• 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:
    Disclosed is a method for stopping and starting a reactor equipped with a heat exchanger, a catalyst settler, a catalyst filter and the like, which method is suitable for use in a process for the preparation of acrylamide by reacting acrylonitrile with water in the presence of a metallic copper-based catalyst used as a suspended bed. According to this method, various undesired phenomena which may occur at the beginning of operation can be prevented by discharging the metallic copper-based catalyst until the total amount of metallic copper and copper oxides present in the catalyst remaining in the reactor is not greater than a certain level based on the amount of metallic copper catalyst used at the beginning of the operation, or by discharging the catalyst until the amount of copper oxides is not greater than a certain level and then establishing an inert environment within the reactor.
    公开号:SU1757461A3
    申请号:SU874028981
    申请日:1987-02-04
    公开日:1992-08-23
    发明作者:Асано Сиро；Сизука Кохеи；Камбара Есихико
    申请人:Мицуи Тоацу Кемикалз, Инкорпорейтед (Фирма)；
    IPC主号:
    专利说明:

    This invention relates to the field of organic chemistry, namely to an improved method for the preparation of acrylamyd used to make polymers. ;
    The aim of the invention is to refine the process by preventing the deterioration of catalyst activity, improving filterability and ability to precipitate.
    Example 1 (comparative) .V
    Catalyst Preparation: René copper alloy, made of aluminum and copper with a weight ratio of 50:50, is pulverized and sieved to remove large particles having a size of 80 mesh or more. To this powdered alloy, add up to a 25% aqueous solution of sodium hydroxide, podder) Kivam6Gb gtrbG 50-60 ° C for an additional hour to form a catalyst based on René copper. This catalyst is thorough
    washed with water using decantation and stored in water.
    The process:
    A 10 liter stainless steel reactor, equipped with a stirrer, an integrated injection coil for steam formation and an integrated catalyst filter, is used for the reaction. First of all, the internal space of the reactor is filled with nitrogen bm and loads 2 kg (of the above catalyst, in the form in which it was immersed in water. Then acrylonitrile and water, through which nitrogen is blown to remove dissolved oxygen, are fed into the reactor at a rate of 3 kg / h and 6 kg / h, respectively. Thus, using a heating coil for steam to maintain a temperature of 120 °, the reaction lasts for three weeks with stirring.
    VI with
    2
    Os

    with
    Reaction Results:
    The reaction solution obtained after filtering the catalyst is collected and analyzed. Analytical results are shown in Table. one.
    Catalyst unloading:
    After about three weeks, the supply of acrylonitrile is suspended, the temperature of the reactor is lowered and the reactor is washed by supplying water to it. Then the water supply is stopped. With continued agitation, the catalyst is discharged through an exhaust valve provided at the bottom of the reactor. As a result of this operation, the inside of the reactor is filled with air. The reactor is left in this state for a week. The experiment shows that about 20 g of the catalyst remains in the reactor after removing the catalyst in accordance with the above operation, and that about 12 g of the residual catalyst would oxidize if left in an atmosphere of air for a week.
    Resumption of reaction:
    After a week, the reactor is charged with another portion of unused catalyst that was previously prepared and stored, and the reaction is resumed by applying the same operation and conditions as described previously. Within 4 hours after the resumption, the reaction appeared normal. However, after 24 hours, the flow resistance of the catalyst filter increased from a normal value of 0.1 kg / cm or less to 0.5 kg / cm2, indicating that the filter is clogged. After 48 hours, the flow resistance increased to 2.6 kg / cm2, so it became difficult to continue the experiment. Thus, the entire system was stopped in accordance with the same operation as previously described, and there was an attempt to remove the catalyst from the bottom of the bottom of the reactor. However, its removal was impossible due to clogging of the pipeline. In this experiment, the amount of copper oxides present in the catalyst used since the beginning of the operation was 0.6 wt.%. 4
    Results of renewed reaction:
    As can be seen from the data in the table. 2, it is believed that the activity of the catalyst has rapidly decreased.
    Check reactor and catalyst:
    When the reactor was opened and tested, a large amount of polymer was mixed with the catalyst. In addition, it was noted that a large amount of polymer adhered to the helix to heat the steam and to the catalyst filter.
    Example 1A The reaction is carried out for three weeks in the same manner as described in Comparative Example 1. The catalyst is then discharged when into the reactor.
    nitrogen is introduced in such a way as to prevent air from entering the reactor. Thus, the reactor is maintained at a nitrogen pressure of 2 kg / cm for a week. Another experiment showed that if the reactor was maintained in this state, only 1 g or less of catalyst remaining in the reactor was oxidized. After a week, 2 kg of unused catalyst is loaded into the reactor, renewed
    reaction and continue it for about 3 weeks in such a way as described in comparative example 1. In this experiment, the amount of copper oxides was 0.05 wt.% The results of the reaction carried out during the above two periods are given in table. 3
    During the whole experimental period, the resistance to flow of the catalyst filter remained at the level of 0.1 kg / cm2
    or less. After the completion of the experiment, the reactor was washed with water as described in Example 1. Then the catalyst was removed, immersed in water and stored under nitrogen. The polymer is not admixed with this catalyst. When the reactor was open, “tested inside, no polymer was found.
    Example 1B After completing Example 1A, most of the catalyst remaining in the reactor is thoroughly washed out with a water jet under pressure. Another experiment showed that according to this operation, the amount of catalyst remaining in the reactor is approximately
    0.2 g, and all of it is oxidized as a result of the reactor being in an air atmosphere for a week. After this reactor has been in an atmosphere of air for one week, a catalyst is loaded into it,
    which was recovered in Example 1A and was in storage. The reaction was resumed in the same manner as described in Example 1A. The results obtained for about 3 weeks are shown in Table. four.
    During the entire experimental period, the resistance to flow of the catalyst filter remained at a level of 0.1 kg / cm2 or less. When the inside of the reactor was tested after the experiment was completed, no polymer was detected. In this experiment, the amount of copper oxides was 0.01 wt.%.
    Comparative Catalyst:
    example 2.
    A catalyst prepared in the same manner as described in Comparative Example 1 is used.
    A 10-liter stainless steel reactor (Fig. 1) is used with a catalyst sump section 3, a steam heating coil 4 and a stirrer 5 installed in it. This reactor is designed as a vertically arranged cylindrical main body with a diameter of 220 mm, with a conical bottom and upper lid, consisting of a flat plate. The sump section is the space formed between the dummy body and the inner 170 mm diameter pipe located in it. In this space, there are 12 slots 7 at regular intervals with the possibility of tilting. The feed is fed through the feed pipe 1 to the feed to the top of the reactor and reacts in the inner tube. The reacted solution moves obliquely along the inclined plates of the settling section and exits the reactor through the outlet pipe 2 for the reacted solution. To remove the catalyst after completing the experiment, a catalyst outlet valve 6 is installed at the bottom of the reactor.
    The process:
    The reaction was carried out for about 1 week under the same conditions as described in comparative example 1. The results obtained in this way are shown in Table. five.
    Catalyst unloading:
    After about 1 week, the supply of acrylonitrile is stopped, the temperature of the reactor is lowered and its washing is continued with water. Then the water supply is also interrupted, although stirring is continued. The catalyst is discharged through an exhaust valve for the catalyst in the reactor vessel. This catalyst is stored in water. The gas phase of the reactor is replaced with nitrogen. Next, the remaining catalyst is washed out in the reactor using a water jet under pressure. Another experiment showed that about 100 g of catalyst remained in the reactor (mainly on inclined plates of the settling section) after removing the catalyst in accordance with the above operation, and that about 40 g of residual catalyst was oxidized while leaving the reactor in an atmosphere of air for a week.
    Resumption of reaction:
    After the reactor has been in air for a week, it is loaded again with a catalyst that has been stored in such a way that it does not enter
    contact with air, and the reaction is resumed under the same conditions as described above. On the day of the resumption, the reaction is normal. However, after 12 hours, a sample of the reacted solution, which was divided into two layers upon cooling, indicated that
    0 dropped to 50% or less. After 16 hours, not only the reacted solution, which was divided more noticeably into two layers, but also a large number of polymer particles was found mixed with the reacted solution. Thus, the entire system was stopped in accordance with the same operation as described earlier. Check reactor and catalyst: When the reactor was opened and tested,
    0 a large amount of polymer mixed with catalyst was found. In addition, it was noted that a large amount of polymer along with a small amount of catalyst stuck to the inclined
    5 plates of the settling section. In this experiment, the amount of copper oxides was 2 wt.%.
    Example 2. The reaction is carried out during the week as described in Comparative Example 2. The catalyst is then discharged, immersed in water and stored under a nitrogen atmosphere. The reactor is immediately filled with water and left in this position for a week. Another experiment showed that the amount of catalyst oxidized under these conditions was 1 g or less. After a week, the reactor was loaded with the stored catalyst / the reaction was resumed and continued for
    0 about 1 week in the same manner as described in comparative example 2.
