WO2021180195A1 - 在流化床反应器内转化甲醇的方法 - Google Patents

在流化床反应器内转化甲醇的方法 Download PDF

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Publication number
WO2021180195A1
WO2021180195A1 PCT/CN2021/080383 CN2021080383W WO2021180195A1 WO 2021180195 A1 WO2021180195 A1 WO 2021180195A1 CN 2021080383 W CN2021080383 W CN 2021080383W WO 2021180195 A1 WO2021180195 A1 WO 2021180195A1
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weight
catalyst
fluidized bed
bed reactor
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PCT/CN2021/080383
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English (en)
French (fr)
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齐国祯
曹静
李晓红
王洪涛
王莉
王艳学
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中国石油化工股份有限公司
中国石油化工股份有限公司上海石油化工研究院
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Priority to CN202180020778.7A priority Critical patent/CN115244026A/zh
Priority to US17/906,234 priority patent/US20230118300A1/en
Priority to BR112022018227A priority patent/BR112022018227A2/pt
Priority to AU2021233968A priority patent/AU2021233968A1/en
Publication of WO2021180195A1 publication Critical patent/WO2021180195A1/zh
Priority to ZA2022/11240A priority patent/ZA202211240B/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/90—Regeneration or reactivation
    • 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
    • B01J8/0015—Feeding of the particles in the reactor; Evacuation of the particles out of the reactor
    • B01J8/0035—Periodical feeding or evacuation
    • 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
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/02—Alkenes
    • C07C11/06—Propene
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/82—Phosphates
    • B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
    • B01J29/85—Silicoaluminophosphates [SAPO compounds]
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/82—Phosphates
    • C07C2529/84—Aluminophosphates containing other elements, e.g. metals, boron
    • C07C2529/85—Silicoaluminophosphates (SAPO compounds)
    • 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
    • Y02P20/584—Recycling of catalysts
    • 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
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
    • 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
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/40—Ethylene production

Definitions

  • the invention relates to a method for converting methanol in a fluidized bed reactor.
  • Low-carbon olefins namely ethylene and propylene
  • ethylene and propylene are essential basic materials in modern petrochemical and chemical industries.
  • people have devoted themselves to finding non-petroleum sources to meet the demand for these light olefin materials.
  • Most of the focus of the prior art has focused on the possibility of using hydrocarbon oxygenates, especially methanol as the main source of necessary alternative raw materials.
  • hydrocarbon oxygenates especially methanol
  • silicoaluminophosphate molecular sieves especially SAPO-34 molecular sieves, show relatively high product selectivity for ethylene and propylene, and low selectivity for paraffins and C4 and above olefins. .
  • the document CN1404462A discloses an operating method for the conversion reaction of oxygenates to olefins to provide a large amount of main olefins.
  • the product is provided by operating within the required parameters of weight hourly space velocity and oxygenate partial pressure. Operate the reaction to supply oxygenate at an oxygenate ratio index of at least 0.5, and control the weight hourly space velocity and the molar flow rate of oxygenate supplied to the reactor to maintain a fraction of at least 0.1 psia -1 hr -1
  • the pressure-speed compensation factor can maintain at least 45% (weight) selectivity of the main olefin.
  • Document CN1723262A discloses a multi-stage riser reaction device with a central catalyst loop for the conversion of oxides to low-carbon olefins.
  • the device includes multiple riser reactors, gas-solid separation zones, multiple offset elements, etc.
  • Each riser reactor has its own port for injecting the catalyst, which is collected into the set separation zone to separate the catalyst from the product gas.
  • the yield of low-carbon olefin carbon base is generally between 75% and 80%.
  • the document CN101270020B discloses a method for producing low-carbon olefins from methanol, which includes heating the oxygen-containing compound raw material including methanol at a reaction temperature of 300 to 600°C, the weight hourly space velocity of the oxygen-containing compound raw material is 1 to 50 hours-1, and the reaction pressure Under the condition of (gauge pressure) of 0.05-10 MPa, the raw material is in contact with the silicoaluminophosphate molecular sieve catalyst in the reactor.
  • the inventors of the present invention found that for the method of converting methanol in a fluidized bed reactor, in the area where methanol exists, especially in the area where methanol is not completely converted, it is very important to control the temperature difference within 20°C, which can ensure High methanol conversion rate can ensure high selectivity of low-carbon olefins.
  • the inventors of the present invention have found that for the method of converting methanol in a fluidized bed reactor, the temperature difference is more controlled in the area where methanol exists, especially in the area where the methanol concentration is large, such as the dense phase area or the fast bed area. Conducive to obtaining high selectivity for low-carbon olefins.
  • the inventors of the present invention also found that for the method of converting methanol in a fluidized bed reactor, in the area where methanol exists, in addition to the above dense phase zone, further controlling the temperature difference in the dilute phase zone is more conducive to obtaining high and low carbon. Olefin selectivity.
  • the inventors of the present invention also found that the mixing quality of the low coke deposit catalyst and the high coke deposit catalyst is very important for improving the selectivity of olefins.
  • the inventor of the present invention also found that the reaction performance of methanol feedstock on catalysts with different coke deposits varies greatly, especially when methanol is reacted on a catalyst with coke deposits less than 3% by weight, the selectivity of low-carbon olefins is greatly reduced; but it must be ensured A high methanol conversion rate and a coke deposit less than 3% by weight of the catalyst are also indispensable.
  • the inventor of the present invention also found that when the regenerated catalyst is returned from the regenerator to the fluidized bed reactor, a good distribution of the regenerated catalyst in the reactor is very important. This part of the catalyst not only affects the average carbon deposit in the reactor, but also affects the temperature distribution of the reactor. When methanol feedstock comes in contact with this high-temperature, high-activity regenerated catalyst, the selectivity of olefins will be greatly reduced; if the regenerated catalyst is unevenly distributed, it will affect the uneven temperature in the reactor and also affect the selectivity of olefins.
  • the present invention has been completed based on these findings.
  • the present invention provides, for example, embodiments in the following aspects:
  • a method for converting methanol in a fluidized bed reactor which includes feeding a raw material containing methanol into the fluidized bed reactor, contacting with a catalyst, and generating products including ethylene and propylene under effective conditions; the fluidized bed reaction
  • the reactor includes a dilute phase zone and a dense phase zone, and is characterized in that the dilute phase temperature difference between any zone where the methanol concentration in the dilute phase zone in the fluidized bed reactor is greater than 0.1% by weight (preferably greater than 0.01% by weight) is controlled to be less than 20°C, and control the dense phase temperature difference between any areas where the methanol concentration in the dense phase zone in the fluidized bed reactor is greater than 0.1% by weight (preferably greater than 0.01% by weight) to be less than 10°C.
  • the effective conditions include: based on the mass of molecular sieve in the catalyst, the methanol concentration in the fluidized bed reactor is greater than 0.01% by weight.
  • the amount of soot deposited on the catalyst is 1.5 to 10% by weight, preferably 2 to 8% by weight, and more preferably 4 to 7% by weight.
  • the catalyst accounts for 10 to 70% by weight, preferably 15 to 60% by weight, 20 to 50% by weight, or 30 to 45% by weight; the catalyst with a coke deposit of 5-10% by weight accounts for 10 to 88% by weight, preferably 15 to 80% by weight, 20 to 70% by weight, or 30 to 60% by weight.
  • the active component of the catalyst is a silicoaluminophosphate molecular sieve
  • the silicoaluminophosphate molecular sieve is, for example, SAPO-18, SAPO-34, SAPO-5 or The combination thereof is preferably SAPO-34
  • the fluidized bed reactor is of dense phase, turbulent or fast fluidized type.
  • the conveying medium in the catalyst distributor is selected from at least one of steam, oxygen-containing by-products, and C4 hydrocarbons; the oxygen-containing by-products Including acetone and acetaldehyde.
  • both high raw material conversion rate and high low-carbon olefin selectivity can be ensured.
  • the amount of coke deposited on the catalyst in the reactor is an average concept. Because in the fluidized bed reactor, there is a catalyst cycle between reaction and regeneration, and there are catalysts with low carbon deposits and catalysts with high carbon deposits, so there must be a mixture of multiple catalysts in the reactor.
  • the method for calculating the amount of soot on the catalyst is the mass of soot on the catalyst divided by the mass of the catalyst.
  • the method for measuring the quality of coke deposits on the catalyst is as follows: weigh 0.1 to 1 g of the catalyst with carbon and burn it in a high-temperature carbon analyzer, and measure the mass of carbon dioxide generated by the combustion by infrared to obtain the quality of coke deposits on the catalyst. In order to determine the amount of carbon deposited on the catalyst in the reaction zone, a small amount of catalyst can be drawn out continuously or periodically or directly from various positions in the reaction zone.
  • any two or more embodiments of the present invention can be combined arbitrarily, and the technical solutions formed thereby belong to a part of the original disclosure of this specification and also fall into the protection scope of the present invention.
  • the methanol feedstock enters the reaction zone of the fast fluidized bed reactor (hereinafter referred to as the fluidized bed reaction zone), contacts with the SAPO-34 molecular sieve catalyst, and produces products including ethylene and propylene under effective conditions.
  • the catalyst in the reaction zone of the bed is deactivated to form a spent catalyst.
  • the spent catalyst enters the regenerator for regeneration to form a regenerated catalyst.
  • the regenerated catalyst is returned to the fluidized bed reaction zone.
  • the difference between the amount of coke deposited on the spent catalyst and the regenerated catalyst is 5 wt%.
  • the gas phase and catalyst in the fluidized bed reaction zone are quickly separated by separation equipment after the reaction is completed or after leaving the fluidized bed reaction zone.
  • the effective conditions are: the reaction temperature is 450°C, the reaction gauge pressure is 0.15MPa, the temperature difference in the area where the methanol concentration is greater than 0.1% in the fluidized bed reactor is 4°C, and the amount of coke deposited on the catalyst based on the mass of the molecular sieve on the catalyst.
  • the catalyst with a coke deposit of less than 3% by weight accounts for 2% by weight of the total catalyst mass in the fluidized bed reactor, and the catalyst with a coke deposit of 3 to less than 5% by weight accounts for 68% by weight.
  • the catalyst with a carbon deposit of 5-10% by weight accounts for 23% by weight.
  • the outlet of the regeneration pipeline is provided with a catalyst distributor, which is arranged horizontally along the radial direction of the fluidized bed reactor to uniformly distribute the regenerated catalyst on the radial plane of the reaction zone of the fluidized bed reactor.
  • the transport medium in the catalyst distributor is water vapor. Sampling analysis results show that the methanol conversion rate is 99.98%, and the ethylene + propylene carbon-based selectivity is 83.07%.
  • the methanol feedstock enters the fast fluidized bed reaction zone, contacts with SAPO-34 molecular sieve catalyst, and produces products including ethylene and propylene under effective conditions.
  • the catalyst in the fluidized bed reaction zone is deactivated to form standby catalyst.
  • the spent catalyst enters the regenerator for regeneration to form a regenerated catalyst.
  • the regenerated catalyst is returned to the fluidized bed reaction zone.
  • the difference between the amount of coke deposited on the spent catalyst and the regenerated catalyst is 5 wt%.
  • the gas phase and catalyst in the fluidized bed reaction zone are quickly separated by separation equipment after the reaction is completed or after leaving the fluidized bed reaction zone.
  • the effective conditions are: the reaction temperature is 450°C, the reaction gauge pressure is 0.15MPa, the temperature difference in the area where the methanol concentration is greater than 0.1% in the fluidized bed reactor is 4°C, and the amount of coke deposited on the catalyst based on the mass of the molecular sieve on the catalyst.
  • the catalyst with a coke deposit of less than 3% by weight accounts for 10% by weight of the total catalyst mass in the fluidized bed reactor, and the catalyst with a coke deposit of 3 to less than 5% by weight accounts for 50% by weight.
  • the catalyst with a carbon deposit of 5-10% by weight accounts for 35% by weight.
  • the outlet of the regeneration pipeline is provided with a catalyst distributor, which is arranged horizontally along the radial direction of the fluidized bed reactor to uniformly distribute the regenerated catalyst on the radial plane of the reaction zone of the fluidized bed reactor.
  • the transport medium in the catalyst distributor is water vapor.
  • the methanol feedstock enters the fast fluidized bed reaction zone, contacts with SAPO-34 molecular sieve catalyst, and produces products including ethylene and propylene under effective conditions.
  • the catalyst in the fluidized bed reaction zone is deactivated to form standby catalyst.
  • the spent catalyst enters the regenerator for regeneration to form a regenerated catalyst.
  • the regenerated catalyst is returned to the fluidized bed reaction zone.
  • the difference between the amount of coke deposited on the spent catalyst and the regenerated catalyst is 5 wt%.
  • the gas phase and catalyst in the fluidized bed reaction zone are quickly separated by separation equipment after the reaction is completed or after leaving the fluidized bed reaction zone.
  • the effective conditions are: the reaction temperature is 400°C, the reaction gauge pressure is 0.05MPa, the temperature difference in the area where the methanol concentration is greater than 0.1% in the fluidized bed reactor is 9°C, and the amount of coke deposited on the catalyst based on the mass of the molecular sieve on the catalyst.
  • the catalyst with a coke deposit of less than 3% by weight accounts for 1.5% by weight of the total catalyst mass in the fluidized bed reactor, and the catalyst with a coke deposit of 3 to less than 5% by weight accounts for 43% by weight.
  • the catalyst with a carbon deposit of 5-10% by weight accounts for 53% by weight.
  • the outlet of the regeneration pipeline is provided with a catalyst distributor, which is arranged horizontally along the radial direction of the fluidized bed reactor to uniformly distribute the regenerated catalyst on the radial plane of the reaction zone of the fluidized bed reactor.
  • the transport medium in the catalyst distributor is water vapor. Sampling analysis results show that the methanol conversion rate is 99.06%, and the ethylene + propylene carbon-based selectivity is 82.56%.
  • the methanol feedstock enters the fast fluidized bed reaction zone, contacts with SAPO-34 molecular sieve catalyst, and produces products including ethylene and propylene under effective conditions.
  • the catalyst in the fluidized bed reaction zone is deactivated to form standby catalyst.
  • the spent catalyst enters the regenerator for regeneration to form a regenerated catalyst.
  • the regenerated catalyst is returned to the fluidized bed reaction zone.
  • the difference between the amount of coke deposited on the spent catalyst and the regenerated catalyst is 6 wt%.
  • the gas phase and catalyst in the fluidized bed reaction zone are quickly separated by separation equipment after the reaction is completed or after leaving the fluidized bed reaction zone.
  • the effective conditions are: the reaction temperature is 550°C, the reaction gauge pressure is 1.0MPa, the temperature difference in the area where the methanol concentration is greater than 0.1% in the fluidized bed reactor is 9°C, and the amount of coke deposited on the catalyst, based on the mass of the molecular sieve on the catalyst.
  • the catalyst with a coke deposit of less than 3% by weight accounts for 18% by weight of the total catalyst mass in the fluidized bed reactor, and the catalyst with a coke deposit of 3 to less than 5% by weight accounts for 30% by weight,
  • the catalyst with a coke deposit amount of 5-10% by weight accounts for 48% by weight.
  • the outlet of the regeneration pipeline is provided with a catalyst distributor, which is arranged horizontally along the radial direction of the fluidized bed reactor to uniformly distribute the regenerated catalyst on the radial plane of the reaction zone of the fluidized bed reactor.
  • the conveying medium in the catalyst distributor is C4. Sampling analysis results show that the methanol conversion rate is 99.99%, and the ethylene + propylene carbon-based selectivity is 85.44%.
  • the methanol feedstock enters the turbulent fluidized bed reaction zone, contacts with SAPO-34 molecular sieve catalyst, and produces products including ethylene and propylene under effective conditions.
  • the catalyst in the fluidized bed reaction zone is deactivated to form a standby Health catalyst.
  • the spent catalyst enters the regenerator for regeneration to form a regenerated catalyst.
  • the regenerated catalyst is returned to the fluidized bed reaction zone.
  • the difference between the amount of coke deposited on the spent catalyst and the regenerated catalyst is 5 wt%.
  • the gas phase and catalyst in the fluidized bed reaction zone are quickly separated by separation equipment after the reaction is completed or after leaving the fluidized bed reaction zone.
  • the effective conditions are: the reaction temperature is 480°C, the reaction gauge pressure is 0.15MPa, the temperature difference in the area where the methanol concentration is greater than 0.1% in the fluidized bed reactor is 2°C, and the amount of coke deposited on the catalyst based on the mass of the molecular sieve on the catalyst.
  • the catalyst with a coke deposit of less than 3% by weight accounts for 5% by weight of the total catalyst mass in the fluidized bed reactor, and the catalyst with a coke deposit of 3 to less than 5% by weight accounts for 65% by weight.
  • the catalyst with a carbon deposit of 5-10% by weight accounts for 25% by weight.
  • the outlet of the regeneration pipeline is provided with a catalyst distributor, which is arranged horizontally along the radial direction of the fluidized bed reactor to uniformly distribute the regenerated catalyst on the radial plane of the reaction zone of the fluidized bed reactor.
  • the conveying medium in the catalyst distributor is the by-product of oxygen-containing compounds. Sampling analysis results show that the methanol conversion rate is 99.93%, and the ethylene + propylene carbon-based selectivity is 84.09%.
  • the method of the present invention can achieve the purpose of improving the yield of low-carbon olefins, and can be used in the industrial production of low-carbon olefins.

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Abstract

本发明涉及一种在流化床反应器内转化甲醇的方法，包括使含甲醇的原料进入流化床反应器，与催化剂接触，在有效条件下生成包括乙烯、丙烯的产品；该流化床反应器包括稀相区和密相区，其特征在于，控制所述流化床反应器内稀相区中甲醇浓度大于0.1重量％(优选大于0.01重量％)的任何区域间的稀相温度差小于20℃，并且控制该流化床反应器内的密相区中甲醇浓度大于0.1重量％(优选大于0.01重量％)的任何区域间的密相温度差小于10℃。

Description

在流化床反应器内转化甲醇的方法 技术领域
本发明涉及一种在流化床反应器内转化甲醇的方法。
背景技术
低碳烯烃，即乙烯和丙烯，是现代石化和化学工业中的必要基础材料。近年来，人们致力于寻找非石油源，用于获得满足对这些轻烯烃物质的需求。现有技术关注的焦点大部分集中在使用烃含氧物，特别是甲醇作为必要可替代原料主要来源的可能性。在甲醇到烯烃的转化过程中，硅铝磷酸盐分子筛，特别是SAPO-34分子筛表现出相对高的乙烯和丙烯的产物选择性，对链烷烃和C4及其以上烯烃表现出较低的选择性。
文献CN1404462A公布了一种含氧化合物至烯烃的转化反应的操作方法以提供大量的主烯烃。通过在要求的重时空速和含氧化合物分压的参数内操作提供所述产品。操作所述反应在至少0.5的含氧化合物比例指数下供应含氧化合物，并控制重时空速和供入所述反应器的含氧化合物的摩尔流量以保持至少0.1psia -1hr -1的分压-速度补偿因子，可保持至少45％(重)的主烯烃选择性。
文献CN1723262A公布了带有中央催化剂回路的多级提升管反应装置用于氧化物转化为低碳烯烃工艺，该套装置包括多个提升管反应器、气固分离区、多个偏移元件等，每个提升管反应器各自具有注入催化剂的端口，汇集到设置的分离区，将催化剂与产品气分开。该方法中低碳烯烃碳基收率一般均在75～80％之间。
文献CN101270020B公开了甲醇生产低碳烯烃的方法，包括将包括甲醇的含氧化合物原料加热，在反应温度为300～600℃、含氧化合物的原料重时空速为1～50小时-1、反应压力(表压)为0.05～10MPa的条件下，原料与硅铝磷酸盐分子筛催化剂在反应器内接触。
然而，随着市场上对乙烯、丙烯需求量的不断增加，如何通过优化反应条件提高双烯收率，始终是本领域追求的目标。
发明内容
本发明的发明人发现，对于流化床反应器内转化甲醇的方法，在有甲醇存在的区域内，特别是甲醇未转化完全的区域内，控制温差在20℃以内至关重要，既能保证高的甲醇转化率，又能保证高的低碳烯烃选择性。
本发明的发明人发现，对于流化床反应器内转化甲醇的方法，在有甲醇存在的区域内，特别是在甲醇浓度较大的区域内，例如密相区或快床区，控制温差更有利于获得高的低碳烯烃选择性。
本发明的发明人还发现，对于流化床反应器内转化甲醇的方法，在有甲醇存在的区域内，除了上述密相区外，进一步在稀相区控制温差更有利于获得高的低碳烯烃选择性。
本发明的发明人还发现，低积炭量催化剂与高积炭量催化剂的混合质量对于提高烯烃选择性至关重要。
本发明的发明人还发现，甲醇原料在不同积炭量催化剂上的反应性能差异巨大，尤其是甲醇在积炭量小于3重量％催化剂上反应时，低碳烯烃选择性大幅降低；但是要保证高的甲醇转化率，积炭量小于3重量％催化剂又是必不可少的。
本发明的发明人还发现，再生催化剂从再生器返回流化床反应器时，再生催化剂在反应器内的良好分布至关重要。这部分催化剂不但影响反应器内的平均积炭量，同时还影响反应器的温度分布。甲醇原料与这股高温、高活性再生催化剂接触，烯烃选择性会大幅降低；这股再生催化剂如果分布不均匀，会影响反应器内温度不均，同样会影响烯烃选择性。
本发明基于这些发现而完成。
具体而言，本发明例如提供了以下方面的实施方式：
1、一种在流化床反应器内转化甲醇的方法，包括使含甲醇的原料进入流化床反应器，与催化剂接触，在有效条件下生成包括乙烯、丙烯的产品；该流化床反应器包括稀相区和密相区，其特征在于，控制所述流化床反应器内稀相区中甲醇浓度大于0.1重量％(优选大于0.01重量％)的任何区域间的稀相温度差小于20℃，并且控制该流化床反应器内的密相区中甲醇浓度大于0.1重量％(优选大于0.01重量％)的任何区域间的密相温度差小于10℃。
2、根据实施方式1所述的方法，其特征在于，所述流化床反应器 内的所述稀相温度差小于10℃，和/或所述流化床反应器内的所述密相温度差小于10℃。
