CN102180756B - Device and method for complete methanation of synthesis gas - Google Patents

Device and method for complete methanation of synthesis gas Download PDF

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CN102180756B
CN102180756B CN 201110058130 CN201110058130A CN102180756B CN 102180756 B CN102180756 B CN 102180756B CN 201110058130 CN201110058130 CN 201110058130 CN 201110058130 A CN201110058130 A CN 201110058130A CN 102180756 B CN102180756 B CN 102180756B
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gas
solid
reactor
methanation
synthesis gas
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CN102180756A (en
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程易
储博钊
翟绪丽
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清华大学
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Abstract

本发明公开了属于煤化工技术领域的一种合成气完全甲烷化的装置及方法。 The present invention discloses apparatus and methods belong to a technical field of chemical coal a complete methanation of synthesis gas. 本发明的装置由混合器、气-固-固反应器、旋风分离器、热回收容器、第一料封、第二料封构成。 By the mixer device of the invention, the gas - solid - solid reactor, cyclones, heat recovery vessel, a first seal material, the second material constituting the seal. 本发明的方法包括原料气携带惰性热载体颗粒的合成气完全甲烷化、产物与惰性热载体颗粒分离和惰性热载体颗粒回收循环使用三个主要步骤,原料气携带惰性热载体颗粒的合成气完全甲烷化能够大幅度降低反应温度,减缓了催化剂积炭速率,同时降低了反应器材质的热负荷,惰性热载体颗粒由反应气体携带通过反应器,反应装置能够连续操作。 The method of the present invention comprises an inert gas feed synthesis gas carrying the heat carrier particles methanation complete, the product with the inert heat carrier particles are separated and recycled inert heat carrier particles using three main steps, the feed gas inert heat carrier particles carrying the synthesis gas is completely the methanation reaction temperature can be greatly reduced, slowing the rate of catalyst coke formation, while reducing the thermal load of the material of the reactor, an inert heat carrier particles are carried from the reaction gas through the reactor, the reaction apparatus can be operated continuously.

Description

一种合成气完全甲烷化的装置及方法 A synthetic gas apparatus and method for fully methanation

技术领域 FIELD

[0001] 本发明属于煤化工技术领域,具体涉及一种合成气完全甲烷化的装置及方法。 [0001] The present invention belongs to the field of chemical technology of coal, particularly relates to an apparatus and method methanation of synthesis gas completely.

背景技术 Background technique

[0002] 由于上世纪70年代的石油危机引发了世界各大能源公司致力于煤制合成天然气的研究,合成气甲烷化是上述过程的关键部分,其核心是甲烷化催化剂和工艺的研究。 [0002] Since the oil crisis of the 70s of the last century led to research methanation catalyst and process of the world's major energy companies working on coal to synthetic natural gas, synthesis gas methanation is a key part of this process, the core yes. 1984年,Lurgi公司完成了两步法完全甲烷化的整套工艺技术的开发,并成功应用于美国大平原工厂12亿标方/年的煤制合成天然气工厂。 In 1984, Lurgi company completed the entire two-step method to develop technology completely methanation, and successfully applied in the Great Plains plant 1.2 billion US standard side / year of coal to synthetic natural gas plant. Lurgi完全甲烷化工艺过程包括:煤气化生成合成气,合成气经水汽变换调整氢气与一氧化碳摩尔比至合适值,甲醇洗脱硫,两段固定床绝热反应器进行完全甲烷化反应,尾气冷凝净化处理,其核心是绝热固定床反应器。 Lurgi complete methanation process comprising: generating a synthesis gas gasification, water-gas shift adjusted synthesis gas of hydrogen and carbon monoxide molar ratio to a suitable value, desulfurization methanol wash, two-stage fixed bed adiabatic methanation reactor is complete, the exhaust gas purification condensed , the core is an adiabatic fixed bed reactor.

