阅读说明：本技术 一种利用流态化技术生产烃类的方法 (Method for producing hydrocarbon by using fluidization technology ) 是由 刘罡 王振维 孙丽丽 盛在行 聂毅强 李少鹏 丁利伟 赵百仁 于 2019-03-27 设计创作，主要内容包括：本发明属于石油化工领域,涉及一种利用流态化技术生产烃类的方法。将富甲烷气体与富氧气体接触形成原料气,进行氧化偶联反应,得到产品气；所述反应在一组或多组串联的流化床反应器内完成,每一组反应器具备以下特征：反应器内部设置有隔热结构,反应器出口就近设置一组或多组催化剂分离措施,氧化偶联反应出料进入所述催化剂分离措施进行分离,分离得到的产品气对原料气进行第一次加热,分离得到的催化剂不经再生循环直接回用至反应器,同时用于原料气的第二次加热。本发明基于流态化技术,结合甲烷氧化强放热的特征,充分利用了流化床反应器热容量大,换热速率高的特点,可实现强放热条件下的氧化偶联反应的稳定进行。(The invention belongs to the field of petrochemical industry, and relates to a method for producing hydrocarbons by using a fluidization technology. Contacting the methane-rich gas with the oxygen-rich gas to form a feed gas, and carrying out oxidative coupling reaction to obtain a product gas; the reaction is completed in one or more groups of fluidized bed reactors connected in series, and each group of reactors has the following characteristics: the reactor is internally provided with a heat insulation structure, one or more groups of catalyst separation measures are arranged near the outlet of the reactor, the discharge of the oxidative coupling reaction enters the catalyst separation measures for separation, the product gas obtained by separation is used for heating the raw material gas for the first time, and the catalyst obtained by separation is directly recycled to the reactor without regeneration and circulation and is used for heating the raw material gas for the second time. The invention is based on the fluidization technology, combines the characteristic of strong heat release of methane oxidation, fully utilizes the characteristics of large thermal capacity and high heat exchange rate of the fluidized bed reactor, and can realize the stable operation of the oxidative coupling reaction under the condition of strong heat release.)

1. A process for preparing hydrocarbon by fluidized method features that the methane-rich gas is contacted with oxygen-rich gas to obtain raw material gas, and the raw material gas is oxidized and coupled to obtain the product containing at least CO and CO₂Product gas of ethylene, ethane, carbon three and above components;

the reaction is completed in one or more groups of fluidized bed reactors connected in series, and each group of reactors has the following characteristics: the reactor is internally provided with a heat insulation structure, one or more groups of catalyst separation measures are arranged near the outlet of the reactor, the discharge of the oxidative coupling reaction enters the catalyst separation measures for separation, the product gas obtained by separation is used for heating the raw material gas for the first time, and the catalyst obtained by separation is directly recycled to the reactor without regeneration and circulation and is used for heating the raw material gas for the second time.

2. The method of claim 1, wherein the unconverted feed components in the product gas are separated and partially or completely recycled to the reactor for reaction.

3. A method for the fluidized production of hydrocarbons according to claim 1, wherein the reactor is provided with a separate injection port for oxygen-rich gas and a separate injection port for methane-rich gas.

4. A method of producing hydrocarbons using fluidization techniques according to claim 1, wherein the volume ratio of methane to oxygen at the reactor inlet is 0.5: 1-50: 1.

5. the method of claim 1, wherein the temperature of the oxidative coupling reaction is 650 to 950 ℃ and the pressure is 0.01 to 1.5MPaG, preferably 0.05 to 1.0 MPaG.

6. The process of claim 1, wherein the first heating of the feed gas by the separated product gas is performed in a heat exchanger.

7. The method of claim 1, wherein the residence time of the material from the reaction zone to the heat exchange zone of the product gas is 0.01-120 s.

8. The method of claim 1, wherein the insulating structure is made of a ceramic material.

9. The method of claim 1, wherein the reaction is carried out in two series-connected fluidized bed reactors, the product gas from the first series reactor exchanges heat with the feed gas and then enters the second series reactor, and the product gas from the second series reactor exchanges heat with the make-up feed gas.

10. The method of claim 1, wherein the methane-rich gas has a methane content of > 50% by volume, preferably > 90% by volume, and further preferably the methane-rich gas is natural gas and/or shale gas; the volume content of oxygen in the oxygen-enriched gas is 12-100%.

Technical Field

The invention belongs to the field of petrochemical industry, and particularly relates to a method for producing hydrocarbons by using a fluidization technology.

Background

Ethylene is one of the chemical products with the largest yield in the world, the ethylene industry is the core of the petrochemical industry, and the ethylene product accounts for more than 75 percent of petrochemical products and occupies an important position in national economy. Ethylene production has been used worldwide as one of the important indicators for the development of petrochemical in one country.

With the large fluctuation of the international crude oil price and the technical progress, in order to change the condition that the raw materials for producing ethylene depend on petroleum resources excessively, the raw materials for producing ethylene are changed, and the technology for producing ethylene by taking methanol as the raw material is developed and becomes a technology with wide industrial application in the novel coal chemical industry technology.

The technology for preparing ethylene by Oxidative Coupling of Methane (OCM) is an important technology for producing ethylene, takes natural gas as a raw material, can prepare ethylene by only one-step reaction process, and has high theoretical value and economic value. After more than 30 years of research, the research on ethylene preparation by a methane one-step method has made a breakthrough, and the industrial demonstration device for preparing ethylene by methane coupling is successfully put into production, which is moving towards the beginning of industrialization. The method has great significance for breaking the bottleneck of raw material sources in the ethylene industry, reducing the production cost and enhancing the competitiveness of the ethylene industry and downstream industries.

