• 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:
    The present disclosure relates to a method of reactivation of certain catalytic properties of a phosphorous-vanadium-oxygen complex catalyst which is used for the oxidation of hydrocarbons in particular acyclic aliphatics such as alkanes or alkenes to oxidation products including aldehydes, ketones, acids and anhydrides. The present method of reactivation is implemented by passing a material containing a halide over the catalyst during normal oxidation operations or in a separate procedure for process improvements. A process using a phosphorous-vanadium-oxygen complex zinc promoted catalyst wherein butane is passed along with air or oxygen over said catalyst to effect the production of maleic anhydride is suitable for the claimed reactivating procedure.
    公开号:SU1071221A3
    申请号:SU762399516
    申请日:1976-09-17
    公开日:1984-01-30
    发明作者:Партенхаймер Вальтер
    申请人:Стандарт Ойл Компани (Фирма)；
    IPC主号:
    专利说明:

    ABOUT
    "H
    o This invention relates to methods for producing maleic anhydride by the oxidation of i-butane. The closest to the present invention is a method for producing maleic anhydride by oxidizing H-butane with an oxygen-containing gas at 400-460 ° C in the presence of an oxide pho- forvadium catalyst, prepared by an element selected from the group consisting of zinc, copper, bismuth, lithium or their mixtures, with the atomic ratio phosphorus vanadium: promoter (.0.5--5): 1: (0.05-0.5 G13. The disadvantages of the known method are not sufficiently high selectivity. The purpose of the invention is to increase the electoral process. This the goal is achieved according to But what about the method of producing maleic anhydride by oxidizing n-butane with an oxygen-containing gas at 4004 oC in the presence of a zinc-promoted phosphorus-vanadium catalyst, with an atomic ratio of phosphorus: vanadium: zinc {1.15-1.2): 1: 0, 2 treated with a reaction agent selected from the groups containing chlorine, hydrogen chloride, carbon tetrachloride, dichloromethane, dichloroethane, tetrachloroethane, by, giving on the catalyst in an amount (0.02-0.9 weight, h. on 1 weight. catalyst with an addition rate of 0.002-0.35 mmop / s, or by feeding it into a gas oil reagent stream. The method is described as follows. Through an oxide phosphorus-vanadium catalyst promoted with zinc, with an atomic ratio of phosphorus: guanadium: zinc (1.15-1.2 hl: 0.2, the flow of reagents — H-butane and oxygen-containing gas 1 — is passed into a reactivation agent selected from the group consisting of chlorine, hydrogen chloride, carbon tetrachloride,; dichloromethane, dichloroethane, tetrachloroethane. Reactivation agents must be in the gas phase under conditions of reactivation. The catalyst can be treated with a re-activation agent in a separate stage, in this case for transfer nta reactivation through a catalyst bed using aerated gas. In the case of a catalyst being treated with a reactivation agent, a washing gas is passed through the catalyst before and after passing through the reactivation agent to remove the reactive agent being carried away and other materials from the catalyst bed. nitrogen or other inert gases or light hydrocarbons {butane K. The treatment temperature is in the range of 300-5 pO ° C. Example 1. The catalyst is in contact with n-butane and air the mixture for a period of time, after which it is treated with carbon tetrachloride and returned to the stream in order to determine the effect of treatment with a halide on the spent catalyst. An increase in yield and selectivity is observed. The carbon tetrachloride treatment is carried out by adding carbon tetrachloride to n-butane and air, which is a feed mixture. The feed stream contains about 1.1% by volume of the load of normal butane in an artificially created atmosphere air | 1. The feed stream is passed through a reactor in which a catalyst with an atomic ratio of phosphorus: vanadium:, 2: 1: 0.2, is located. During normal operation, the weight spatial velocity is about 1.4 at atmospheric pressure. The same spatial velocity and. the pressure is maintained by adding: the Research Institute of carbon tetrachloride to the feed stream. During the thirty-minute period of treatment with carbon tetrachloride 3, an aggregable stream with 1.1% by volume of butane is passed through a scrubber, in which liquid carbon tetrachloride is located, maintained during and after which the reaction zone is introduced with a temperature that is maintained at a level. Calculations of vapor pressure showed that the addition rate was 0.002 mmol / s. The results of the treatment with carbon tetrachloride are shown in Table 1. The results indicate a significant improvement in the selectivity of the catalyst in terms of producing maleic anhydride after 22 hours of operation. Table 1 shows also the performance characteristics of the original fresh atalizer at the reaction temperature and the temperature of the spent catalyst, showing the conversion temperature, the selectivity of the weight output at the reax temperature to treatment for the purpose of recovery.
    Source Fresh Catalyst
    Used catalyst
    18
    Processing CC1l
    Lt Lt mm
    83
    87
    62
    27 50
    94 82
    43 69
    Example 2. 10 g of spent catalyst to produce maleic anhydride, having the same composition as in example 1, is placed in a glass-lined tube furnace heated to, through which a stream of nitrogen gas is passed. Then a stream of nitrogen is passed through a concentrated aqueous solution of hydrogen chloride at room temperature. The acid saturated stream is passed through the furnace tube. After holding for 4 hours at 400 ° C, the treatment with hydrogen chloride is completed and the catalyst is cooled in a stream of pure nitrogen gas. Then, the catalyst was loaded into the reactor as in Example 1, and 1.1% n-butane was introduced along with the air flow with a weight spatial clock C1 {or 1.4, at atmospheric pressure. The results of determining the degree of conversion, selectivity, and yield for the spent catalyst before treatment with hydrogen chloride and for the treated catalyst when operating in the stream for a period of time are given in Table. 2
    Spent Example 3. The example describes the addition of hydrogen chloride in place in the reaction zone of the flow-inlet-20. During the reaction, a stream containing about; 1.1% by weight of n-butane in air is passed over the catalyst, which is maintained at a temperature of 25 about, at atmospheric pressure and weight spatial hourly speed of about 1.4. At various intervals during the reaction, the formation of maleic anhydride from butane over a layer of catalyst passes hydrogen chloride mixed with the load-. emitted stream. PO400 Chloride Treatment
    257
    263,400 0 н NSR
    281
    400
    286 400 0 min NSG
    400
    288 400
    305,400
    310 0 min HCf
    400
    312,400
    329 400
    333
    5 к «н НС 425
    400
    Table 2 30
    67
    51
    70
    54
    66 71
    53 56
    75 75
    67 73
    53 58
    74
    59 by gas flow by passing the first feed stream at atmospheric pressure through a gas scrubber, which does not contain concentrated hydrochloric acid at room temperature. An air stream of n-butane, iasi 11 | enriched with chlorine hydrogen at room temperature, was introduced into the reaction zone through time. After four treatments with chloride, both yields and the catalytic selectivity improved significantly. The result of processing hlsfidom in the stream are given in table. 3
    Example 4. In this example, a catalyst similar to that described in example 1 is used to illustrate the effect of chlorine gas treatments on the catalytic characteristics.
    During normal processing, a 1.1% by volume n-butane in air is passed through the reactor at atmospheric pressure and adjusted weight spatial hourly speed of about 1.4. At certain intervals of time (17, 45, 179, 212 and 227 hours of stay in the stream), gas was passed over the catalyst bed 45499. 3.3 0.055 450
    452. 96 18,00,055450454 93
    .
    590.055450
    44894
    330,055459
    44889
    Example 5. The catalyst, similar to that described in Example 4, is in contact with gaseous chlorine for 3 hours at atmospheric pressure and a weight spatial hourly velocity of about 0.3. Number up, 65
    a shaped stream containing chlorine, with a weight spatial rate of 1.4 per hour for periods of time ranging between 1 and 30 minutes. The rate of addition, the reactivation agent is 0.055 mmol / s. After that, the feed is resumed, and after a period of time between 3 and 28 hours, the effluent is analyzed on a gas-liquid chromatograph to determine the effect. chlorine on the characteristics of the catalyst, the results of these tests are given in table. four.
    Table 4
    55
    33
    63
    39
    74
    47
    47
    74
    73
    48
    The reactive agent is 132 mmol, the addition is 0.12 mmol / s.
    After 65 hours in the stream together with the load under conditions similar to those described in Example 4, the conversion was found to be 99%, the selectivity was 29% and the weight yield was 48% at, After three hours of chlorine treatment and after another 46 hours Steam treatment is a conversion rate of 100%, a selectivity of 16% and a weight yield of 27% for all measurements at 450c. These results show that excessive treatment with chlorine with a concentration does not improve the characteristics of the catalyst and has an adverse effect on its working characteristics. Example 6, The example describes the repeated treatments of the catalyst as in Example 4 to illustrate the effectiveness of repeated treatments with carbon tetrachloride and using water vapor washing to modify the properties of the catalyst, t Oxidation process and -butane and the flow is carried out under the same conditions as and in Example 4. Carbon tetrachloride is processed after the mixture of n-butane and air is switched to nitrogen flushing for 1/2 hour. After treatment with carbon tetrachloride, it is again washed 1/2 h of nitrogen. Then the mixture of N-butane and air begins to be supplied, and the degree of conversion, selectivity and yield are determined at the indicated temperature at specified intervals of time. Reactivation with carbon tetrachloride is carried out at the specified catalyst cycle by injecting nitrogen into the stream using a flush that passes through a spatial weight hourly rate of 1.4, 0.07 ml of carbon tetrachloride for 15 seconds. The amount of reactivation agent added is 0.73 mmol, the addition rate is 0.049 mmol / s. For a time; personal periods served as a catalyst. the supply of butane to the feed stream is stopped and the clean air is brought into contact with the catalyst for extended periods of time. Contact with air is carried out to accelerate the deactivation of the catalyst so that a more rapid assessment can be made of the effectiveness of reactivation with halogen using carbon tetrachloride as a reactivation agent. Contact with air leads to the appearance of all the qualitative characteristics of a conventional spent catalyst, i.e., a decrease in selectivity and a molar ratio between carbon monoxide and carbon dioxide and an increase in conversion. After several reactivation procedures, carbon tetrachloride is treated with steam to illustrate the beneficial effects on catalyst performance. Steam treatment produces by skip-. nor above the catalyst at the indicated temperature a mixture of 85% by volume of water and nitrogen with a weight hourly space velocity of about 1.4 for a specified period of time. After steam treatment, the usual filling is introduced, consisting of a mixture of n-butane with air, which is passed over the catalyst and the degree of conversion, selectivity and volume output is determined. The results of the described experiments are given in Table. 5. From table. 5, it can be seen that deactivation of the catalyst becomes more difficult with air treatment after each successive reactivation of four trichlorides with carbon. The table shows data relating to the specified periods of service life of the catalyst. All conversions, selections, and yields are related to the specified mixture of n-butane and air. The temperature during various treatments is maintained close to in order to be able to make the maximum number of changes to the process parameters without the need to heat or cool the catalyst or load. Various sequential treatments are given in table. 5, illustrate a marked improvement in performance, in particular, the selectivity of the catalyst when using the reactivation process. It can be considered that varying the temperature creates an additional improvement in selectivity and output. Carbon tetrachloride is treated after 67,119, 240, 288, 454, and 617 hours of catalyst service, the mash, all treatments lead to su -. {{{a natural improvement in catalyst selectivity. In cases where the yields decrease, the additional duration and / or subsequent treatment with water vapor increases the conversion, which leads to the final attempt on the release of maleic anhydride. The combination of tetrachloride carbon treatment after 617 hours and steam treatment after 644 hours results in a very significant increase in yield (from 51 to 88% with a very small decrease in the selective degree.
    Treatment with carbon tetrachloride and water vapor after 751 and 753 hours and after 777 and 844 hours, respectively, leads to an increase in the overall yield with a stable or slightly reduced selectivity. The catalyst characteristics after treatment with carbon tetrachloride and water vapor increase as 940 hours conversion rate and catalyst selectivity.
    Final treatment with carbon tetrachloride after 991 hours of loading
    CC2 processing
    Loading
    Loading
    3 h Air treatment
    Loading
    CC1 Processing
    Loading
    3h air handling
    SS 9ts Processing
    Loading
    5 hours air handling
    Loading
    FID Processing Loading
    Loading
    4h Air Handling Download
    SCC Processing
    Loading
    Loading
    increases selectivity, but has (1) a positive effect on the degree
    transform. The subsequent treatment of the waters with steam after 1083 hours more than doubles the degree of conversion and leads to the final working move equal to 92%. These data show that in some cases it is necessary to treat with steam or functionally similar contacting of the catalyst after the treatment with carbon tetrachloride.
    Table 5 Example 7. Reactivation of the catalyst described in example 1 with carbon tetrachloride is carried out under conditions of example 6. After every four hours of activation with carbon tetrachloride, the conversion is determined, and the efficiency and yield are 65 Some of these experiments are repeated
    in order to illustrate the effect on catalyst characteristics of multiple treatments with carbon tetrachloride. When the activation is carried out at the temperature of the reaction zone, it is reduced to from in one of the experiments in order to illustrate the effect of temperature control on the performance of the catalyst.
    Table 6 summarizes the activation of carbon tetrachloride.
    260 S Activation Base CCt Activation Postactivadi
     Activation Basis CC14 Activation Postactivation SS C4 Activation Postactivation
     Activation Basis CCl Activation Postactivation Postactivation CCt4 Activation Postactivation CCI4 Activation Postactivation
     Activation Base CCt4 Activation
    Given in Table. 6 data shows that carbon tetrachloride activation becomes effective when the temperature is in the range of 60 and 300 ° C, the degree of conversion decreases slightly at activation temperatures above 400 ° C} the maximum increase in selectivity is observed when activation is carried out at about 360 C.
    -Table 6
    5B 58 56 88 91 53
    35 35 34 54 6 32
    99 99 98 97 96 99
    82
    52 64
    94 84
    91
    90 93
    56 59.
    95 93 97 56 34
    400 C Activation Base CCE Activation Postaction 450 s Activation
    Foundation SS Activation
    Example 8. In this example, various catalysts are tested and the chloride content is determined after performing certain operations. All primes catalysts {% 1 contain phosphorus, vanadium, oxygen, without a carrier, and metallic zinc as a promoter, with an atomic ratio of phosphorus: vanadium and zinc 1.15: 1: 0.2. The otrarthanol catalyst contains 0.02% by weight chlorine. This catalyst has not been in contact for a lifetime with an activation agent. The second catalyst, activated by contacting it with a charge mixture consisting of butane and air, was subjected to CCE treatment in a stream of nitrogen used by pressing a flow of about 0.1 g of CCt4 for 15 s, at a weight rate of about 1 hour. , 43, catalytic bed at a bladder temperature of 300 ° C. The amount of reactive agent Avacii added is 0.74 mmol, the addition rate is 0.002 mmol / s. After 3 hours from the treatment, the CCl4 gas and nitrogen were welded and catalyzed). The catalyst was found to contain 0.02% by weight of chlorine. The third catalyst, deactivated, is treated with CCt as described above and then subjected to steam treatment as described in Example 6 for 2 hours. Then nitrogen is proshchivanie in .98
    35
    58
    90
    63
    97
    94
    33
    59
    50
    66
    5 B
    V 3 hours. Found that this catalyst contains 0.01% by weight of chlorine. Example 9. The carbon tetrachloride drainage rate influences the success of the catalyst regeneration. Sequential reactivations are performed at a rate of adding 10 ml to the charge passed over 4 g of catalyst. The amount of the reactivation agent introduced is 0.002 mmol, the addition property is 0.002 kmol / s. Suspension reactivation is observed when, at 4 g of a catalyst bed, CCt4 stays in the boot, passes over the catalyst, occurs at a rate of 2x10 and CCt4 / c. The most desirable minimum minimization is that when the weight of the catalyst bed is 4 g, it is approximately 1x10 1 1 1 CCt4 / c "Example 10. Katgizizor in contact with butane and WHO; E | The IVC mixture is reactivated in place for a certain period of time with dichloromethane, and then returned to the stream to determine the effect of the catalytic treatment; but. There is an increase in yield and selectivity as a result of processing. Reactivation treatments Carry out passing gaseous dihpormethane to a carrier gas through a reactant containing a phosphorus-vanadium catalyst, zinc-rich, 1 PHI, atomic ratio of phosphorus to vanagium, 1.16: 1
    the period of time at atmospheric pressure and the regulation of the hourly weight rate, was Nh. 1.43. After treatment, a stream containing 1 vol.% N-butane in the air is passed through the reactor at a time-weighted
    451
    18 46 451 Treatment entered CH2C12
    451 451
    451 Treatment of CH2Cl2f with 0.092 ml (1.4 mmol) in the addition of 0.093 mmol / s
    451
    451 451 Treatment, 0.018 ml (0.28 mmolJ per connection rate 1.26-10 mmol / s
    451
    450
    450 Treatment 0047 ml (o, 73 mmol /, rate of addition 0,0122 mmol / s
    Example 11. This example illustrates the treatment of the phosphorus-vanadium catalyst promoted-. zinc (the atomic ratio of phosphorus to vanadium is 1.14; 1L, 1,1-dichloroethane, and the subsequent oxidation of butane in the presence of a catalyst under conditions similar to those of example 10. Treatments with a substantial rate of 1.43 and at atmospheric pressure.