[0003] 合成气完全甲烷化反应是一个强放热反应,要求在适当温度下进行,300°C〜500°C,同时为了提高转化率要增大压力,反应条件是3.0MPa〜5.0MPa,反应生成的CH4和H2O的摩尔流率之比约为1,因此甲烷化反应器开发的核心是有效控温。 [0003] The complete synthesis gas methanation reaction is a strongly exothermic reaction, at a suitable temperature requires, 300 ° C~500 ° C, and in order to improve the conversion rate to increase the pressure, the reaction conditions 3.0MPa~5.0MPa, the resulting reaction ratio of CH4 and H2O and the flow rate of from about 1 mole, so methanation reactor core development temperature is effective.

[0004] 合成气完全甲烷化装置的技术核心是甲烷化反应工序,关键设备是可实现有效控温的反应器,主要采用固定床反应器或流化床反应器。 Core technology [0004] The complete synthesis gas methanation step is methanation, the key device is effective temperature of the reactor, mainly fixed bed reactor or fluidized bed reactor. 甲烷化固定床反应器目前已出现若干较为成熟的技术,如德国Lurgi公司的甲烷化技术和丹麦Topsoe公司的TREPM工艺,其核心思想是将原料合成气通过多段绝热固定床,通过控制各段反应器的转化率抑制温升,最终结合部分产品气体循环实现反应过程的整体控温。 Currently several methanation bed reactor has occurred mature technology, such as Germany and Lurgi companies methanation techniques Danish company TREPM Topsoe process, the core idea is the raw syngas by an adiabatic fixed bed multi-stage, each stage by controlling the reaction conversion of suppressing the temperature rise control, temperature control portion integral binding final product gas recycle to achieve the reaction process. 但是,多段反应器结构使得设备整体构架相对复杂,成本较高,自动控制相对困难,同时大量产品气冷却后循环使得装置整体能耗较大,并限制了单段反应器的生产能力,使得工艺的经济性降低。 However, multi-stage reactor configuration such that the overall structure of the device is relatively complex and costly, relatively difficult automatic control, while the large product gas cooling circulation device such that the larger overall power consumption, and limiting the capacity of single-stage reactor, such that the process the economy is reduced. 流化床反应器主要利用其高效的传热传质效率实现对甲烷化反应温度的控制。 The main fluid bed reactor using its highly efficient heat and mass transfer efficiency to achieve temperature control of the methanation reaction. 然而,由于流化床内的返混现象,会影响甲烷化反应的转化率,同时还要考虑催化剂磨损等问题,因此完全甲烷化流化床工艺的开发仍处于实验室阶段,目前尚无成熟的完全甲烷化流化床工艺可用于工业化。 However, due to the back mixing within the fluidized bed, will affect the conversion rate of the methanation reaction, but also consider issues such as catalyst attrition, thus completely fluidized bed methanation process of development is still at the laboratory stage, there is no mature full methanation fluidized bed process can be used for industrialization.

发明内容 SUMMARY

[0005] 本发明的目的在于提供一种利用气-固-固反应器合成气完全甲烷化反应装置。 [0005] The object of the present invention is to provide a use of gas - solid - solid syngas reactor complete methanation reactor.

[0006] 本发明的目的还在于提供一种利用气-固-固反应器装置进行合成气完全甲烷化反应的方法,克服现有固定床反应器的缺点,降低合成气完全甲烷化过程的能耗,进一步降低生产成本。 [0006] The object of the present invention is to provide a use of gas - solid - solid reaction apparatus for synthesis gas methanation reaction is complete, to overcome the disadvantages of conventional fixed bed reactor, synthesis gas can be reduced to complete methanation consumption, to further reduce production costs.

[0007] —种合成气完全甲烷化的装置,其特征在于,所述装置由混合器la、气-固-固反应器2、旋风分离器3、热回收容器lb、第一料封4a、第二料封4b构成;气-固-固反应器2设置在混合器Ia出口处,旋风分离器3入口与气-固-固反应器2的出口通过管道相连;热回收容器Ib分别通过第一料封4a和第二料封4b与旋风分离器3和混合器Ia相连。 [0007] - means Species complete methanation of synthesis gas, characterized in that the said mixer means La, gas - solid - solid reactor 2, the cyclone 3, the heat recovery vessel LB, a first sealing material 4a, 4b constituting the second seal material; gas - solid - solid reactor 2 is provided at the outlet of the mixer Ia, cyclone inlet 3 and gas - solid - solid outlet connected to the reactor 2 via conduit; Ib respectively heat recovery container section a sealing material sealing materials 4a and 4b connected to the second cyclone 3 and a mixer Ia.

[0008] 一种合成气完全甲烷化的方法,其特征在于,按照如下步骤进行: [0008] A method for complete methanation of synthesis gas, which is characterized by performing the following steps:

[0009] a、以合成气作为原料气,将原料气与惰性热载体颗粒在混和器Ia内混和,混合后进入装有甲烷化催化剂的气-固-固反应器2内,并在气-固-固反应器2中进行充分接触和反应;合成气中氢气与一氧化碳摩尔比为3.0〜3.5,气-固-固反应器2的进口温度与出口温度分别为300°C〜500°C和340°C〜540°C,操作压力为3.0MPa〜5.0MPa ; [0009] a, to the synthesis gas as a raw material gas, the feed gas with an inert particulate heat carrier within the mixing Ia mixer, after mixing with the methanation catalyst into the gas - solid - solid inside the reactor 2 and the gas - solid - full contact and reaction in reactor 2 solid; synthesis gas hydrogen to carbon monoxide molar ratio of 3.0~3.5, gas - solid - solid reactor inlet temperature and the outlet temperature for 2 were 300 ° C~500 ° C and 340 ° C~540 ° C, the operating pressure is 3.0MPa~5.0MPa;

[0010] b、从气-固-固反应器2出来的气固混和物进入旋风分离器3进行分离,分离出来的气体经工业处理装置处理后,最终得到纯净的甲烷; [0010] b, from the gas-solid - solid reaction into the cyclone 2 out of 3-solid mixture was separated, and the separated gas after treatment apparatus industrial process, the finally obtained pure methane;

[0011] C、从旋风分离器3出来的惰性热载体颗在热回收容器Ib中回收,使惰性热载体颗粒冷却至室温; [0011] C, from 3 out of the inert heat carrier particles recovered in the cyclone heat recovery container Ib, the inert heat carrier particles are cooled to room temperature;

[0012] d、从热回收容器Ib出来的惰性热载体颗粒通过管路重新进入混合器la,并加入少量惰性新鲜热载体颗粒用于补充上述过程中的损耗,再通过合成气携带进入气-固-固反应器2进行新一轮的合成气完全甲烷化反应。 [0012] d, the inert particulate heat carrier from the heat recovery vessel Ib out re-entering the mixer through line La, and add a small amount of fresh inert particulate heat carrier to compensate for the losses for the process, and then carried into the synthesis gas through a gas - solid - solid reactor 2 for a new round of synthesis gas methanation reaction is complete.

[0013] 所述惰性热载体为氧化铝微球、石英砂或氟矿砂。 [0013] The inert heat carrier is alumina microspheres, quartz sand ore or fluoro.

[0014] 所述惰性热载体颗粒的粒径大小为5〜200微米,优选为50〜100微米。 [0014] The inert heat carrier particles particle size of 5~200 microns, preferably 50~100 microns.

[0015] 所述气-固-固反应器2在固定床状态下操作时,使用催化剂颗粒粒径在5〜10毫米,在流化床状态下操作时,使用催化剂颗粒粒径在I〜5毫米。 [0015] The gas - solid - solid reactor 2 when operated in a fixed bed state in the catalyst particle size 5 to 10 mm, while operating in the fluidized state, the catalyst particle size I~5 mm.

[0016] 本发明的有益效果:1、本发明采用原料气携带惰性热载体颗粒的合成气完全甲烷化固定床装置可以通过单段绝热反应器实现甲烷化过程的高转化率,利用惰性热载体颗粒大幅度提高了反应气相的移热能力,使得满足高转化率要求的单段气-固-固反应器能够实现绝热操作的操作温度在300°C〜540°C范围内。 [0016] Advantageous effects of the present invention are: 1, the present invention uses a feed gas carrying high conversion of inert heat carrier particles entirely methanation of synthesis gas methanation bed apparatus may be implemented by a single-stage adiabatic reactor with an inert heat carrier particles greatly improve the heat removal capability of the gas phase reaction, high conversion rate so as to satisfy the requirements of a single stage gas - solid - solid reactor operating temperature can be achieved in adiabatic operation within the range of 300 ° C~540 ° C. 2、本发明在气-固-固反应器中实现合成气甲烷化反应,催化剂始终停留在气-固-固反应器中,惰性热载体颗粒随着气体进入并离开气-固-固反应器,只需将反应器出口的惰性热载体经过旋分分离器进行气固分离后循环,无需将大量产品气相循环,因此该过程能够连续操作,进一步降低生产成本。 2, the present invention in a gas - synthesis gas methanation reactor to achieve solid reaction, the catalyst always stay in the gas - - Solid Solid - Solid reactor, with an inert particulate heat carrier gases enter and exit the gas - solid - solid reactor after just an inert heat carrier outlet of the reactor through the cyclone separator for gas-solid separation cycle, a large amount of product without gas circulation, so that the process can operate continuously, to further reduce production costs.

附图说明 BRIEF DESCRIPTION

[0017] 图1为本发明合成气完全甲烷化的装置示意图; [0017] FIG. 1 is a schematic complete methanation of a synthesis gas apparatus of the present invention;

[0018] 图中,Ia-混合器、Ib-热回收容器、2-气-固-固反应器、3_旋风分离器、4a_第一料封、4b-第二料封、A-原料气、B-气体产物和使用后的惰性热载体颗粒、C-气体产物、D-使用后的惰性热载体颗粒、E-新鲜冷却剂、F-使用后的冷却剂、G-冷却后的惰性热载体颗粒、H-新鲜的惰性热载体颗粒。 [0018] FIG, Ia- mixer, Ib - heat recovery vessel, 2 gas - solid - solid reactor, cyclone 3_, 4a_ first seal material, the second seal-4b-, A- material after the inert particulate heat carrier after the inert gas, B- and use of the product gas, C- product gas, the inert heat carrier particles after use D-, E- fresh coolant, the coolant used F-, G-cooled heat carrier particles, H- fresh inert heat carrier particles.

具体实施方式 Detailed ways

[0019] 下面结合附图和具体实施例对本发明做进一步说明。 [0019] conjunction with the accompanying drawings and the following Examples further illustrate specific embodiments of the present invention.

[0020] 以下实施例采用如图1所示合成气完全甲烷化的装置,该装置由混合器la、气-固-固反应器2、旋风分离器3、热回收容器lb、第一料封4a、第二料封4b构成;气-固-固反应器2设置在混合器Ia出口处,旋风分离器3入口与气-固-固反应器2的出口通过管道相连;热回收容器Ib分别通过第一料封4a和第二料封4b与旋风分离器3和混合器Ia相连。 [0020] The following examples employ FIG complete methanation of synthesis gas apparatus 1, the device consists of La mixer, gas - solid - solid reactor 2, the cyclone 3, the heat recovery vessel LB, a first sealing material 4a, 4b constituting the second seal material; gas - solid - solid reactor 2 is provided at the outlet of the mixer Ia, cyclone inlet 3 and gas - solid - solid outlet connected to the reactor 2 via conduit; Ib, respectively, the heat recovery vessel 4a through said first sealing material and a second seal 4b is connected to the cyclone 3 and the mixer Ia.

[0021] 实施例1 [0021] Example 1

[0022] 采用如图1所示的气-固-固合成气完全甲烷化装置,操作步骤如下: [0022] The use of gas as shown in FIG. 1 - Solid - Solid complete methanation of synthesis gas, following these steps:

[0023] a、以合成气作为原料气,将原料气与氧化招微球在混和器Ia内混和,混合后进入装有甲烷化催化剂的气-固-固反应器2内,并在气-固-固反应器2中进行充分接触和反应;合成气中氢气与一氧化碳摩尔比为3.1,总体积流率为5m3/h,气-固-固反应器2的进口温度与出口温度分别为370°C和410°C,操作压力为3.0MPa ;催化剂颗粒的粒径为Φ 5mm长3mm的圆柱体,圆柱体内有三叶草状的通道;气-固-固反应器的内径为100mm,催化剂床层高度400mm ;氧化铝微球颗粒粒径为75微米。 [0023] a, to the synthesis gas as a raw material gas, the feed gas with an oxidizing move within the microspheres Ia mixing mixer, after mixing with the methanation catalyst into the gas - solid - solid inside the reactor 2 and the gas - solid - solid reactor 2 for full contact and reaction; synthesis gas hydrogen to carbon monoxide molar ratio of 3.1, a total volume flow rate of 5m3 / h, gas - solid - solid reactor inlet temperature and outlet temperature were 370 2 ° C and 410 ° C, an operating pressure of 3.0MPa; diameter of the catalyst particles is 3mm Φ 5mm long cylinders, clover-shaped passage within the cylinder; gas - solid - solid inner diameter of the reactor is 100mm, the catalyst bed height 400mm; alumina microspheres has particle size of 75 microns.

[0024] b、从气-固-固反应器2出来的气固混和物进入旋风分离器3进行分离,分离出来的气体经工业处理装置处理后,最终得到纯净的甲烷; [0024] b, from the gas-solid - solid reaction into the cyclone 2 out of 3-solid mixture was separated, and the separated gas after treatment apparatus industrial process, the finally obtained pure methane;

[0025] C、从旋风分离器3出来的氧化铝微球颗粒在热回收容器Ib中回收,使氧化铝微球颗粒冷却至室温; [0025] C, recovered from the cyclone 3 out of alumina microspheres particles in the heat recovery vessel Ib, the alumina particles were cooled to room temperature, the microspheres;

[0026] d、从热回收容器Ib出来的氧化铝微球颗粒通过管路重新进入混合器la,并加入少量新鲜氧化铝微球用于补充上述过程中的损耗,再通过合成气携带进入气-固-固反应器2进行新一轮的合成气完全甲烷化反应。 [0026] d, from the heat recovery vessel Ib out alumina particles re-enter the microspheres through line La mixer, and adding a small amount of fresh alumina microspheres has to compensate for the losses in the process, and then carried by gas into the synthesis gas - solid - solid reactor 2 for a new round of synthesis gas methanation reaction is complete.

[0027] 本实施例一氧化碳转化率为99%,甲烷选择性为95%。 [0027] The present embodiment is 99% carbon monoxide conversion, methane selectivity of 95%.

[0028] 实施例2 [0028] Example 2

[0029] 采用如图1所示的气-固-固合成气完全甲烷化装置,操作步骤如下: [0029] The use of gas as shown in FIG. 1 - Solid - Solid complete methanation of synthesis gas, following these steps:

[0030] a、以合成气作为原料气,将原料气与石英砂在混和器Ia内混和,混合后进入装有甲烷化催化剂的气-固-固反应器2内,并在气-固-固反应器2中进行充分接触和反应;合成气中氢气与一氧化碳摩尔比为3.5,总体积流率为5m3/h,气-固-固反应器2的进口温度与出口温度分别为350°C和390°C,操作压力为3.0MPa ;催化剂颗粒的粒径为Φ IOmm长8mm的圆柱体,圆柱体内有三叶草状的通道;气-固-固反应器的内径为100mm,催化剂床层高度400mm ;石英砂颗粒粒径为50微米。 [0030] a, to the synthesis gas as a raw material gas, the raw material gas mixed with quartz sand in the mixer Ia, mixed with the methanation catalyst into the gas - solid - solid inside the reactor 2 and the gas - solid - solid 2 reactor sufficient contact and reaction; synthesis gas hydrogen to carbon monoxide molar ratio of 3.5, a total volume flow rate of 5m3 / h, gas - solid - solid reactor inlet temperature and the outlet temperature for 2 were 350 ° C and 390 ° C, an operating pressure of 3.0MPa; diameter of the catalyst particles is cylindrical Φ IOmm 8mm long, clover-shaped passage within the cylinder; gas - solid - solid inner diameter of the reactor is 100mm, the catalyst bed height 400mm ; quartz sand particle size of 50 microns.

[0031] b、从气-固-固反应器2出来的气固混和物进入旋风分离器3进行分离,分离出来的气体经工业处理装置处理后,最终得到纯净的甲烷; [0031] b, from the gas-solid - solid reaction into the cyclone 2 out of 3-solid mixture was separated, and the separated gas after treatment apparatus industrial process, the finally obtained pure methane;

[0032] C、从旋风分离器3出来的石英砂颗粒在热回收容器Ib中回收,使石英砂颗粒冷却 [0032] C, from the cyclone 3 out of silica particles is recovered in the heat recovery vessel Ib of the cooled silica particles

至室温; To room temperature;

[0033] d、从热回收容器Ib出来的石英砂颗粒通过管路重新进入混合器la,并加入少量新鲜石英砂颗粒用于补充上述过程中的损耗,再通过合成气携带进入气-固-固反应器2进行新一轮的合成气完全甲烷化反应。 [0033] d, from the heat recovery vessel Ib of silica particles out of the re-entering the mixer through line La, and add a small amount of fresh silica particles used in the process to compensate for the loss, and then carried into the synthesis gas through the gas - solid - reactor 2 solid new round of synthesis gas methanation reaction is complete.

[0034] 本实施例一氧化碳转化率为98%,甲烷选择性为95%。 [0034] The present embodiment was 98% conversion of carbon monoxide, methane selectivity of 95%.

[0035] 实施例3 [0035] Example 3

[0036] 采用如图1所示的气-固-固合成气完全甲烷化装置,操作步骤如下: [0036] The use of gas as shown in FIG. 1 - Solid - Solid complete methanation of synthesis gas, following these steps:

[0037] a、以合成气作为原料气,将原料气与石英砂在混和器Ia内混和,混合后进入装有甲烷化催化剂的气-固-固反应器2内,并在气-固-固反应器2中进行充分接触和反应;合成气中氢气与一氧化碳摩尔比为3.5,总体积流率为5m3/h,气-固-固反应器2的进口温度与出口温度分别为350°C和390°C,操作压力为4.0MPa ;催化剂颗粒的粒径为Φ IOmm长6mm的圆柱体,圆柱体内有三叶草状的通道;气-固-固反应器的内径为100mm,催化剂床层高度400mm ;石英砂颗粒粒径为75微米。 [0037] a, to the synthesis gas as a raw material gas, the raw material gas mixed with quartz sand in the mixer Ia, mixed with the methanation catalyst into the gas - solid - solid inside the reactor 2 and the gas - solid - solid 2 reactor sufficient contact and reaction; synthesis gas hydrogen to carbon monoxide molar ratio of 3.5, a total volume flow rate of 5m3 / h, gas - solid - solid reactor inlet temperature and the outlet temperature for 2 were 350 ° C and 390 ° C, an operating pressure of 4.0MPa; diameter of the catalyst particles is cylindrical Φ IOmm 6mm long, clover-shaped passage within the cylinder; gas - solid - solid inner diameter of the reactor is 100mm, the catalyst bed height 400mm ; quartz sand particle size of 75 microns.

[0038] b、从气-固-固反应器2出来的气固混和物进入旋风分离器3进行分离,分离出来的气体经工业处理装置处理后,最终得到纯净的甲烷; [0038] b, from the gas-solid - solid reaction into the cyclone 2 out of 3-solid mixture was separated, and the separated gas after treatment apparatus industrial process, the finally obtained pure methane;

[0039] C、从旋风分离器3出来的石英砂颗粒在热回收容器Ib中回收,使石英砂颗粒冷却至室温; [0039] C, recovered from the cyclone 3 out of silica particles in the heat recovery vessel Ib of the silica particles was cooled to room temperature;

[0040] d、从热回收容器Ib出来的石英砂颗粒通过管路重新进入混合器la,并加入少量新鲜石英砂颗粒用于补充上述过程中的损耗,再通过合成气携带进入气-固-固反应器2进行新一轮的合成气完全甲烷化反应。 [0040] d, from the heat recovery vessel Ib of silica particles out of the re-entering the mixer through line La, and add a small amount of fresh silica particles used in the process to compensate for the loss, and then carried into the synthesis gas through the gas - solid - reactor 2 solid new round of synthesis gas methanation reaction is complete.

[0041] 本实施例一氧化碳转化率为98%,甲烷选择性为95%。 [0041] The present embodiment was 98% conversion of carbon monoxide, methane selectivity of 95%.

[0042] 实施例4 [0042] Example 4

[0043] 采用如图1所示的气-固-固合成气完全甲烷化装置,操作步骤如下: [0043] The use of gas as shown in FIG. 1 - Solid - Solid complete methanation of synthesis gas, following these steps:

[0044] a、以合成气作为原料气,将原料气与氧化招微球在混和器Ia内混和,混合后进入装有甲烷化催化剂的气-固-固反应器2内,并在气-固-固反应器2中进行充分接触和反应;合成气中氢气与一氧化碳摩尔比为3.1,总体积流率为5m3/h,气-固-固反应器2的进口温度与出口温度分别为400°C和440°C,操作压力为3.0MPa ;催化剂颗粒的粒径为Φ Imm的球体;气-固-固反应器的内径为IOOmm ;氧化铝微球颗粒粒径为50微米。 [0044] a, to the synthesis gas as a raw material gas, the feed gas with an oxidizing move within the microspheres Ia mixing mixer, after mixing with the methanation catalyst into the gas - solid - solid inside the reactor 2 and the gas - solid - solid reactor 2 for full contact and reaction; synthesis gas hydrogen to carbon monoxide molar ratio of 3.1, a total volume flow rate of 5m3 / h, gas - solid - solid reactor inlet temperature and outlet temperature were 400 2 ° C and 440 ° C, an operating pressure of 3.0MPa; diameter of the catalyst particles is Φ Imm sphere; gas - solid - solid reactor having an inner diameter IOOmm; alumina microsphere particle size of 50 micrometers.

[0045] b、从气-固-固反应器2出来的气固混和物进入旋风分离器3进行分离,分离出来的气体经工业处理装置处理后,最终得到纯净的甲烷; [0045] b, from the gas-solid - solid reaction into the cyclone 2 out of 3-solid mixture was separated, and the separated gas after treatment apparatus industrial process, the finally obtained pure methane;

[0046] C、从旋风分离器3出来的氧化铝微球颗粒在热回收容器Ib中回收,使氧化铝微球颗粒冷却至室温; [0046] C, recovered from the cyclone 3 out of alumina microspheres particles in the heat recovery vessel Ib, the alumina particles were cooled to room temperature, the microspheres;

[0047] d、从热回收容器Ib出来的氧化铝微球颗粒通过管路重新进入混合器la,并加入少量新鲜用于补充上述过程中的损耗,再通过合成气携带进入气-固-固反应器2进行新一轮的合成气完全甲烷化反应。 [0047] d, from the heat recovery vessel Ib out alumina particles re-enter the microspheres la through line mixer, add a small amount of fresh and used to supplement the loss of the above process, and then carried into the synthesis gas through the gas - solid - solid the reactor 2 for a new round of synthesis gas methanation reaction is complete.

[0048] 本实施例一氧化碳转化率为99%,甲烷选择性为95%。 [0048] The present embodiment is 99% carbon monoxide conversion, methane selectivity of 95%.

Claims (4)

1.一种合成气完全甲烷化的装置,其特征在于,所述装置由混合器(la)、气-固-固反应器(2)、旋风分离器(3)、热回收容器(lb)、第一料封(4a)、第二料封(4b)构成;气-固-固反应器(2)设置在混合器(Ia)出口处,旋风分离器(3)入口与气-固-固反应器(2)的出口通过管道相连;热回收容器(Ib)分别通过第一料封(4a)和旋风分离器(3)相连,通过第二料封(4b)和混合器(Ia)相连。 A complete methanation of synthesis gas plant, characterized in that the said mixer means (La), gas - solid - solid reactor (2), the cyclone (3), heat recovery container (LB) , a first sealing material (. 4A), a second sealing material (4b) configured; gas - solid - solid reaction (2) disposed in a mixer (Ia) at the outlet of the cyclone separator (3) and an inlet gas - solid - the reactor solids outlet (2) is connected through a conduit; heat recovery container (Ib) through the first sealing material (4a) and a cyclone (3) is connected, through a second sealing material (4b) and the mixer (Ia) connected.
2.一种合成气完全甲烷化的方法,其特征在于,按照如下步骤进行: a、以合成气作为原料气,将原料气与惰性热载体颗粒在混合器(Ia)内混合,混合后进入装有甲烷化催化剂的气-固-固反应器(2)内,并在气-固-固反应器(2)中进行充分接触和反应;合成气中氢气与一氧化碳摩尔比为3.(Γ3.5,气-固-固反应器(2)的进口温度与出口温度分别为300°C〜500°C和340°C〜540°C,操作压力为3.0〜5.0 MPa ; b、从气-固-固反应器(2)出来的气固混合物进入旋风分离器(3)进行分离,分离出来的气体经工业处理装置处理后,最终得到纯净的甲烷; C、从旋风分离器(3)出来的惰性热载体颗粒在热回收容器(Ib)中回收,使惰性热载体颗粒冷却至室温;所述惰性热载体为氧化铝微球、石英砂或氟矿砂; d、从热回收容器(Ib)出来的惰性热载体颗粒通过管路重新进入混合器(Ia),并加入少量惰性 2. A method of complete methanation of synthesis gas, which is characterized by performing the following steps: a, synthesis gas as a raw material gas, the raw material gas and the inner inert heat carrier particles in a mixer (Ia) were mixed in into the methanation catalysts containing gas - solid - solid reactor (2), and gas - solid full contact and reaction reactor (2) - solid; synthesis gas hydrogen to carbon monoxide molar ratio is 3. (Γ3 .5, gas - solid - solid reactor (2) inlet temperature and outlet temperature of 300 ° C~500 ° C and 340 ° C~540 ° C, the operating pressure of 3.0~5.0 MPa; b, from the gas - solid - solid reactor (2) out of the gas-solid mixture enters the cyclone (3) separation, the separated gas after treatment apparatus industrial process, the finally obtained pure methane; C, (3) from the cyclone inert particulate heat carrier in the heat recovery container (Ib) recovering the inert particulate heat carrier is cooled to room temperature; the inert heat carrier is alumina microspheres, quartz sand ore or fluoro; D, from the heat recovery vessel (Ib) out of the inert particulate heat carrier to re-enter the mixer through line (Ia), and add a small amount of an inert 鲜热载体颗粒用于补充上述过程中的损耗,再通过合成气携带进入气-固-固反应器(2)进行新一轮的合成气完全甲烷化反应。 Fresh hot replenish depleted carrier particles used in the above process, and then carried into the gas by the synthesis gas - a new round of synthesis gas solid reaction (2) complete methanation reactor - solid.
3.根据权利要求2所述一种合成气完全甲烷化的方法,其特征在于,所述惰性热载体颗粒的粒径大小为5〜200微米。 3. The method of synthesizing 2 gas methanation completely claim, wherein the inert heat carrier particles microns particle size of 5~200.
4.根据权利要求2所述一种合成气完全甲烷化的方法,其特征在于,所述气-固-固反应器(2)在固定床状态下操作时,使用催化剂颗粒粒径在5〜10毫米,在流化床状态下操作时,使用催化剂颗粒粒径在Γ5毫米。 4. The method of synthesizing 2 gas methanation completely claim, characterized in that the gas - solid - solid reaction (2) is operated in the state of a fixed bed, catalyst particle size at -5 to 10 mm, while operating in the fluidized state, the catalyst particle size Γ5 mm.
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CN101559924A (en) 2009-05-26 2009-10-21 清华大学 Methane vapor reforming hydrogen production process and devices thereof
CN101665395A (en) 2009-09-18 2010-03-10 清华大学 Fluidized bed process and device for preparing methane by synthetic gas

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