Research and development at home and abroad are most typical of Siluria technology company in the United states, and the Siluria develops an industrially feasible methane direct ethylene catalyst by precisely synthesizing a nanowire catalyst by using a biological template. The catalyst can efficiently catalyze the conversion of methane into ethylene under the condition of 200-300 ℃ lower than the operation temperature of the traditional steam cracking method and under the pressure of 5-10 atmospheric pressures. The technology prolongs the service life of the catalyst, greatly reduces the operation temperature, but has no substantial breakthrough on the conversion rate of methane and the yield of ethylene.

The reactor types used in the reaction process of preparing ethylene by oxidative coupling of methane include fluidized bed reactor, fixed bed reactor, membrane reactor, etc., but the industrial application of these reactors is yet to be further developed.

Disclosure of Invention

The invention aims to provide a method for producing hydrocarbons by using a fluidization technology, so that the high-efficiency conversion of methane is realized to produce hydrocarbon products with high added values.

In order to achieve the purpose, the invention provides a method for producing hydrocarbons by using a fluidization technology, which comprises the steps of contacting a methane-rich gas with an oxygen-rich gas to form a raw material gas, and carrying out an oxidative coupling reaction to obtain a product gas at least containing CO and CO₂Product gas of ethylene, ethane, carbon three and above components;

the reaction is completed in one or more groups of fluidized bed reactors connected in series, and each group of reactors has the following characteristics: the reactor is internally provided with a heat insulation structure, one or more groups of catalyst separation measures are arranged near the outlet of the reactor, the discharge of the oxidative coupling reaction enters the catalyst separation measures for separation, the product gas obtained by separation is used for heating the raw material gas for the first time, and the catalyst obtained by separation is directly recycled to the reactor without regeneration and circulation and is used for heating the raw material gas for the second time. The inlet temperature between the sections was controlled by the above method.

According to the invention, the unconverted feed components in the product gas are preferably separated and partly or completely recycled to the reactor for reaction.

According to the present invention, it is preferred that the reactor is provided with separate oxygen-rich gas injection ports and methane-rich gas injection ports, respectively, for the injection of additional oxygen-rich gas and methane-rich gas.

In the process of the present invention, the ratio of alkoxy to oxygen fed to the reactor is controlled, and preferably, the volume ratio of methane to oxygen at the inlet of the reactor is 0.5: 1-50: 1.

According to the present invention, the temperature of the oxidative coupling reaction is preferably 650 to 950 ℃, and the pressure is preferably 0.01 to 1.5MPaG, more preferably 0.05 to 1.0 MPaG.

According to the present invention, preferably, the first heating of the feed gas by the separated product gas is performed in a heat exchanger.

According to the invention, preferably, the residence time of the materials from the reaction area to the heat exchange area of the product gas is 0.01-120 s, and the residence time is selected to effectively avoid the product loss caused by the occurrence of secondary reaction.

In the present invention, the heat insulating structure is used to separate a high temperature region from a low temperature region. Useful insulation structures may use refractory materials as the primary material of construction to separate high temperature regions within the reactor from low temperature regions such as the outer walls, heat extraction structures, pipelines, etc. According to the invention, the material of the heat insulation structure is preferably ceramic material.

The reaction of the invention can be completed in one or more groups of fluidized bed reactors connected in series, and when the reaction is completed in a plurality of groups of fluidized bed reactors connected in series, the product gas obtained from each group of reactors enters the next group of reactors after heat exchange with the feed gas.

According to a preferred embodiment of the present invention, the reaction is carried out in two sets of fluidized bed reactors connected in series, the product gas obtained from the first set of reactors exchanges heat with the feed gas and then enters the second set of reactors, and the product gas obtained from the second set of reactors exchanges heat with the make-up feed gas. The feed gas may comprise a portion of the product gas that is recycled back after separation of unconverted methane.

The invention has the beneficial effects that: based on the fluidization technology, the characteristics of large thermal capacity and high heat exchange rate of the fluidized bed reactor are fully utilized by combining the characteristic of strong heat release of methane oxidation, and the stable operation of the oxidative coupling reaction under the condition of strong heat release can be realized; after the catalyst and the reaction product gas are separated, the low-temperature feed gas is sequentially heated, so that the reaction conditions can be accurately controlled, and the high yield is ensured.

Additional features and advantages of the invention will be set forth in the detailed description which follows.

Drawings

The above and other objects, features and advantages of the present invention will become more apparent by describing in more detail exemplary embodiments thereof with reference to the attached drawings.

Figure 1 shows a schematic diagram of a solution using two sets of fluidized bed reactors with make-up feed.

Figure 2 shows a schematic of a solution using 1 group of fluidized bed reactors.

Description of the reference numerals

1. A first fluidized bed reactor; 2. a first catalyst separation facility; 3. a first heat exchanger; 4. a first secondary heating zone; 5. a second fluidized bed reactor; 6. a second catalyst separation facility; 7. a second heat exchanger; 4. a second secondary heating zone.

S1, raw material gas; s2, heating the raw material gas for the first time; s3, discharging the first oxidative coupling reaction; s4, first product gas; s5, a first separation catalyst; s6, first heat-exchanged product gas; s7, a catalyst; s8, supplementing raw material gas; s9, supplementing raw material gas after primary heating; s10, discharging the second oxidation coupling reaction; s11, second product gas; s12, separating the catalyst; s13, and performing second heat exchange on the product gas.

Detailed Description

Preferred embodiments of the present invention will be described in more detail below. While the following describes preferred embodiments of the present invention, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein.