WO1998007510A1 - Procede de reaction catalytique execute pres de la temperature optimale - Google Patents

Procede de reaction catalytique execute pres de la temperature optimale Download PDF

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Publication number
WO1998007510A1
WO1998007510A1 PCT/CN1997/000082 CN9700082W WO9807510A1 WO 1998007510 A1 WO1998007510 A1 WO 1998007510A1 CN 9700082 W CN9700082 W CN 9700082W WO 9807510 A1 WO9807510 A1 WO 9807510A1
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WO
WIPO (PCT)
Prior art keywords
cold
gas
tube
pipe
catalyst
Prior art date
Application number
PCT/CN1997/000082
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English (en)
French (fr)
Inventor
Shoulin Lou
Ren Lou
Original Assignee
LU, Mushu
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Filing date
Publication date
Application filed by LU, Mushu filed Critical LU, Mushu
Priority to US09/242,574 priority Critical patent/US6214296B1/en
Publication of WO1998007510A1 publication Critical patent/WO1998007510A1/zh

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/02—Preparation, purification or separation of ammonia
    • C01C1/04—Preparation of ammonia by synthesis in the gas phase
    • C01C1/0405—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst
    • C01C1/0417—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst characterised by the synthesis reactor, e.g. arrangement of catalyst beds and heat exchangers in the reactor
    • C01C1/0423—Cold wall reactors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/0207—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid flow within the bed being predominantly horizontal
    • B01J8/0214—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid flow within the bed being predominantly horizontal in a cylindrical annular shaped bed
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/0242—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid flow within the bed being predominantly vertical
    • B01J8/0257—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid flow within the bed being predominantly vertical in a cylindrical annular shaped bed
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/0285—Heating or cooling the reactor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00017—Controlling the temperature
    • B01J2208/00106—Controlling the temperature by indirect heat exchange
    • B01J2208/00115—Controlling the temperature by indirect heat exchange with heat exchange elements inside the bed of solid particles
    • B01J2208/00132—Tubes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the invention relates to a gas-solid phase catalytic reaction process method and a reaction device for implementing the method, which are used for the gas-solid phase catalytic reaction and heat transfer process.
  • the invention belongs to the field of chemical engineering and is particularly suitable for the ammonia synthesis reaction process. It can also be used in the synthesis of methanol, formamidine and methyl ether. Background technique
  • This reactor affects the synthesis rate because the temperature of the reaction gas and the concentration of the reactants are reduced during the cold shock of the raw material gas. Therefore, an improved form has appeared.
  • the better one is to divide the catalyst into three beds. Cold shock is used between the first and second stages, and indirect heat exchange is used between the second and third stages. See CN 1 030878, 89 filed by Casale. It was published on February 8, 2014, but this type of reactor has not completely eliminated the influence of the cold shock raw material gas on the concentration of the reactants, and the equipment structure is complicated due to the indirect heat exchangers installed between the bed sections. Summary of invention
  • the purpose of the present invention is to overcome the shortcomings of the prior art based on the characteristics of gas-solid phase catalytic exothermic reversible reaction, and to provide a reactor with reasonable temperature distribution of the catalyst layer, high catalyst activity, simple and reliable structure, and good operating performance, and a reactor. Process method for reacting at the optimal temperature.
  • the present invention mainly achieves the object of the present invention through the following improved methods:
  • the raw material gas is mainly divided into two streams: gas stream 1 and gas stream 2, which are heated separately.
  • Gas stream 1 exchanges heat with the reaction gas at the catalyst layer outlet.
  • Gas stream 2 heats up in countercurrent with the reaction gas in the cold tube above the catalyst layer and outside the catalyst layer in the catalyst layer.
  • the gas volume and temperature of the gas stream 2 in the cold tube can be based on the temperature of the catalyst layer.
  • the second is to mix the heated raw gas stream 1 and gas stream 2 to react in the cold tube catalyst layer and exchange heat with the raw gas in the cold tube, and then enter the adiabatic reaction in the lower catalyst layer.
  • a countercurrent cold pipe is used for heat exchange before the reaction, so that The reaction can begin-in near-adiabatic conditions, so that the optimal temperature is reached quickly, and then with the counter-current heat exchange of the cold tube, the temperature difference between the inside and the outside of the tube increases, and the catalyst temperature decreases along the optimal line to the exit of the cold tube layer It can fall below the optimal line to create conditions for the adiabatic reaction in the later stage.
  • the synthesis reactor of the present invention is mainly composed of a shell P, a catalyst basket R and a heat exchanger E.
  • the shell P is under pressure, and the general reaction pressure is 14 to 32 MPa.
  • the cover plate H of the catalyst basket R, the barrel S, and the bottom of the catalyst basket R The flower plate supports the catalyst layer in the catalyst basket.
  • the catalyst layer is composed of a cold-tube catalyst layer K 1 and an adiabatic catalyst layer K 2 with a countercurrent cold-tube bladder Cb.
  • the cold-tube bladder Cb is mainly composed of an intake pipe a , a cold pipe 1, and a ring pipe dl connecting the intake pipe a and the cold pipe b.
  • the cold pipe bladder Cb may also be composed of an intake pipe a , a cold pipe b, an outlet pipe c, a ring pipe dl connecting the inlet pipe a and the cold pipe b, and a ring pipe d2 connecting the cold pipe b and the outlet pipe c.
  • the cold pipe catalyst layer K 1 may have one or several coaxial cold tube bladder cb. Each cold tube bladder has coaxial multiple rows of cold tubes b arranged in different circle diameters.
  • the raw material gas enters through the inlet pipe a, and is distributed to each cold pipe b through the ring pipe dl.
  • the raw material gas stream 2 in the pipe is heated by the high-temperature reaction gas in the catalyst layer K 1 outside the pipe to be heated in countercurrent, and the temperature is raised. Then, it is directly exported from the cold pipe b or through the ring pipe d2 and the outlet of the air pipe c, and is mixed with the airflow 1 heated by the heat exchanger and exited from the central pipe I to reach the catalyst activation temperature, and then enters the cold pipe catalyst layer K 1 in sequence. It reacts and exchanges heat with the gas in the cold pipe b countercurrently, and then enters the adiabatic catalyst layer K2 to react.
  • the ratio of the temperature of the airflow 2 from the cold pipe to the temperature of the mixed gas in the catalyst layer of the cold pipe is 0.75 to 1.25.
  • the catalyst in the cold pipe catalyst layer accounts for 15-80% of the total tower catalyst, and the best is 30-50%.
  • the gas can be an axis in the cold pipe catalyst layer K1 and the adiabatic catalyst layer K2. It can also flow in the axial direction in the cold pipe catalyst layer K 1 and then in the thermal insulation catalyst layer K2 in the radial and axial radial directions; or in the thermal insulation catalyst layer K2 in the opposite direction.
  • the cold pipe b can be a circular single pipe or a flat pipe.
  • the ratio of the heat transfer area of the cold pipe to the volume of the contact medium is 3-20M2 / M2.
  • Figure 1 is a schematic diagram of a reactor consisting of an axial countercurrent cold pipe layer and an insulation layer.
  • Figures 2 and 3 are schematic diagrams of a reactor consisting of an axial countercurrent cold pipe layer and a radial insulation layer.
  • Figure 4 is a schematic diagram of a reactor used to transform an existing large-scale ammonia synthesis tower into an axial countercurrent cold pipe layer and a radial insulation layer.
  • Figure 5 is a schematic diagram of a reactor consisting of an axial countercurrent cold pipe layer and an opposite cocurrent axial insulation layer.
  • Figure 6 is the connection diagram between the reactor and the equipment outside the tower.
  • Fig. 7 and Fig. 8 are tx diagrams of the reactor.
  • the horizontal coordinate on the graph is the reaction temperature 'C, and the vertical coordinate is the molar concentration of ammonia.
  • Figure 1 shows a type of reactor suitable for the present invention, such as an ammonia synthesis tower.
  • the inner part is installed in a pressure-containing outer cylinder P, and the outer cylinder and the inner cylinder wall S have a ring shape.
  • the gap, the upper part of the inner part is the catalyst basket R, there is a central tube I in the middle, and the catalyst basket contains the catalyst, :
  • the upper catalyst layer K 1 is equipped with a cold tube bladder Cb.
  • the cold tube bladder has a plurality of cold tubes b, which are divided into 2 to 4 rows coaxially, and connect the lower ring tube dl and the upper ring tube d2, and the lower ring tube dl.
  • the air inlet pipe a passes through the catalyst cover H and is sealed with a stuffing box or sealed with a corrugated hose.
  • the ring pipe d2 is located in the space above the catalyst layer after reduction.
  • the cold tube can be expanded and contracted freely when heated.
  • the cold tube is supported by the support frame L and supported on the porous flower plate J together with the catalyst.
  • the lower part of the inner part is a column tube heat exchanger E, or a spiral plate heat exchanger.
  • the inlet gas 1 and 2 are separated by the cylinder and the bottom head U.
  • the bottom cover V of the heat exchanger separates the inlet gas 1 and the outlet gas 4.
  • the cold air passes through the tower and passes through it.
  • the heat exchange between the bottom head U and the bottom cover V of the internal heat exchanger enters the heat exchanger E and exits the catalyst layer, and is heated by the electric heater in the central tube I, and then the catalyst layer is heated and reduced by the catalyst.
  • the gas entering the tower is mainly divided into two streams: airflow 1 and airflow 2. Airflow 1 is exchanged by the heat exchanger E and the reaction gas and exits from the central tube I.
  • the flow 2 After the flow 2 enters the tower, it passes through the annulus between the outer tube P and the inner parts, and enters the cold pipe bladder C b through the inlet pipe a, and is evenly distributed from the lower ring pipe dl to each of the cold pipes b and flows from bottom to top.
  • the reaction gas outside the tube is counter-heated to increase the temperature until the upper ring tube d2 is collected and passed through the outlet of the gas tube c, and then mixed with the raw material gas 1 from the central tube I.
  • a mixed gas with a temperature of 350-430 'C First react in the cold tube layer ammonia catalyst K 1 to increase the product concentration. During the reaction, heat M is released to increase the gas temperature.
  • the heat exchange with the cold air in the cold tube b will increase the temperature of the reaction gas to a hot spot temperature of 450-5
  • the temperature began to decrease to about 380-430' C, and then the adiabatic reaction in the lower adiabatic catalyst layer K2, and then increased to a temperature of about 460 'C, the product concentration further increased, such as ammonia synthesis is 15 ⁇ 20% mole
  • the gas flows axially in the cold pipe layer K1 and the heat insulation layer K2, and the reaction gas exits the catalyst layer and then enters the heat exchanger E to exchange heat with the inlet gas 1 to form the outlet gas 4 Tower.
  • the gas 3 in the picture is the cold auxiliary line gas used to adjust the zero-meter temperature into the catalyst layer.
  • Figure 2 is a reactor with a relatively large diameter. Gas flows axially in the catalyst layer of the cold pipe.
  • the difference from Figure 1 is that the lower part of the catalyst basket R is a radial flow insulation layer and the catalyst support plate. J is not vented, and there is a porous outer distribution tube X inside the catalyst basket cylinder S, and a concentric porous inner distribution tube Y outside the center tube I.
  • Most of the reaction gas passing through the upper cold tube catalyst layer K 1 enters the outer distribution first.
  • a radial flow reaction is performed until the inner distribution cylinder Y enters the annular space of the inner distribution cylinder Y and the central pipe I, and the small Part of the reaction gas flowing from the axial direction of the cold tube layer into the confluence of the people here, to the lower heat exchanger E, the column-type heat exchanger and the inlet gas 1 are heat-exchanged, and then the outlet gas 4 is shown in Fig. 3.
  • the bladder is supported on the inner tube wall S by the support frame L, and there are two cold tube bladder Cb.
  • the other illustrations and symbols in FIG. 2 are the same as those in FIG. 1, of course, the lower insulation layer can also be designed so that the gas is radially from the inside to the outside.
  • the distribution cylinder in the figure is also attached with a metal wire mesh, and can be provided with reinforced supports, spacers, and nozzles. These are known techniques and have not been drawn.
  • Fig. 3 is a reactor with the same reaction and heat exchange flow mode as Fig. 2.
  • the cold tube bladder Cb is mainly composed of an inlet pipe a, a cold pipe b, and a ring pipe connecting the inlet pipe a and the cold pipe b. It is composed of dl, and the cold pipe b directly protrudes from the catalyst layer to produce gas. Therefore, the structure is simple and the processing is convenient.
  • the cold pipe shown in FIG. Other illustrations and symbols in FIG. 3 are the same as those in FIG. 2.
  • Figure 4 is a reactor used to retrofit an existing large ammonia plant.
  • a Kellogg bottle-type large ammonia synthesis tower is transformed into a reactor of the present invention.
  • Figure 4 is the same as Figure 2.
  • the upper part of the catalyst layer is an axial flow countercurrent cold pipe layer.
  • each cold pipe is respectively composed of the inlet pipe a, the outlet pipe c, and the cold
  • the pipe b and the ring pipes d1 and d2 are composed, and the air inlet pipe a may be connected by a bellows when passing through the cover H of the inner casing, and the lower part is a shaft radial flow insulation layer K2.
  • the heat exchanger ⁇ is installed in the upper part of the reactor, and the catalyst can be discharged through the lower bottom hole Q after opening the hole cover, and the airflow 2 entering the tower from the bottom enters the cold tube bladder through the annular gap between the outer tube P and the inner part.
  • Airflow 1 enters the shell of heat exchanger E between heat exchanger head U and V and enters the shell side of heat exchanger E and exchanges heat with reaction gas 4 in the tube. After exiting the heat exchanger, it is mixed with gas 2 heated by the cold tube Cb.
  • the reaction in the cold tube catalyst layer kl reacts with the gas in the cold tube b in countercurrent heat transfer. Except for a small amount of the axial flow of the cold tube layer, most of the gas flows from the outer distribution tube X into the adiabatic catalyst layer and flows in the radial direction.
  • the inner distribution tube Y heat is exchanged with the inlet gas 1 through the central tube i to the upper heat exchanger E tube, which is the outlet gas 4 and the cold air 3 inlet to adjust the zero-meter temperature of the catalyst layer.
  • the axial radial reactor resistance is smaller than the axial direction, so the operating airspeed, that is, the ratio of the total air volume of the tower to the volume of the contact medium, can take a larger value.
  • FIG. 5 is another type of the axial tower of the present invention.
  • the countercurrent cold-tube bladder Cb is supported by the support frame L on the inner tube wall S, and
  • the collector Z is connected to the heat exchanger E through the sleeve N.
  • the tube heat exchanger is shown in the figure.
  • the porous plate J in the catalyst basket There is a partition G between the heat exchanger E and the heat exchanger E.
  • the inlet gas 1 heated by the heat exchanger E and the gas 2 heated by the cold tube are mixed and then reacted through the upper cold tube catalyst layer K 1 and exchanged with the gas in the cold tube b in countercurrent heat exchange to exit the cold tube catalyst layer.
  • Half of the gas continues to react in the upper part of the catalyst layer K2 from top to bottom, and the other half of the gas enters the collector W and passes through the connecting pipe M to the space below the catalyst basket plate J, and then reacts from the bottom to the lower part of the adiabatic catalyst layer K2.
  • the two reaction gases flow in the opposite direction in the thermal insulation layer K2 to the central inlet gas collector Z, and then pass through the casing N.
  • the annular space between the tube and the central tube I- flows down to the space below the partition G, and heat is exchanged into the tower gas 1 through the heat exchanger E and outside the tube into the tower gas 4 and the tower inlet gas 3 is used for regulation.
  • the secondary line of the catalyst layer temperature is used for regulation.
  • FIG 6 is the connection diagram of the reactor and the equipment outside the tower, where R 1 is the reactor, the internal structure is shown in Figure 1-5, E2 is the cold and hot air heat exchanger outside the tower, E3 is the pre-production steam boiler, and E4 is the cooling
  • the condenser, VI is a product separator such as an ammonia separator, and T 1 is a cycle machine.
  • the incoming tower gas sent by the cycle machine is divided into three streams, of which the gas stream 1 is heated by the external heat exchanger E2 and then further heated in the reactor, and the gas stream 2 enters the reactor and the cold tube bile absorbs the cold tube layer catalyst.
  • the heat of reaction is adjustable.
  • the air volume of airflow 1 and airflow 2 can be adjusted.
  • the airflow of airflow 2 into the cold tube is generally 30-70% of the total air volume.
  • the temperature of the airflow 2 can be adjusted by the ratio of the air volume passing through and not passing through the heat exchanger E2, for adjusting the temperature of the catalyst layer according to the different periods of use of the catalyst;
  • the heat is recovered by the boiler E3 and then goes to the heat exchanger E2 to heat the raw gas of the tower.
  • 5 is a separated product such as liquid ammonia or methanol
  • 6 is a purge gas
  • 7 is a supplementary feed gas.
  • the cycle machine is located between the ammonia separator V I and the heat exchanger E2. In large ammonia plants, the cycle machine is mostly between the heat exchangers E2 and E4.
  • the heat exchanger inside the tower shown in Figure 1-5 can also be located outside the tower.
  • the gas stream 1 heated by the heat exchanger E2 outside the tower shown in Figure 6 enters the reactor R 1 and is directly heated by the cold tube. 2 mixed into the catalyst layer reaction.
  • the airflow 2 can also enter the tower from the upper part of the outer cylinder, along the ring gap to the bottom.
  • the air inlet pipe a of the cold tube is upward from the bottom.
  • the inlet pipe a is imported from the bottom or middle inlet of the reactor ⁇ .
  • the present invention has the following significant advantages:
  • FIG. 7 is a graph of ammonia concentration and corresponding temperature in a reaction gas for synthesizing ammonia from hydrogen and nitrogen.
  • Te is the equilibrium temperature line of ammonia synthesis
  • Tm is the optimal temperature line. Both of them decrease with the increase of the reactant concentration.
  • the aforementioned Casale company uses cold shock between the first and second stages, and indirect between the second and third stages.
  • the heat exchange reactor operation line is shown by the solid line ABCDEF.
  • the dotted line in the figure is the operation curve of a four-bed ammonia synthesis tower with cold shock between the Kellogg sections. The concentration also decreased. Most of the reactions in these two reactors are performed under conditions far from the optimal temperature line Tm.
  • the operation line ALMN in FIG. 8 shows the situation of the ammonia synthesis reactor using the improved process of the present invention. Since the reaction starts in the cold-tube catalyst layer, part of the heat is transferred as the reaction proceeds, so the corresponding hot spot temperature L when the same ammonia concentration is reached is higher than The B point on the adiabatic reaction line is low, which is beneficial to prevent the catalyst from overheating and deactivation. Due to the countercurrent heat transfer, the heat transferred to the cold air is greater than the heat of reaction generated during the continuous reaction after passing through the hot spot, so the reaction temperature decreases along the optimal line until the point M at the exit of the cold pipe layer.
  • the one-step reaction in the adiabatic layer creates the conditions, and because the airflow 2 entering the cooling tube and the airflow 1 passing through the heat exchanger are split, two The proportion can be adjusted in 4 weeks, and the inlet temperature of airflow 2 can be adjusted within the range of 30-190 'C, which is convenient for controlling the temperature of each point of the catalyst layer. For example, to prevent the hot spot temperature from being too high before the catalyst is used, the airflow 2 temperature can be reduced.
  • the reactor operation line composed of the countercurrent cooling pipe catalyst layer and the adiabatic catalyst layer is closer to the optimal temperature line Tm. Therefore, the ammonia synthesis rate obtained is higher than that of the prior art, and the production capacity is large.
  • the ammonia content in the exit gas is increased from 12-14% mol to 15-20% mol.
  • the catalyst layer in the reactor of the present invention is a single bed connected from the cold pipe layer to the thermal insulation layer without separation, which not only significantly increases the catalyst loading capacity but also makes it very convenient to load and unload the catalyst.
  • Each cold pipe has only an air inlet pipe a Through the catalyst basket cover, it can be sealed with stuffing boxes or connected with bellows.
  • the inlet pipe a is generally set with two symmetrical centers, reducing the sealing point, and the structure is simple and reliable.
  • axial, radial The axially combined or countercurrent flow mode can effectively reduce the resistance and save power consumption.
  • a 1000 ton / day ammonia synthesis tower is selected, the inner diameter of the outer cylinder is 2.87M, the total height is 25M, and the synthesis pressure is 24MPa.
  • the internal parts are modified with the present invention, and the total catalyst capacity is 58M3, of which the upper axial countercurrent cooling pipe layer is ⁇ 4.7-6.7 mm ammonia catalyst, the amount of loading 20M3, lower radial heat insulating layer with ⁇ 1.5-3mm ammonia catalyst, the amount of loading 38M 3, synthesis column feed stream 1 flow rate 261000 NM3 / h, heating to the heat exchanger; stream 2 flow 319000NM3 / h, Go to countercurrent cold tube bile heating.

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Description

一种接近最佳温度的
催化反应改进工艺及其合成反应器 技术领域
本发明涉及一种气-固相催化反应工艺方法及其实施该方法的反应装 置， 用于气固相催化反应和传热过程， 属化学工程领域， 特别适用于氨合 成反应过程。 也可用于甲醇、 甲垸、 甲醚合成过程。 背景技术
众所周知， 对于由氢、 氮气加压下合成氨这类气固相放热催化反应， 在一定压力和一定反应物组成的条件下， 存在着反应速度最大的最佳温 度。 这一最佳温度又随着合成率的提高逐渐降低， 然而随着反应过程的进 行， 又因不断放出反应热使催化剂层温度提高， 为 Γ提高反应器的效率， 因此需要把反应热移出以降低反^气体的温度。 在工业反应器中曾广为使 用的一种是多段原料气冷激式反应器， 如我国引进的大型氨厂所用的 Kel l ogg公司的四段触媒床， 各段间用原料气冷激来降低反应气温度， 这种 反应器因原料气冷激时在降低反应气温度的同时也降低了反应物浓度而影 响了合成率。 因此出现了改进形式， 较好一种是将催化剂分为三个床层， 第一、 二段间用冷激， 第二、 三段间用间接换热见 Casale 公司申请的 CN 1 030878 , 89年 2月 8 日公开， 但这种反应器既未完全消除冷激原料 气对反应物浓度的影响 又由于在床层段间设置了间接换热器而使设备结 构复杂。 发明概述
本发明的目的是依据气 -固相催化放热可逆反应的特点， 克服现有技术 的缺点， 提供一个触媒层温度分布合理、 触媒活性高、 结构简单可靠、 操 作性能好的反应器和一种符合最佳温度进行反应的工艺方法.
气 -固相催化放热可逆反应和反应热主要集中在反应过程的前面阶段， 因此本发明主要通过以下改进方法来实现本发明的目的：一是原料气主要 分成气流 1和气流 2二股分别加热， 气流 1与触媒层出口反应气换热升温， 气流 2 在触媒层上部的冷管内与管外触媒层中的反应气逆流换热升温， 冷 管内气流 2的气量和温度可以根据触媒层温度需要来调节， 二是经加热后 的原料气流 1 和气流 2混合， 先在冷管触媒层中反应并与冷管内的原料气 换热， 再进下部触媒层中绝热反应。 这样反应前阶段用逆流冷管换热， 使 确认本 反应开始可-以在接近绝热的工况下进行， 以便较快达到最佳温度， 而后随 着冷管逆流换热， 管内外温差加大， 触媒温度沿最佳线下降， 到冷管层出 口可以降到最佳线以下， 为后阶段绝热反应创造条件。
本发明的合成反应器主要由外壳 P、 触媒筐 R和换热器 E组成， 外壳 P承 受压力， 一般反应压力为 14 ~ 32MPa , 触媒筐 R的盖板 H , 筒体 S， 触 媒筐 R底部的花板〗支承触媒筐中的触媒层。 触媒层由内带逆流冷管胆 Cb 的冷管触媒层 K 1 和绝热触媒层 K2组成， 冷管胆 Cb主要由进气管 a、 冷 管 1 、 连接进气管 a和冷管 b的环管 d l组成， 冷管胆 Cb也可由进气管 a、 冷管 b、 出气管 c、 连接进气管 a和冷管 b的环管 d l 、 连接冷管 b和出气 管 c的环管 d2组成。 冷管触媒层 K 1 可有一个或数个同轴心套装的冷管胆 cb , 每个冷管胆上有按不同圈径排列的同轴心多排冷管 b , 触媒层中心有 连接换热器 E的中心管 I . 原料气由进气管 a进入， 经过环管 d l 分配到各 根冷管 b中， 管内的原料气流 2被管外触媒层 K 1 中的高温反应气逆流加 热， 升温后或由冷管 b直接出口或者经环管 d2和出气管 c 出口， 并与经 换热器加热由中心管 I 出口的气流 1 混合， 达到触媒活性温度以上， 依次 进冷管触媒层 K 1 反应并与冷管 b内的气体逆流换热， 再进绝热触媒层 K2 反应， 出冷管气流 2 的温度与进冷管触媒层混合气温度之比值为 0.75 ~ 1 .25。 冷管触媒层的触媒占全塔触媒总量的 15-80 %， 最佳为 30-50 % , 随 反应条件而变， 气体可以在冷管触媒层 K 1和绝热触媒层 K2中均呈轴向流 动， 也可先在冷管触媒层 K 1 中作轴向流动尔后在绝热触媒层 K2 中作径 向、 轴径向流动； 或在绝热触媒层 K2中作对向流动。 冷管 b可用园形单管 或扁平管。 冷管传热面积与触媒体积之比为 3-20M2 /M2 。 附图的简要说明
图 1 是轴向逆流冷管层和绝热层组成的反应器示意图。
图 2和图 3 是由轴向逆流冷管层和径向绝热层组成的反应器示意图。 图 4 是用于现有大型氨合成塔改造为轴向逆流冷管层和径向绝热层组 成的反应器示意图。
图 5 是轴向逆流冷管层和对向并流的轴向绝热层组成的反应器示意 图。
图 6 是反应器与塔外设备管路连接图。
图 7和图 8 是反应器的 t-x图， 图上横座标为反应温度' C， 纵座标为氨 浓度摩尔％。 发明的详细描述
图 1 表示本发明中适用反应器高径比不大的一种反应器， 例如氨合成 塔. 在承压外筒 P中安装内件， 外筒和内筒器壁 S之 |¾?有环形空隙， 内件 上部是触媒筐 R , 中间有中心管 I , 触媒筐内装有触媒， ？: t上部触媒层 K 1 中装有冷管胆 Cb， 冷管胆有多根冷管 b , 分成同轴心的 2到 4排， 连通下 环管 d l 和上环管 d2， 下环管 d l连通进气管 a , 上环管 £12连通¾气管 c， 进气管 a穿过触媒盖板 H并用填料函活动密封或用波形软管连接， 环管 d2 位于还原后触媒层上方空间， 在使用中的冷管胆受热可自由伸缩， 冷管胆 由支承架 L支承并与触媒一起支承在多孔花板 J上， 图中内件下部是列管 式换热器 E , 亦可以是螺旋板换热器. 通过筒体和底封头 U将进塔气 1和 2 隔开， 换热器底盖 V将进塔气 1 与出塔气 4隔开. 在触媒升温还原时， 冷气进塔后经内件换热器底封头 U和底盖 V之间进人换热器 E与出触媒层 的热气换热， 又经中心管 I中的电加热器加热， 再人触媒层进行触媒升温 还原. 在正常生产时， 进塔气主要分为气流 1 和气流 2 二股， 气流 1经换 热器 E与反应气换热后由中心管 I 出口， 气流 2进塔后经外筒 P和内件之 间环隙， 由进气管 a进人冷管胆 C b , 由下环管 d l 均匀分配到各冷管 b 中由下到上流动， 并与管外反应气逆流换热升高温度， 直到上环管 d2汇 集后经出气管 c出口， 再与来自中心管 I的原料气 1 混合. 对于氨合成例 如温度为 350 - 430 'C的混合气先在冷管层氨触媒 K 1 中反应， 产物浓度 提高， 反应中放出热 Μ·使气体温度升高， 同时与冷管 b 内冷气逆流换热， 反应气温度升高到热点温度 450 - 5 1 0 'C后又开始降低温度到 380 - 430 'C左右，然后在下部绝热触媒层 K2中绝热反应，再升高到温度 460 'C左右， 产物浓度进一步提高， 如氨合成为 1 5 ~ 20 %摩尔， 气体在上述冷管层 K 1 和绝热层 K2中均为轴向流动， 反应气出触媒层再到换热器 E中与进塔气 1 换热后即为出塔气 4 出塔. 图中气体 3 为调节进触媒层零米温度用的冷副 线气.
图 2 为适用于高径比较大的一种反应器， 气体在冷管触媒层中也为轴 向流动， 与图 1不同的是触媒筐 R中的下部为径向流动绝热层， 触媒支承 板 J不开孔通气， 在触媒筐筒体 S 内侧有多孔外分布筒 X , 在中心管 I外 侧有同心多孔内分布筒 Y , 经过上部冷管触媒层 K 1 之大部分反应气先进 入外分布筒 X和筒壁 S的环形空间， 然后穿过外分布筒 X进入绝热层 K2 由外向内成径向流动反应直到由内分布筒 Y进入内分布筒 Y和中心管 I的 环形空间， 与小部分由冷管层轴向流动进人这里的反应气体汇合， 去下部 换热器 E图中为列管式换热器与进塔气 1 换热后即为出塔气 4 , 图 3冷管 胆由支承架 L支承于内筒壁 S上， 冷管胆 Cb有二个， 图 2中其它图示和符 号与图 1 相同， 当然， 下部绝热层中也可设计成气体由内向外径向流动， 图中分布筒还贴有金属丝网， 并可设有加强支撑、 隔条、 喷嘴， 这些属已 知技术而未画出，
图 3是一种与图 2反应和换热流动方式一样的反应器，与图 2不同的是 冷管胆 Cb主要由进气管 a、 冷管 b、 连接进气管 a和冷管 b的环管 dl组 成， 由冷管 b直接伸出触媒层而出气， 故结构简单， 加工制造方便， 但图 2 的冷管用环管 d2连接出气管 c， 方便了组装和冷管胆试压査漏。 图 3中其 它图示和符号与图 2相同。
图 4是用于改造现有大型氨厂的反应器， 例如 Kellogg 瓶式大型氨合 成塔改造为本发明的反应器， 图 4与图 2—样， 触媒层上部是轴向流动逆 流冷管层 K l ， 冷管层中有多个同轴套装的冷管胆 Cb l , Cb2......图中只画 二个， 每个冷管胆分别由进气管 a、 出气管 c、 冷管 b和环管 d l 、 d2组 成， 进气管 a穿过内件壳体盖板 H时可用波纹管连接， 下部是轴径向流动 绝热层 K2。 换热器 Ε安装在反应器上部， 触媒可由下底孔 Q打开孔盖后 卸出， 由底部进塔的气流 2 经外筒 Ρ 和内件之间环隙到顶部进入冷管胆 内。 气流 1通过换热器封头 U和 V之间进入换热器 Ε的壳程间与管内反应 气 4换热后出换热器并与冷管胆 Cb加热后的气体 2混合， 先在上部冷管触 媒层 k l 中反应并与冷管 b 中的气体逆流换热， 出冷管层气体除少量继续 轴向流动外大部分由外分布筒 X进绝热触媒层中径向流动反应， 再汇集在 内分布筒 Y中经中心管 i到上部换热器 E管内与进塔气 1 换热后即为出塔 气 4 出塔， 冷气 3进塔用于调节进触媒层零米温度。 轴径向反应器阻力比 轴向的小， 故操作空速即人塔气总量与触媒体积之比可取较大值。
图 5 是本发明轴向塔的另一种型式， 在触媒层上部有一个轴向冷管型 触媒层 K 1 , 逆流冷管胆 Cb由支承架 L支承于内件筒壁 S上， 紧接冷管胆 Cb下部有一个集气器 W , 集气器 W有管 M连通到触媒筐底部花板 J , 绝 热触媒层 K2的中部有一个集气器 Z , 集气器 W和 Z器壁上设有只供气体 进人而不会让触媒进人的许多小孔， 集气器 Z经套管 N连通到换热器 E图 中为列管式换热器， 在触媒筐多孔花板 J和换热器 E之间有隔板 G。 经换 热器 E加热的进塔气 1和经冷管胆加热的气体 2混合后先经上部冷管触媒 层 K 1反应， 并与冷管 b内气体逆流换热， 出冷管触媒层的气体一半继续自 上而下在触媒层 K2上部反应， 另一半气体进人集气器 W中并经连通管 M 到触媒筐花板 J下面空间， 然后由下而上在绝热触媒层 K2下部反应， 这二 股反应气在绝热层 K2中对向流动到中部进人集气器 Z汇合，再通过套管 N 和中心管 I -之间的环形空间向下流到隔板 G下面空间， 经换热器 E管内与 管外进塔气 1换热成出塔气 4出塔， 底部进塔气 3用作调节触媒层温度的 副线。
图 6为反应器与塔外设备管路连接图， 其中 R 1 为反应器， 内部结构见 图 1 -5 , E2为塔外冷热气换热器， E3 为付产蒸汽锅炉， E4 为冷却冷凝 器， V I 为产品分离器例如氨分离器， T 1为循环机。 由循环机送来的进塔 气分为三股， 其中气流 1经塔外换热器 E2加热后进反应器内的换热器再进 一步加热， 气流 2进反应器内冷管胆吸收冷管层触媒反应热， 气流 1 和气 流 2的气量可调节， 进冷管胆的气流 2的气量一般为总气量的 30 - 70 % 。 气流 2的温度可用经过和不经过换热器 E2的气量比来调节， 以用于根据不 同触媒使用时期调整触媒层温度;气流 3为调节触媒层零米温度用的冷副线 气， 气流 4为出塔反应气， 经锅炉 E3回收热量后去换热器 E2加热人塔原 料气。 图中 5为分离的产品如液氨或甲醇， 6为弛放气， 7为补充原料气。 图中循环机位于氨分离器 V I 与换热器 E2之间， 在大型氨厂中循环机多在 换热器 E2和 E4之间。
在图 1 -5 中的塔内换热器亦可设在塔外， 这时图 6 中经塔外换热器 E2 加热的气流 1进反应器 R 1后直接与经冷管胆加热的气流 2混合进触媒层反 应。 图中气流 2亦可由外筒上部进塔， 沿环隙到底部， 这时冷管胆的进气 管 a 由底部向上。 当反应器用热壁容器， 不单独设外筒时， 进气管 a 由反 应器底部或中部进口均^ .
本发明与现有技术比较有以下显著优点：
1工艺性能优良， 合成率高。 图 7是由氢、 氮气合成氨的反应气中的氨 浓度和相应温度曲线图。 图中 Te为氨合成的平衡温度线， Tm为最佳温度 线， 二者都随反应物浓度的提高而降低， 前述 Casale公司的一、 二段间用 冷激， 二、 三段间用间接换热的反应器操作线见实线 ABCDEF , 图中虚线 为 Kellogg 段间都用冷激的四床层氨合成塔操作曲线图， 由图可见用冷激 气加人后反应气体降温的同时氨浓度也降低。 这二种反应器大部分反应在 离最佳温度线 Tm较远工况下进行。 图 8中操作线 ALMN表示使用本发明 改进工艺的氨合成反应器情况， 因反应开始在冷管触媒层， 故随反应进行 传递出部分热量， 因此达到同样氨浓度时对应的热点温度 L要比上述绝热 反应线上 B点低， 这有利于防止触媒过热失活。 又因逆流换热， 在经过热 点后继续反应时传给冷气的热量大于其间产生的反应热， 故反应温度沿最 适线下降， 直到冷管层出口时的 M点， 这一温度下降为下一步在绝热层 反应创造了条件， 又由于进冷管胆的气流 2与经换热器的气流 1 分流， 二 者比例可以 4周节， 气流 2的进口温度可以在 30 - 190 'C范围内调， 为控制 触媒层各点温度提供了方便， 例如在触媒使用前期为防止热点温度过高可 降低气流 2温度， 使出冷管气温低于进冷管触媒层混合气温度， 绝热反应 出口达 N点， 由图可见逆流冷管触媒层和绝热触媒层组成的反应器操作线 更接近最佳温度线 Tm ， 故结果所得到的氨合成率比已有技术高， 生产能 力大， 出塔气中的氨含量由 12-14 %摩尔提高到 15-20 %摩尔。
2结构简单可靠， 安装使用方便。 现有一些合成反应器多具有 3个或更 多个触媒床， 床层间又被分隔， 或装有换热器， 结构复杂。 本发明反应器 中触媒层从冷管层到绝热层为连在一起的单个床层， 未加分隔， 既显著增 加了触媒装量又使装卸触媒十分方便. 每个冷管胆只有进气管 a穿过触媒 筐盖板， 可用填料函密封， 或用波纹管连接， 进气管 a—般设中心对称二 根， 减少了密封点， 结构简单可靠. 对于大直径反应器可用轴向、 径向、 轴径向结合或对向流的流动方式， 可使阻力有效降低， 节约电耗 实施例
下面以图 4的反应器为例说明本发明的实施方案：
选用 1000吨 /日的氨合成塔， 外筒内径 2.87M , 总高 25M , 合成压力 24MPa , 应用本发明改造内件， 总触媒装量 58M3 ， 其中上部轴向逆流冷 管层用 Φ 4.7-6.7mm氨触媒， 装量 20M3 ， 下部径向绝热层用 Φ 1.5-3mm 氨触媒， 装量 38M3 , 进合成塔气流 1流量 261000 NM3 /h , 去换热器加 热； 气流 2流量 319000NM3 /h , 去逆流冷管胆加热。 然后气流 1与气流 2 混合， 混合温度达 390 'C , 再进冷管触媒层合成氨， 热点 492 出冷管 层温度 415 °C， 反应气氨含量由 1.78 %摩尔提高到 15.2 %摩尔， 然后进径 向绝热层进一步合成氨， 出绝热层反应气 4温度为 448 'C , 氨含量 19.5 % 摩尔， 进塔气总量 580000 NM3 /h , 出塔气总量 493974 NM3 /h , 具体见 图 8中操作线 ALMN。 气体再经塔内换热器与气流 1换热， 然后出塔去锅 炉回收反应热。 反应器压力降 0.2MPa， 进出塔气组成如下： 进塔气％摩尔 出塔气％摩尔
H2 65.83 51.27
N2 21.94 17.06
CH4 7.39 8.68
Ar 3.06 3.59
NH3 1.78 19.50 由上可见， 该反应器改造后的产量达 1567 吨 /日， 比已有技术提高 56 % , 氨净值由已有技术的 11.1 %提高到 17.72 % 。

Claims

权 利 要 求 书
1.一种用于气固相催化放热可逆反应的工艺方法， 原料气加到一定压力下， 经 过换热升温达到触媒的活性温度， 进人触媒床层进行放热催化反应， 其特征在于 所述的原料气主要分成气流（1)与气流 (2)二股， 气流（1 )与触媒层出口反应气换热 升温， 气流 (2)进触媒层中的冷管内被管外触媒层中的反应气逆流加热， 加热后的 原料气流 (1 )与气流 (2)混合后，先在冷管触媒层中反应并与冷管内的原料气逆流换 热， 再进下部触媒层中绝热反应。
2. —种用于权利要求 1 所述工艺方法的合成反应器， 主要有外筒 P、 触媒筐
R和换热器 E , 触媒筐 R有盖板 H , 筒体 S , 触媒筐 R的底部有花板 J支承触媒 筐中的触媒层， 其特征在于所述的触媒层由内带逆流冷管胆 Cb的冷管触媒层 K1 和绝热触媒层 K2组成， 冷管胆 Cb主要由进气管 a、 冷管 b、 连接进气管 a和冷 管 b的环管 d l组成， 或者由进气管 a、 冷管 b、 出气管 c、 连接进气管 a和冷管 b的环管 dl、 连接冷管 b和出气管 c的环管 d2组成， 使在冷管胆 Cb中被加热的 气流 (2)出冷管与经换热器 E加热的气流 ( 1 )混合后在冷管 b管外的触媒层 K 1中反 应并与冷管 b内气体逆流换热， 再进触媒层 K2绝热反应。
3. 根据权利要求 2的反应器， 其特征在于冷管触媒层 K1和绝热触媒层 K2中 气体均为轴向流动。
4. 根据权利要求 2的反应器， 其特征在于冷管触媒层 K1 中气体为轴向流动， 绝热层 K2中设有多孔外分布筒 X和我孔内分布筒 Y供气体径向流过绝热层。
5. 根据权利要求 3的反应器， 其特征在于绝热层 K2中有集气室 W和 Z , 管
M连通触媒筐底部花板 J和上部集气管 W , 管 N连通换热器 E和设于绝热层中 部的集气室 Z , 构成反应气在绝热层 K2中作对向流动。
6. 根据权利要求 3所述的反应器， 其特征在于触媒筐 R的冷管触媒层 K1 中 有一个或数个同轴心套装的冷管胆 Cb , 每个冷管胆具有分成不同圈径的同轴心 的多排冷管 b 。
PCT/CN1997/000082 1996-08-21 1997-08-20 Procede de reaction catalytique execute pres de la temperature optimale WO1998007510A1 (fr)

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