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    • 专利摘要:
    Oxychlorination of ethylene is carried out using a three-reactor system containing beds of a catalyst comprising a spherical, high-surface area activated alumina impregnated with cupric chloride and potassium chloride. In the first two reactors, the catalyst bed is divided into two sections, with a more active catalyst in the lower section than in the upper. The catalyst is substantially undiluted with inert particles.
    公开号:SU743576A3
    申请号:SU762378586
    申请日:1976-07-13
    公开日:1980-06-25
    发明作者:Гордон Кэмпбелл Рамсей；Портер Доан Эллиот；Генри Хейнес Майер；Джон Вогт Гарви；Сильвестр Наворски Джозеф
    申请人:Стауффер Кемикал Компани (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to methods for producing 1,2-dichloroethane, which finds use as a solvent, as well as an intermediate for the production of vinyl chloride. A method is known for producing 1,2-dichloroethane by oxychlorinating ethylene with a mixture of hydrogen chloride and oxygen-containing gas at a temperature of 200-340 s in the presence of a fixed catalyst bed containing 12 wt.% Copper chloride, 6 wt.% Potassium chloride, 3 wt.% Molybdenum oxide and 79% by weight of inert carrier. In this case, a catalyst is used, the particle size of which decreases along the length of the reaction zone from the inlet to the outlet 1. The process is carried out in three successively located catalyst catches. Conversion of ethylene is 96-98%, the selectivity of the formation of 1,2-dichloroethane is 97-98%. When carrying out the oxychlorination process on a fixed bed of the catalyst, the problem of controlling the reaction temperature arises. The oxychlorination reaction is highly exothermic and, in addition, the regulation of the TeMnepaTypla reaction is made difficult by the fact that the catalyst layer has a low thermal conductivity, resulting in the risk of forming undesirable localized superheating zones in the catalyst layer, which quickly removes the catalyst from its structure. Therefore, in order to reduce the overheating of the catalyst particles in a known method, a catalyst is used with a reduced particle size along the length of the reaction zone. However, such a process requires careful implementation in order to ensure that the size of the particles is necessary and requires production, according to. at least two, or even better, three or even four different catalysts in order to achieve success in such a process. All this complicates the process technology. The aim of the invention is to simplify the process technology and eliminate the overheating of the catalyst bed. The proposed method for producing 1,2-dichloroethane is that ethylene is subjected to oxychlorination by a mixture of hydrogen chloride and oxygen-containing at a temperature
    200-320 C in the presence of a fixed catalyst layer containing copper chloride and potassium chloride on an inert carrier, in three consecutively located catalyst zones.
    In the first catalyst zone, the catalyst layer is divided into two layers in the direction of flow of the reaction gases through it. The first layer contains 45-75% of the entire zone and the second layer 25-55% of the entire zones, while the catalyst of the first layer contains 4.5-12.5 copper chloride and 1.5-7-7 wt.% Potassium chloride, the weight ratio of copper chloride and potassium chloride 1.5-4: 1. The catalyst of the second layer contains 1225 wt.% Copper chloride and 0.5-4 wt.% Potassium chloride, the weight ratio of copper chloride and potassium chloride is 5-15: 1
    In the second catalyst zone, the catalyst layer is divided into two layers in the direction of flow of the reaction gases through it. The first layer contains 45-75% of the entire zone and the second layer 25-55% of the entire zone, while the catalyst of the first layer contains 5.5-15 wt.% Copper chloride and 1-5 wt.% Potassium chloride, the weight ratio of copper chloride and Kyoshi chloride 2-6: 1. The catalyst of the second layer contains 12-25 wt.% Copper chloride and 0.5-4 wt.% Potassium chloride, the weight ratio of copper chloride and potassium chloride 5-15: 1.
    In the third catalyst zone, the catalyst contains 12-25 wt.% Copper chloride and 0.5-4 wt.% Potassium chloride, the weight ratio of copper chloride and potassium chloride is 5-15: 1.
    Practically, the process is conducted in three reactors, the process flow diagram is shown in the drawing.
    Gaseous hydrogen chloride is introduced through line 1 after being preheated to the preheater. Ethylene is introduced via line 2 after being preheated in the preheater and mixed with the supplied n line 1 - hydrogen chloride. An oxygen-containing gas, which can be air, a molecular oxygen or oxygen-enriched air, is introduced through line 3 and divided into three parts, following the lines 4.5 and 6, respectively. The separation can be into three equal or three unequal parts. A portion of line 4 is mixed with hydrogen chloride / ethylene feed and introduced into reactor 7 via line 8. The temperature of the mixed gaseous feed is usually about 120-220 seconds, preferably about 135-180. C. The mixed feed passes through the catalyst bed of the reactor 7 (the catalyst is typically located in the tubes) and is withdrawn from the reactor 7 through line 9.
    The products from the reactor 7 are directed through line 9, combined with the second part of oxygen-containing gas from line 5, introduced into the reactor 10 through line 11 and in contact with the catalyst in the bed in the reactor 10. The reaction products are removed through line 12, in contact with the third part oxygen-containing gas from line 6 and injected through line 13 into the catalyst bed of reactor 14. The reaction products are removed through line 15, cooled in a heat exchanger and condensed in a condenser. The reaction products are withdrawn via line 16, they contain mostly 1,2-dichloroethane with small amounts of ethyl chloride and other chlorinated hydrocarbons.
    In general, the process is carried out at a total pressure in the system of 2.10937.031 kg / cm, preferably 2.81246, 3279 kg / cm. In order to control the temperature in the reactors, these reactors are mainly manufactured with jackets, shirts surround the pipes with layers of catalysts and contain heat exchanging liquids, such as boiling water, steam or Dauterm liquid. In general, the reaction is carried out at temperatures of about 200-340 ° C. In reactor 7, the superheat temperature is usually maintained below about 300 ° C, in reactor 10 - below 330 ° C, preferably below 300 ° C, and in reactor 14 - below 320 ° C, preferably lower Another important factor is the control of the location of the overheating zone in the reactors. In each reactor, the overheating zone should be localized in the direction towards the inlet end of the catalyst bed. In reactors 7 and 10, the overheating zone should actually be located in the direction towards the inlet end in the first or less active part of the bed. If overheating is detected very far (in the direction of the exit from the bed), this is an indication that the reaction proceeds too slowly in the bed, i.e. that the catalyst is not used effectively enough. In addition, if the superheat proves to be very close to leaving the bed, this can lead to a cumulative result with an increase in the reaction in a stronger catalyst in the second layer, as a result, undesirable high temperatures will be observed at this point.
    The distribution of oxygen in a gas through the lines 4,5 and 6 can be carried out, that equal quantities enter all three reactors, or, if necessary, quantities, entering into the reactor, can be different -. Variations in the amount of this gas introduced into the reactor may affect temterixypy and localization of superheating in the reactor.
    The drawing shows a system in which all three reactors are down-flow reactors (reactants are introduced into the upper part of the reactor, and products are removed from the bottom). The method can, however, be carried out in both downstream and upstream reactors using an appropriate catalyst maintained by devices used for upstream reactors. Combining reactors with alternating downward and upward flows may reduce the cost of pipes. Thus, reactors 7 and 14 may be upstream reactors, and downstream reactor 10. In contrast, reactors 7 and 14 may be downstream, and reactor 10 may be downflow.
    The loading of hydrogen chloride does not necessarily have to be introduced into the reactor 7, part of it can be separated and introduced into the reactor 10 with the second part of oxygen-containing gas.
    In general, the process is carried out with an excess of both oxygen-containing gas and ethylene relative to hydrogen chloride in order to achieve the most complete conversion of hydrogen chloride. When air is used, it is desirable to keep the excess of these reagents as low as possible in order to avoid transporting large quantities of gas. In this case, an excess of ethylene is maintained at a maximum level of approximately 35%, preferably approximately 5-20%, and an excess of air is maintained at a maximum level of approximately 25%, preferably approximately 5-20%.
    The process is described here mainly in terms of oxychlorination, in which the oxygen-containing gas is air. However, the catalyst system and process are also suitable for use in such processes in which Molecular oxygen or air enriched with oxygen is used.
    The catalyst used in the following examples was obtained as follows. A certain amount of spherical non-impregnated alumina particles is placed in a beaker and weighed. Alumina has the following properties:
    Surface area (BET), Density, kg / m - 592.62-704.81 Losses during ignition (300 s) wt.% Maximum 5
    Hardness to abrasion. at least 90
    Pore volume, cm / g 0.44 Average pore diameter (WET), X 64-70 The pore volume with dimensions 80-600 A was 20-37% of the total pore volume, 5 Sieve analysis:
    3 mesh max. 1, O wt.% 3-4 mesh25-70 wt.%
    4-5 mesh25-70 wt.%
    5-6 mesh maximum 10 wt.%
    6 mesh
    maximum. 3 wt.%
    0
    The experimental data presented in the tables were obtained using catalysts prepared in accordance with the described process, and devices
    5 constructed as shown in the drawing. Each of the three reactors 7, 10 and 14 contains 40 nickel tubes with a length of 3.8 NT and a diameter of 6.35 cm with a downward flow of reagents. The heat of reaction is removed using Dowderm liquid circulating in the annular space between the pipes. Temperatures (overheating sites) inside the catalytic bed of each reactor are measured by means of a movable thermocouple with a length of 3.657 m, which is introduced from the bottom of each reactor.
    As shown in the drawing, hydrogen chloride is introduced into the system via line 1 through a preheater. Ethylene is introduced into the system via line 2 also a preheater. Air is fed to line 3 and divided into three streams.
    5 (lines 4., 5 and 6). Air through line 4 is introduced into reactor 7, through line 5 into reactor 10, and through line 6 into reactor 14. Mixed loading for reactor 7 after heating has a temperature of about 140 ° C. Download speed
    Air and ethylene were calculated as a percentage excess relative to hydrogen chloride in order to carry out a stoichiometric reaction to obtain 1,2-dichloroethane. five
    The gas exiting the reactor 14 after depressurization is cooled in a water-cooled glass condenser,
    0 in which all unreacted hydrogen chloride is condensed as an aqueous phase and most of the 1,2-dichloroethane obtained is relatively pure (approximately 98.6%)
    5 organic phase. The conversion of hydrogen chloride is determined by titration of the aqueous phase with sodium hydroxide.
    The uncondensed gas from the cooled condenser is analyzed by gas chromatography.
    The following are the conditions of the experiments carried out by the proposed method. Test 1, which lasted a total of 320 hours, was carried out in two stages. In the first stage, continued-:
    from 298 h, the process is carried out at 125% hydrocapacity of hydrogen chloride and other reagents. During the last 22 hours, the process is carried out at a 100% transmission rate.
    Three compositions of the proposed catalyst (A, B, and C), shown in Table 1, are prepared. The required amounts of cupric chloride and potassium chloride are as follows.
    Table
    The composition of the catalyst
    copper chloride, wt. %
    potassium chloride, wt.%
    iron in the form of Fe, ppm
    sulfate in the form.%
    silica as S i 0,
    0.25 weight. %
    Losses when calcinated at,
    6.0 weight. %
    Hardness, wt.% MINIMUM 93
    2045 196.5 149-165 0.25 0.25 0.25 Catalyst A: 6.0 ± 0, .5 wt.% CICPd 3.0 ± 0.3 wt.% KCi (weight ratio 2; 1). Catalyst B: 10.0 ± 0.7 ve (.% CuCfg. 3.0 i; 0.3 wt.% KCf (weight correlation 3.3: 1). Catalyst C: 18.0t1.8 wt.% CuCfg 1, Si 0.25 wt.% CS (weight ratio 10: 1). In all three reactors the length of the catalyst bed is 342.9 s. The first (upper) part is 205.74 cm long (60% of the total length of the layer) , i the second (lower) part has a length of 137.16 cm (40% of the total layer length). Catalyst A is used in the first part of the reactor bed 7, catcher B in the first part of the reactor bed 10, catalyst C in the reactor 14 and the lower parts of reactors 7 and 10. in i eaKTOpe 14 and in the lower parts of reactors 7 and 10.
    18.4-19.6
    1.84-1.92
    800
    0.5
    0.25
    6.0 95 During the first 60 hours of experience, adjust and stabilize the process. Similarly, the time from 265 to 298 hours is used to re-stabilize the process, followed by a one-month break between the stages of the experiment. During the process, as can be seen from Table 2, some changes are made in the total pressure of the system, in excess air and ethylene, and in the air distribution between the three reactors in order to determine the effect of these conditions on the conversion of hydrogen chloride, the selectivity of conversion 1 , 2-dichloroethane, as well as the effect on temperature and location of overheating zones. The data of the experiments are given in table 2.
    Beating mode
    10 97.7 0.6 22.79 4.9217 17
    22.79 4.921717 13 98.6 0.8 13.5 93.3 0.9
    22.79 4.921717
    22.79 4.9217171098.00.9
    22.79 4.9217171099.51.9
    22.79 4.9217171098.61.1
    22.79 5.6245171099,11.5
    22.79 5.6248101099.01.4
    22.79 5.6248221098.51.2
    22.79 5.6248171099,21.5
    22.79 5.6248171098.91.1
    22.79 5.6248171098.71.4
    Single stop after
    operating mode
    8-18, 23 4,429517
    899,21,5
    18.23 4.640517
    899,21,8
    18.23 4.781117
    ,
    18.23 4.921717 Note.
    Similar to experiment 1, additional experiments 2–9 were carried out, the results of which were given in Table 3, using various combinations of catalysts and reaction conditions in accordance with the proposed method. In all experiments, as was the case in experiment 1, a layer of catalyst is a 6 l and c a 2
    268/37285/44252 / 730.8788
    185., 37288/45253 / 740.9140
    284/37290/45253 / 560,9140
    286/37290/45255 / 740.8788
    286/37290/45278 / 36.0,8437
    287/37292/45258 / 550,8437
    280/36290/45264 / 480,7734
    275/37293/45288 / 370,7381
    282/37290/45253 / 730.8084
    278/37293/44268 / 380,7734
    297/45270/48254 / 570,7734
    300/52286/46262 / 560,8084 re-stabilization
    269/37284/28255/58
    280/38290/28256 / 580,5273
    294/35295/28260 / 560,4922
    297/36301/28 -0.5273
    ra has a length of 34.9 cm. In both
    reactors 7 and 10, the first upper zone is 205.74 cm or 60% of the total bed length, while the second zone is 137.16 cm or 40% of the total bed length. The catalyst in reactor 14 was similar to the catalyst used in experiment 1. The temperature of the cooler was maintained for reactor 7 210-215 ° C, for reactor 10 209-215 ° C, for reactor 14 219-227 C.
