using raw material A. Desorbent is 25% v / v hexene-1 in H-Cd. The peak width is an expression of the mass transfer rate or the anti-diffusion rate between the adsorbed molecule and the desorbent. Typically, broad peaks are an indication of low anti-diffusion rates h, on the contrary, narrow peaks are an indication of high speeds. The limiting value of the peak widths. In terms of its narrowness, is the day value of n-butane, which is practically not adsorbed. Thus, the closer the width of the peak of the adsorbed olefin molecules to the non-adsorbed sample, the better the adsorbent - desorbent to the system. Selectivity is a crude equivalent to the term volatility in distillation and is a characteristic of the effectiveness of an adsorbent with respect to the separation of various substances. For successful industrial separation usually requires selectivity of at least 2.0. Lower selectivity requires more thorough testing of the adsorbent to effect the release. High selectivity need for thorough testing of adsorbents. The amount of butene-1 retention is a qualitative characteristic of selectivity between butene-1 and desorbent. A large retention volume indicates a high 426 selectivity of butene-1 with respect to the desorbent and vice versa, a low retention volume is an indication of a low selectivity. Usually, under the conditions of experience, the amount of retention of butene-1 should be in the range of 20–13 cm. A value of 13 cm means j that the selectivity of butene-1 with respect to desorbent is less than one, which is undesirable. A value of 20 cm indicates the fact that for desorption of butene-1, too much adsorbent will be required. Example 2. These experiments were repeated on different adsorbents, i.e. on fresh loads of K-X adsorbent. Sly-1-154. Sample 81У- 1-154 is subjected to a second ionization treatment with potassium and is designated as Qiy-l-164-C. For all these experiments, the desorbent is hexene-1 in H — C. In contrast, the desorbent in Example 1 is hexene-I in H-Cg. Example 1 indicates the fact that desorbent, containing 25% vol. hexene-1 in H-Cg is satisfactory in terms of selectivity, but the amount of retention of butene-1 is unacceptably high (35.6 and 34.7 cm) and the rate of anti-diffusion is poor, which is high peak widths. Example 2 indicates that replacing H — C with H — C results in a process that is unacceptable from the point of view of selectivity, and also due to undesirably high retention volumes for butene-1. These experiments confirm the fact that there is a certain effect associated with the use of various diluents in the desorbent and confirm that the use of normal paraffinic diluents and, of course, H-C as a diluent in such a system is undesirable. Example 3. Experiments are being made to establish that the method of adding a sample of raw materials is an act of considerable significance. In one case, the raw material is diluted to a concentration of 25% by volume. in desorption and injected in the form of a pulse with a volume of 10 cm into the adsorption tower. 79 According to another type of injection of the sample, the raw material is introduced in diluted form from a 3 cm sample pipe into an adsorption tower using a desorbent, with which the raw material is forced out into the column. The results are presented in tables. From the data presented in the table, it can be seen that isooctane is an excellent desorben B Tim, as regards selectivity, but a poor desorbent for the amount of butene 1 retention. From-octane displaces butene-1 from the adsorbent fast enough to use it in industrial process. Pure cyclohexane is a sample of a completely different selectivity, but it does not quickly desorb butene-1, which can be judged by the retention volume of butene-1 in order to use it in industry. Pure cyclohexane has the disadvantage that | c is that the selectivity for bute well-1 relative to tert-butene-2 is unacceptably low. Example 4. In order to establish whether a commercially used desorbent can be obtained, a series of experiments were performed on a KX X zeolite using mixtures of hexene in various diluents, mainly in cyclohexene and cyclohexane. For the sake of comparison, experiments using pure 1-hexene and pure cyclohexene were also tested. The results are presented in Table 5. From the results of the experiments, it follows that two different types of desorbent compositions are optimal. When olefin cyclic diluent is used, the optimum concentration of each of the components, 1-hexene and 1-cyclohexene is 50% by volume. This mixture provides a desorbent which has a high selectivity for butene-1 relative to isobutylene and cis and trans-butene-2. The amount of retention of butene-1 is satisfactory and is 17.73 cm. When using cyclohexane as a diluent for desorbent, other compositions turned out to be optimal instead of cyclohexene. For example, a mixture of hexene-1 and cyclohexene in a ratio of 50/50 gave desorbent, which has good selectivity, however, the amount of retention of butene-1 was slightly higher than preferred. As a result of the use of a mixture consisting of 75% 1-hexene and 25% cyclohexane, a desorbent is obtained, having desirable properties with respect to the retention volume of butene-1, which in this case has a value of 16.39 cm, which is significantly lower than using a mixture of 1-hexene and cyclohexane in a 50/50 ratio. The selectivities obtained using a desorbent consisting of 75% 1-hexene and 25% cyclohexane are satisfactory. The use of cyclohexane as a diluent is preferred, however, this is due to its availability and low cost, rather than a significant advantage over the use of a cyclohexenes diluent. Table 1
    9f204210
    Continued table. I
    table 2
    retention volume for butane cm
    35.6
    Continue tab. 3
    34.5
    72.1
    权利要求:
    Claims (1)
    [1]
    1. US Patent No. 3723561, cl. 260-677, published 1973 rototype.
    类似技术:
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    同族专利:
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    FR2397382A1|1979-02-09|
    IT7825572D0|1978-07-11|
    AU3770678A|1980-01-10|
    IT1099570B|1985-09-18|
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    FR2397382B1|1981-07-24|
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3723561A|1971-12-01|1973-03-27|Universal Oil Prod Co|The selective separation of butene-1 from a c{11 {11 hydrocarbon mixture employing zeolites x and y|
    US3969223A|1973-12-10|1976-07-13|Universal Oil Products Company|Olefin separation process|US4567309A|1984-05-29|1986-01-28|Uop Inc.|Separation of 1,3-butadiene|
    US5132485A|1990-11-21|1992-07-21|Exxon Chemical Patents Inc.|Adsorptive separation of alpha-olefins and internal olefins|
    US5276246A|1991-12-23|1994-01-04|Uop|Process for separating normal olefins from non-normal olefins|
    US5220102A|1991-12-23|1993-06-15|Uop|Process for separating normal olefins from non-normal olefins|
    KR100822847B1|2007-03-29|2008-04-16|한국에너지기술연구원|Separation of olefins from olefins/paraffins mixed gas|
    KR100836707B1|2007-04-25|2008-06-10|한국에너지기술연구원|Production of high purity of butene-1 from c4 olefins/paraffins mixed gas|
    CA2931123A1|2013-11-26|2015-06-04|Uop Llc|Separation of iso-olefins from paraffins|
    EP3558908A1|2016-12-21|2019-10-30|SABIC Global Technologies B.V.|Process to produce olefins from a catalytically cracked hydrocarbons stream|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US05/815,041|US4119678A|1977-07-12|1977-07-12|Desorbent for separation of butene-1 from a C4 hydrocarbon mixture using zeolite X|
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