3、根据实施方式1-2任一所述的方法，其特征在于，所述有效条件包括：以催化剂中分子筛质量计，所述流化床反应器内甲醇浓度大于0.01重量％的区域内的催化剂积炭量为1.5～10重量％，优选2～8重量％，更优选4～7重量％。
4、根据实施方式3所述的方法，其特征在于，以催化剂中分子筛质量计，所述流化床反应器内甲醇浓度大于0.01重量％的区域内，积炭量小于3重量％的催化剂质量占所述流化床反应器内全部催化剂质量的比例为1～20重量％，优选为1.5～10重量％，更优选为2～5重量％。
5、根据实施方式4所述的方法，其特征在于，以催化剂中分子筛质量计，所述流化床反应器内甲醇浓度大于0.01重量％的区域内，积炭量为3至小于5重量％的催化剂占10～70重量％，优选为15～60重量％，20～50重量％，或30～45重量％；积炭量为5-10重量％的催化剂占10～88重量％，优选为15～80重量％，20～70重量％，或30～60重量％。
6、根据前述实施方式中任一所述的方法，其特征在于，所述有效条件包括：反应温度400～550℃，反应压力0～1MPa。
7、根据前述实施方式中任一所述的方法，其中所述流化床反应器内的催化剂失活后形成待生催化剂，所述待生催化剂通过待生管路进入再生器再生，形成再生催化剂，所述再生催化剂通过再生管路返回到所述流化床反应器；其特征在于，所述待生催化剂与所述再生催化剂的积炭量之差小于7重量％，优选小于6重量％，更优选小于4重量％。
8、根据前述实施方式中任一所述的方法，其特征在于，所述催化剂活性组分为硅铝磷分子筛；所述硅铝磷分子筛例如为SAPO-18、SAPO-34、SAPO-5或其组合，优选为SAPO-34；和/或所述流化床反应器为密相、湍动或快速流态化型式。
9、根据前述实施方式中任一所述的方法，其特征在于，所述流化床反应器内部或/和外部设有温度调节设备。
10、根据前述实施方式中任一所述的方法，其特征在于，所述流化床反应器下部设置有再生管路出口，所述再生管路出口设置有催化剂分布器；所述分布器沿所述流化床反应器径向基本水平布置。
11、根据实施方式10所述的方法，其特征在于，所述催化剂分布器内的输送介质选自水蒸气、含氧化合物副产物、C4烃中的至少一种；所述含氧化合物副产物包括丙酮、乙醛。
技术效果
根据本发明方法，既能保证高的原料转化率，又能保证高的低碳烯烃选择性。
具体实施方式
下面对本发明的具体实施方式进行详细说明，但是需要指出的是，本发明的保护范围并不受这些具体实施方式的限制，而是由附录的权利要求书来确定。
本说明书提到的所有出版物、专利申请、专利和其它参考文献全都引于此供参考。除非另有定义，本说明书所用的所有技术和科学术语都具有本领域技术人员常规理解的含义。在有冲突的情况下，以本说明书的定义为准。
当本说明书以词头“本领域技术人员公知”、“现有技术”或其类似用语来导出材料、物质、方法、步骤、装置或部件等时，该词头导出的对象涵盖本申请提出时本领域常规使用的那些，但也包括目前还不常用，却将变成本领域公认为适用于类似目的的那些。
在本说明书的上下文中，SAPO分子筛或者SAPO分子筛催化剂的制备方法是为本领域所熟知的。
在本说明书的上下文中，反应器内催化剂的积炭量是一个平均的概念。因为在流化床反应器内，存在着反应-再生之间的催化剂循环，存在着低积炭量催化剂与高积炭量催化剂，因而必然反应器内存在多股催化剂的混合。
在本说明书的上下文中，催化剂积炭量(或者平均积碳量)的计算方法为催化剂上的积炭质量除以所述催化剂质量。催化剂上的积炭质量测定方法如下：称量0.1～1克的带碳催化剂置于高温碳分析仪中燃烧，通过红外测定燃烧生成的二氧化碳质量，从而得到催化剂上的积炭质量。为了测定反应区内的催化剂积碳量，可以从反应区的各个位置，连续或周期性引出或者直接取出等量的小份催化剂。
在没有明确指明的情况下，本说明书内所提到的所有百分数、份数、比率等都是以重量为基准的，而且压力是表压。
在本说明书的上下文中，本发明的任何两个或多个实施方式都可以任意组合，由此而形成的技术方案属于本说明书原始公开内容的一部分，同时也落入本发明的保护范围。
【实施例1】
甲醇原料(甲醇纯度95wt％)进入快速流化床反应器的反应区(以下简称流化床反应区)，与SAPO-34分子筛催化剂接触，在有效条件下生成包括乙烯、丙烯的产品，流化床反应区内的催化剂失活后形成待生催化剂。所述待生催化剂进入再生器再生，形成再生催化剂。所述再生催化剂返回到流化床反应区。所述待生催化剂与再生催化剂的积炭量之差为5wt％。流化床反应区内的气相、催化剂在反应完成后或离开所述流化床反应区后通过分离设备快速分离。所述有效条件为：反应温度450℃，反应表压为0.15MPa，以催化剂上分子筛质量计，流化床反应器内甲醇浓度大于0.1％的区域内的温度差为4℃、催化剂积炭量为1.5wt％，积炭量小于3重量％的催化剂质量占所述流化床反应器内全部催化剂质量的比例为2重量％，积炭量为3至小于5重量％的催化剂占68重量％，积炭量为5-10重量％的催化剂占23重量％。再生管路出口设有催化剂分布器，所述分布器沿流化床反应器径向水平布置，将再生催化剂均匀分布于流化床反应器反应区的径向平面上。催化剂分布器内输送介质为水蒸气。取样分析结果表明，甲醇转化率为99.98％，乙烯+丙烯碳基选择性为83.07％。
【实施例2】
甲醇原料(甲醇纯度95wt％)进入快速流化床反应区，与SAPO-34分子筛催化剂接触，在有效条件下生成包括乙烯、丙烯的产品，流化床反应区内的催化剂失活后形成待生催化剂。所述待生催化剂进入再生器再生，形成再生催化剂。所述再生催化剂返回到流化床反应区。所述待生催化剂与再生催化剂的积炭量之差为5wt％。流化床反应区内的气相、催化剂在反应完成后或离开所述流化床反应区后通过分离设备快速分离。所述有效条件为：反应温度450℃，反应表压为0.15MPa， 以催化剂上分子筛质量计，流化床反应器内甲醇浓度大于0.1％的区域内的温度差为4℃、催化剂积炭量为5.5wt％，积炭量小于3重量％的催化剂质量占所述流化床反应器内全部催化剂质量的比例为10重量％，积炭量为3至小于5重量％的催化剂占50重量％，积炭量为5-10重量％的催化剂占35重量％。再生管路出口设有催化剂分布器，所述分布器沿流化床反应器径向水平布置，将再生催化剂均匀分布于流化床反应器反应区的径向平面上。催化剂分布器内输送介质为水蒸气。取样分析结果表明，甲醇转化率为99.95％，乙烯+丙烯碳基选择性为84.13％。
【实施例3】
甲醇原料(甲醇纯度95wt％)进入快速流化床反应区，与SAPO-34分子筛催化剂接触，在有效条件下生成包括乙烯、丙烯的产品，流化床反应区内的催化剂失活后形成待生催化剂。所述待生催化剂进入再生器再生，形成再生催化剂。所述再生催化剂返回到流化床反应区。所述待生催化剂与再生催化剂的积炭量之差为5wt％。流化床反应区内的气相、催化剂在反应完成后或离开所述流化床反应区后通过分离设备快速分离。所述有效条件为：反应温度400℃，反应表压为0.05MPa，以催化剂上分子筛质量计，流化床反应器内甲醇浓度大于0.1％的区域内的温度差为9℃、催化剂积炭量为1.5wt％，积炭量小于3重量％的催化剂质量占所述流化床反应器内全部催化剂质量的比例为1.5重量％，积炭量为3至小于5重量％的催化剂占43重量％，积炭量为5-10重量％的催化剂占53重量％。再生管路出口设有催化剂分布器，所述分布器沿流化床反应器径向水平布置，将再生催化剂均匀分布于流化床反应器反应区的径向平面上。催化剂分布器内输送介质为水蒸气。取样分析结果表明，甲醇转化率为99.06％，乙烯+丙烯碳基选择性为82.56％。
【实施例4】
甲醇原料(甲醇纯度95wt％)进入快速流化床反应区，与SAPO-34分子筛催化剂接触，在有效条件下生成包括乙烯、丙烯的产品，流化床反应区内的催化剂失活后形成待生催化剂。所述待生催化剂进入再生器再生，形成再生催化剂。所述再生催化剂返回到流化床反应区。所述待生催化剂与再生催化剂的积炭量之差为6wt％。流化床反应区内 的气相、催化剂在反应完成后或离开所述流化床反应区后通过分离设备快速分离。所述有效条件为：反应温度550℃，反应表压为1.0MPa，以催化剂上分子筛质量计，流化床反应器内甲醇浓度大于0.1％的区域内的温度差为9℃、催化剂积炭量为8wt％，积炭量小于3重量％的催化剂质量占所述流化床反应器内全部催化剂质量的比例为18重量％，积炭量为3至小于5重量％的催化剂占30重量％，积炭量为5-10重量％的催化剂占48重量％。再生管路出口设有催化剂分布器，所述分布器沿流化床反应器径向水平布置，将再生催化剂均匀分布于流化床反应器反应区的径向平面上。催化剂分布器内输送介质为C4。取样分析结果表明，甲醇转化率为99.99％，乙烯+丙烯碳基选择性为85.44％。
【实施例5】