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    权利要求:
    Claims (2)
    [1]
    m-1 In all experiments (1-9), it can be seen that the use of the catalyst described above under these conditions leads to keeping the superheating temperatures generally below approximately at carrying capacities up to 125% of the required throughput of the reactants The overheating places have an adjustable location and in fact in many cases their temperature is lower. It is particularly important that the pressure drop remains approximately constant throughout the reaction system, even in Test 1, whose duration exceeded 300 hours. Thus, pressure reduction is not required to maintain superheat regulation and the pressure drop does not increase over an extended period of time due to deterioration of the catcher. Moreover, when working with high capacities, an excess of ethylene must be maintained within reasonable limits without significant adverse effects on the conversion of hydrogen chloride. As can be seen from the data in the table. 2 and 3, it is quite enough to work with an excess of ethylene of about 10%. At the same time, conversion of hydrogen chloride to 99% is achieved. Thus, the described catalyst and system are versatile and can be used in existing installations for considerable time without dropping the activity of the catalyst. Claims 1. Method for producing 1,2-dichloroethane by oxychlorinating ethylene. a mixture of hydrogen chloride and oxygen-containing gas at 200-340 ° C in the presence of a fixed catalyst bed containing copper chloride and potassium chloride on an inert carrier, in three consecutive catalytic zones, differing in that, in order to simplify the process, the latter is carried out using in the first catalyst zone of two layers of catcher, the first layer of which contains 4.5-12.5 wt.% copper chloride and 1.5-7 wt.% potassium chloride with a weight ratio of copper chloride and potassium chloride 1.5-4: 1 and takes 4575% of the length The whole zone and the second layer of which contains 12-25 wt.% chloride "of one and 0.5-4 wt.% of potassium chloride with a weight ratio of copper chloride and potassium chloride of 5-15: 1 and takes 2555% of the length of the entire zone, in the second catalytic zone of two catalyst layers, the first layer of which contains 5.5-15 wt.% copper chloride and 1-5 wt.% potassium chloride with a weight ratio of copper chloride and potassium chloride 2-6: 1 and takes 45-75% the length of the entire zone and the second layer of which contains 1225 wt.% copper chloride and 0.5-4 wt.% potassium chloride with a weight ratio of copper chloride and potassium chloride 5-15: 1 and takes em 25-55 wt.% the length of the entire zone, in the third catalyst zone of the catalyst containing 1225 wt.% copper chloride 0.5-4 wt.% potassium chloride with a weight ratio of copper chloride and potassium chloride 5-15: 1.
    [2]
    2. The method according to claim 1, which is also characterized in that activated alumina is used as an inert support for the catalyst. Sources of information taken into account in the examination 1. US patent number 3699178, cl. 260-659, published. 10/17/72 (prototype).
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    同族专利:
    公开号 | 公开日
    US4123467A|1978-10-31|
    BE844056A|1977-01-12|
    SU1225473A3|1986-04-15|
    CS202554B2|1981-01-30|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    CA517009A|1955-09-27|W. Hearne George|Manufacture of olefin dichlorides|
    IT713532A|1962-02-01|
    GB1104666A|1964-05-29|1968-02-28|Stauffer Chemical Co|Oxychlorination of ethylene to ethylenedichloride|
    DE1668749C3|1967-06-23|1974-01-03|Toagosei Chemical Industry Co., Ltd., Tokio|Process for the production of 1,2-dichloroethane|
    US3892816A|1972-12-19|1975-07-01|Shell Oil Co|Process for oxychlorination of ethylene|
    DE2356549C2|1973-11-13|1975-10-30|Basf Ag, 6700 Ludwigshafen|Process for the production of 1,2-dichloroethane by oxychlorination of ethylene|CA1120956A|1977-09-07|1982-03-30|Vulcan Materials Company|Process for the production ofperchloroethylene by catalyticoxychlorination|
    US4849393A|1986-08-21|1989-07-18|The B.F. Goodrich Company|Catalyst and process for the fluid-bed oxychlorination of ethylene to EDC|
    US5227548A|1988-12-20|1993-07-13|Imperial Chemical Industries Plc|Oxychlorination of ethylene to 1,2-dichloroethane|
    US5202511A|1989-08-16|1993-04-13|The Dow Chemical Company|Catalyst diluent for oxychlorination process|
    DE4018512C2|1990-06-09|1992-05-07|Wacker-Chemie Gmbh, 8000 Muenchen, De|
    GB2294262B|1994-10-20|1998-07-08|Evc Tech Ag|Single stage fixed bed oxychlorination of ethylene|
    BR9608539A|1995-06-07|1999-07-06|Dow Chemical Co|Axichlorination method using no more than two oxychlorination reactors|
    DE10003510A1†|2000-01-27|2001-08-02|Basf Ag|Process for the preparation of 1,2-dichloroethane|
    US20040151630A1|2002-08-26|2004-08-05|Hernandez Herbert A.|Total nitrogen and sulphur analysis using a catalytic combustion gas converter system|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US59546575A| true| 1975-07-14|1975-07-14|
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