    The results of the reaction carried out during the above two periods are shown in Table. 6
    5 After the above reaction was completed, the entire system was stopped in the same manner as described in Comparative Example 2. When the reactor was opened and tested, no polymer was detected. In that
    In the experiment, the amount of copper oxides was 0.05 wt.%.
    Comparative Example 3. Catalyst: A catalyst prepared in the same manner as described in Comparative Example 1 is used.
    A 10-liter stainless steel reactor (Fig. 2) is used with a catalyst sump section 3 installed therein, a steam heating coil and a stirrer. This reactor has a vertically arranged cylindrical main body.
    220 mm in diameter, with a conical bottom / bottom and top cover in the form of a flat plate. In the upper part of the reactor, 24 wire nets with a cell size of 3x3 mm are placed horizontally one on top of the other, thus forming a settling tank. The feed is fed through the feed tube 1 to the inside of the reactor and the reaction proceeds at the bottom of the reactor. The reacted solution is sent to the settling section and discharged from the reactor through an outlet pipe 2 for the reacted solution. After removal of the catalyst, an exhaust valve for the catalyst was installed at the bottom of the bottom of the reactor to remove the catalyst.
    Reactions;
    The reaction is carried out for about 1 week under the same conditions as described in comparative example 1. The results are shown in Table. 7
    Catalyst unloading
    After a week, the supply of acrylonitrile is interrupted, the temperature of the reactor is lowered and its washing with water is continued. Then the water supply is also interrupted. While stirring is continued, the catalyst is discharged through an exhaust valve. Further, in order to recover a small amount of the catalyst remaining in the settling section, the reactor is refilled with water and drained. The catalyst thus reduced is stored in water. The gas phase of the reactor is replaced with nitrogen. Another experiment showed that about 50 g of catalyst remained in the reactor (precipitated mainly in the settling section) after removing the catalyst in accordance with the above operation, and that about 40 g of residual catalyst was oxidized when it was in the atmosphere of air for a week.
    Resumption of reaction:
    After the reactor has been in the atmosphere for one week, it is again loaded with a catalyst, which has been unloaded and stored so that it does not come in contact with air, and the reaction is resumed under the same conditions as described above. At the beginning of the reaction, things looked normal. However, after 12 hours, a sample of the reacted solution, which was divided into two layers upon cooling, showed that the conversion rate decreased to 50% or less. In addition, polymer particles were found in the reacted solution. After 24 hours, the separation of the reacted solution into two layers and the presence of polymer particles in it became more noticeable. So the sun system was
    stopped according to the same operation as previously described
    Check reactor and catalyst:
    When the reactor was open and tested, more polymer was mixed with the catalyst. In addition, it was noted that a large amount of polymer along with a small amount of catalyst stuck to the wire mesh of the sump section. In this experiment, the amount of copper oxides was 2 wt.%.
    Example 3. The reaction is carried out during the week in the same manner as described in Comparative Example 3. The catalyst is then discharged. Next, to recover the catalyst that settled in the settling section, the reactor is refilled with water and emptied. As described in comparative example 3, the catalyst thus recovered is immersed in water and stored under a nitrogen atmosphere. The residual catalyst is then dissolved by filling the reactor with 10% nitric acid and stirring it for about 1 hour, and then washing the reactor with water. When the reactor was opened and tested, it was confirmed that there was no catalyst left in it. After a week, the reactor is again charged with the stored catalyst, the reaction is resumed and continued for about 1 week in the same manner as described in comparative example 3.
    The results of the reaction carried out during the above two periods are given in table 8.
    After completion of the above reaction, the entire system was stopped in the same manner as described in comparative example 3. When the reactor was opened and checked, no polymer was detected. In this experiment, the amount of copper oxides was 0 wt.%.
    Comparative example 4.
    Catalyst Preparation:
    The composition of the oxide of copper-chromium oxide was prepared as follows: to 25 wt.h. ammonium dichromate, dissolved in 100 parts of water, is added 30 parts of ammonium hydroxide to obtain ammonium chromate. To this solution of ammonium chromate, a solution of 20.2 hours of copper chloride, dissolved in 150 hours of water, is slowly added with continuous stirring. The resulting precipitate is separated and washed several times with about one liter of water each time. The isolated precipitate is dried at 100 ° C for 8 hours, and then heated at 275 ° C in air for 3 hours. Using a table-forming apparatus, the composition obtained is
    form into cylindrical tablets with a diameter of 5 mm and a thickness of 5 mm. A stainless steel reaction tube with an inner diameter of 50 mm is loaded with 2000 g (1600 g as copper) molded tablets. By passing a gas of hydrogen diluted with nitrogen, a reduction is carried out through this pipe at 250 ° C for 4 hours in order to obtain a catalyst of the so-called reduced copper chromium oxide. This catalyst is then immersed in water and milled under nitrogen to particles of about 1 mm or less.