甲醇原料(甲醇纯度95wt％)进入湍动流化床反应区，与SAPO-34分子筛催化剂接触，在有效条件下生成包括乙烯、丙烯的产品，流化床反应区内的催化剂失活后形成待生催化剂。所述待生催化剂进入再生器再生，形成再生催化剂。所述再生催化剂返回到流化床反应区。所述待生催化剂与再生催化剂的积炭量之差为5wt％。流化床反应区内的气相、催化剂在反应完成后或离开所述流化床反应区后通过分离设备快速分离。所述有效条件为：反应温度480℃，反应表压为0.15MPa，以催化剂上分子筛质量计，流化床反应器内甲醇浓度大于0.1％的区域内的温度差为2℃、催化剂积炭量为4.5wt％，积炭量小于3重量％的催化剂质量占所述流化床反应器内全部催化剂质量的比例为5重量％，积炭量为3至小于5重量％的催化剂占65重量％，积炭量为5-10重量％的催化剂占25重量％。再生管路出口设有催化剂分布器，所述分布器沿流化床反应器径向水平布置，将再生催化剂均匀分布于流化床反应器反应区的径向平面上。催化剂分布器内输送介质为含氧化合物副产物。取样分析结果表明，甲醇转化率为99.93％，乙烯+丙烯碳基选择性为84.09％。
【比较例1】
按照【实施例5】所述的条件和步骤，只是流化床反应器内甲醇浓度大于0.1％的区域内的温度差为22℃。取样分析结果表明，甲醇转化 率为99.74％，乙烯+丙烯碳基选择性为81.17％。
【比较例2】
按照【实施例5】所述的条件和步骤，只是流化床反应器内甲醇浓度大于0.1％的区域内的温度差为27℃。取样分析结果表明，甲醇转化率为99.33％，乙烯+丙烯碳基选择性为80.55％。
显然，采用本发明的方法，可以达到提高低碳烯烃收率的目的，可用于低碳烯烃的工业生产中。

Claims (11)

  1. 一种在流化床反应器内转化甲醇的方法，包括使含甲醇的原料进入流化床反应器，与催化剂接触，在有效条件下生成包括乙烯、丙烯的产品；该流化床反应器包括稀相区和密相区，其特征在于，控制所述流化床反应器内稀相区中甲醇浓度大于0.1重量％(优选大于0.01重量％)的任何区域间的稀相温度差小于20℃，并且控制该流化床反应器内的密相区中甲醇浓度大于0.1重量％(优选大于0.01重量％)的任何区域间的密相温度差小于10℃。
  2. 根据权利要求1所述的方法，其特征在于，所述流化床反应器内的所述稀相温度差小于10℃，和/或所述流化床反应器内的所述密相温度差小于10℃。
  3. 根据权利要求1-2任一所述的方法，其特征在于，所述有效条件包括：以催化剂中分子筛质量计，所述流化床反应器内甲醇浓度大于0.01重量％的区域内的催化剂积炭量为1.5～10重量％，优选2～8重量％，更优选4～7重量％。
  4. 根据权利要求3所述的方法，其特征在于，以催化剂中分子筛质量计，所述流化床反应器内甲醇浓度大于0.01重量％的区域内，积炭量小于3重量％的催化剂质量占所述流化床反应器内全部催化剂质量的比例为1～20重量％，优选为1.5～10重量％，更优选为2～5重量％。
  5. 根据权利要求4所述的方法，其特征在于，以催化剂中分子筛质量计，所述流化床反应器内甲醇浓度大于0.01重量％的区域内，积炭量为3至小于5重量％的催化剂占10～70重量％，优选为15～60重量％，20～50重量％，或30～45重量％；积炭量为5-10重量％的催化剂占10～88重量％，优选为15～80重量％，20～70重量％，或30～60重量％。
  6. 根据前述权利要求中任一所述的方法，其特征在于，所述有效条件包括：反应温度400～550℃，反应压力0～1MPa。
  7. 根据前述权利要求中任一所述的方法，其中所述流化床反应器内的催化剂失活后形成待生催化剂，所述待生催化剂通过待生管路进入再生器再生，形成再生催化剂，所述再生催化剂通过再生管路返回到所述流化床反应器；其特征在于，所述待生催化剂与所述再生催化剂的积炭量之差小于7重量％，优选小于6重量％，更优选小于4重量 ％。
  8. 根据前述权利要求中任一所述的方法，其特征在于，所述催化剂活性组分为硅铝磷分子筛；所述硅铝磷分子筛例如为SAPO-18、SAPO-34、SAPO-5或其组合，优选为SAPO-34；和/或所述流化床反应器为密相、湍动或快速流态化型式。
  9. 根据前述权利要求中任一所述的方法，其特征在于，所述流化床反应器内部或/和外部设有温度调节设备。
  10. 根据前述权利要求中任一所述的方法，其特征在于，所述流化床反应器下部设置有再生管路出口，所述再生管路出口设置有催化剂分布器；所述分布器沿所述流化床反应器径向基本水平布置。
  11. 根据权利要求10所述的方法，其特征在于，所述催化剂分布器内的输送介质选自水蒸气、含氧化合物副产物、C4烃中的至少一种；所述含氧化合物副产物包括丙酮、乙醛。
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