    The concentrations of dichloromethane, the gasers, the temperature of the reactor and the efficiency of the catalyst are shown in Table. 7
    Table 7
    65
    39
    98
    41 39
    67 64
    97 98
    67 62
    41,
    98 96 38
    62 47
    40 29
    92 96
    30 mmoles of 1,150-dichloroethane are passed in a stream of butane and air over the catalyst for 30 minutes. The 1,1-dichloroethane concentration is 28 mol%. The addition rate is 55 0.0167 mmol / s.
    The results are shown in the table. 8. 0.33 mm in nitrogen, injected over 15. s., Amount of 5.2 mmol, addition rate 0.35 mmol / s butane, 15 s. Nitrogen rate, 37 min. butane-air, 60 s.
    d mep 12. This example45 in the subsequent oxidation of butane in
    illustrates reactive processing of catalysation, in terms of the catalyst described in similar conditions of Example 10. Example 10, tetrachloroethane, and: Improved Processing Types and Results, Preceding the Efficiency of Catalyst-Fastener in Table. 9.
    20 21
    450 450
    T.a blitz 8
    Table 9
    thirty
    50
    Treatment with tetrachloroethane (TCE, 0.741 mmol, butane-air, 15 s. Adherence rate 0.0494 mmol / s
    TCA processing is the same as at 21 h
    47 45095 50 80
    117 45097 38 63
    120450
    Treatment of TCA is the same as at 21 h.
    122 45095 53 84
    140 45095 46 75 141 450
    Treatment of TCA is the same as at 21 h.
    143 45092 55 86
    165 45094 52 - 83 168 450
    Treatment of TCA in the same way. Like at 21 hours
    168 45193 58 91
    191 42787 63 93
    212 46298 48 80
    332 46098 35 58 335 500
    Treatment of THC, 0.741 mol, in a stream of nitrogen, 15 s
    337 46092 56. 87
    335 44089 60 90
    359500
    .
    Treatment of TCA in the same way as at 335 h
    362 460i90 60 91
    384,500
    Treatment of TCA as well as 335 h
    Continued table, 9
    I
    iz: i 4I 5
    Continued table. 9
    权利要求:
    Claims (1)
    [1]
    METHOD FOR PRODUCING MALEIC 'ANHYDRIDE ( by oxidation of β-butane with an oxygen-containing gas at 400 ~ 460 ° С in the presence of an oxide phosphorus-vanadium catalyst, rolled with zinc, with an atomic ratio of phosphorus: vanadium: zinc = * (1.15-1.2): 1: 0.2, characterized in that, in order to increase the selectivity of the process, the catalyst is treated with a reactivation agent selected from the group consisting of chlorine, hydrogen chloride, carbon tetrachloride, dichloromethane, dichloroethane, tetrachloroethane, by feeding it to the catalyst in an amount of 0.02 -0.9 parts by weight per 1 part by weight cat connection speed with recuperators 0,002-0,35 mmol / s, or by feeding it into the gas reactants flow.
    g £ in /
    f
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    引用文献:
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    BE756951A|1969-10-01|1971-04-01|Basf Ag|PERFECTED PROCESS FOR PREPARATION OF MALEIC ANHYDRIDE|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US05/616,370|US4020174A|1975-09-24|1975-09-24|Reactivation of maleic anhydride producing phosphorus-vanadium-oxygen complex oxidation catalysts by treatment with halide containing materials|
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