    Reactions:
    The inner space of the same reactor as used in Comparative Example 1 is first filled with nitrogen and then loaded with the above catalyst immersed in water. Acrylonitrile and water, through which nitrogen was previously blown to remove dissolved oxygen, are fed into this reactor at a flow rate of 1.5 kg / h and 3 kg / h, respectively. The reaction proceeds for about 1 week using stirring and a vapor heating coil to maintain the reaction at 120 ° C. The results of the reaction carried out in this way are given in table. 9.
    Catalyst unloading
    After completion of the reaction, the delivery of acrylonitrile is stopped, the temperature in the reactor is reduced, and the rinsing of the reactor with water is continued. Then the water supply is also interrupted. Although stirring is continued, the catalyst, along with the water, is discharged into the reactor through a catalyst outlet valve installed at the bottom of the reactor. To further reduce the reactor remaining in the catalyst, the reactor is filled with water, followed by stirring and draining the water. After removal of the catalyst, it was noted that about 20 g of the catalyst was still settled or stuck to the internal surfaces of the reactor. Then the reactor was left for 1 week in an atmosphere of air. Another experiment showed that most of the copper present in the residual catalyst is oxidized under these conditions. The catalyst withdrawn as described above was stored in water and the gas phase of the reactor was replaced with nitrogen gas.
    Resumption of reaction:
    After a week, the reactor is again charged with a catalyst that has been unloaded and stored, manipulating in such a way as to avoid contact of the catalyst with air, and the reaction is resumed under the same conditions as previously described. On the day of the resumption, the reaction looked normal. After 24 hours, the resistance on the catalyst filter increased to a normal value of 0.1 kg / cm2 or less, to 0.2 kg / cm2. After 48 h flow resistance
    increased to 1.2 kg / cm. Thus, the entire system was stopped in accordance with the same operation as previously described. The results of the renewed reaction. As can be seen from the data in the table. 10, catalyst activity rapidly decreased. Inspection of the reactor and catalyst1 When the reactor was opened and tested, a large amount of polymer was mixed with the catalyst or
    5, the catalyst particles were coated with a gel-like polymer. In this experiment, the amount of oxide in copper was 1.25 wt.%
    Example 4. The reaction is carried out in
    0 for about 1 week in the same manner as described in the previously mentioned step of comparative example 4. Then the catalyst was discharged. Immediately after that, a vacuum pump was connected to the reactor, and
    5, the pressure in the reactor is maintained at 10 tor or less. In this position, the reactor is left for a week. Another experiment showed that the amount of copper oxidized during this period was 1
    0 g or less. Thereafter, the reaction was resumed and continued for about 1 week in the same manner as described in comparative example 4.
    The results of the reaction carried out over the above two periods are shown in Table 11.
    No polymer particles were detected in the reaction solution. In addition, when the internal part of the reactor was tested
    0 after the experiment was completed, the polymer was not detected. In this experiment, the amount of copper oxides was 0.06 wt.%.
    Thus, the method of the present invention prevents the decrease in catalyst activity, which often takes place immediately after the start of operation without contamination of the final product with a stabilizer, and without difficulty. which occur, for example, during the passage of a solution through a catalytic filter.
    权利要求:
    Claims (1)
    [1]
    The invention method for producing acrylamide hydrate by acrylonitrile with water in the presence of a catalyst — Rene copper in a suspended layer in a mixing reactor followed by separation of the target product and discharging the catalyst, characterized in that, in order to simplify the process, the catalyst is discharged to the content of copper oxides in the reactor in terms of metallic copper, not more than 0.06 wt.%, while, if the content of the remaining metallic copper exceeds 0.01 wt.%, the reactor is additionally either evacuated or filled with inert gas or water.
    Note. An is acrychunitrile, HPN is / Hydroxypropionitrile, and DAM is acrylamide. (The same will apply hereafter).
    Table 2
    Table3
    Table4
    Ta lb and c and 5
    Table
    Table
    That b l and tsa8
    E table
    Table 10
    Table 11
    FIG. 2
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    引用文献:
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    JP61022008A|JPH0662526B2|1986-02-05|1986-02-05|How to stop the acrylamide reactor|
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