WO2019109237A1 - 部分再生甲醇制烯烃催化剂的方法和甲醇制烯烃方法 - Google Patents

部分再生甲醇制烯烃催化剂的方法和甲醇制烯烃方法 Download PDF

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WO2019109237A1
WO2019109237A1 PCT/CN2017/114567 CN2017114567W WO2019109237A1 WO 2019109237 A1 WO2019109237 A1 WO 2019109237A1 CN 2017114567 W CN2017114567 W CN 2017114567W WO 2019109237 A1 WO2019109237 A1 WO 2019109237A1
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methanol
catalyst
olefin
reaction
deactivated
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French (fr)
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叶茂
周吉彬
张涛
张今令
赵银峰
王贤高
贾金明
唐海龙
刘中民
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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Priority to KR1020207016344A priority Critical patent/KR102400421B1/ko
Priority to US16/767,268 priority patent/US11504703B2/en
Priority to JP2020527996A priority patent/JP7008138B2/ja
Priority to PCT/CN2017/114567 priority patent/WO2019109237A1/zh
Priority to EP17934137.5A priority patent/EP3721995A4/en
Priority to RU2020122179A priority patent/RU2753348C1/ru
Priority to SG11202005199TA priority patent/SG11202005199TA/en
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    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/82—Phosphates
    • B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
    • B01J29/85—Silicoaluminophosphates [SAPO compounds]
    • 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
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
    • B01J38/06—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst using steam
    • 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
    • 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
    • C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/02—Alkenes
    • C07C11/107—Alkenes with six carbon atoms
    • 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 present application relates to a method for partially regenerating methanol to olefin catalyst and a regenerated catalyst, and belongs to the field of chemical catalysts.
  • Ethylene and propylene are important basic raw materials for the national economy and occupy an important strategic position in the development of petrochemical and chemical industries. China's ethylene production raw materials are mainly naphtha, and its cost is high.
  • Industrial methanol-to-olefin technology Starting from coal, a highly selective low-carbon olefin was successfully prepared by a fluidized bed process using a SAPO-based catalyst. However, after a certain period of reaction, the SAPO-based catalyst causes carbonization to cause deactivation, and it is necessary to carry out charcoal regeneration to restore the activity and selectivity of the catalyst.
  • the regeneration process of the methanol-to-olefin catalyst uses a mixture of nitrogen and air or water vapor and air as a regenerative feed gas, and the regeneration process is prevented by the amount of nitrogen or water vapor in the regeneration feed gas. Flying temperature or "tailing" phenomenon.
  • this method produces a large amount of greenhouse gas CO 2 , which is detrimental to environmental protection and reduces the utilization of methanol carbon atoms.
  • US06/286604 proposes a method for regenerating a catalyst by mixing air and water vapor, wherein the air to water vapor volume ratio is 1:1 and the regeneration temperature is 450 ° C to 480 ° C.
  • the charring rate is fast, the effect of the catalyst regeneration is comparable to that of the fresh agent, and the selectivity of the initial low-carbon olefin is not increased, and the effect is equivalent to complete regeneration.
  • a method of partially regenerating a methanol-to-olefin catalyst which is capable of partially and partially regenerating a deactivated methanol-to-olefin catalyst by utilizing partial carbon deposition in a steam-deactivated catalyst. It is more favorable for methanol to olefin reaction than completely regenerating the catalyst.
  • the modification and structural modification of the fresh SAPO-34 molecular sieve catalyst are performed before the MTO reaction.
  • the modification method of the shipbuilding cage in the bottle starts from the mechanism of the hydrocarbon pool, and forms a large molecule in the molecular sieve cage, which not only reduces the number of acid centers in the cage, but also reduces the cage volume, thereby shortening the MTO reaction induction period and improving the low carbon. Olefin selectivity.
  • the molecules reported in the literature that can be modified are mainly PH 3 , SiH 4 , Si 2 H 6 and B 2 H 6 .
  • the cage structure is modified by residual carbon deposition, and there are few reports and patent applications.
  • deactivated catalysts need to remove carbon deposits as much as possible for complete regeneration to achieve better catalyst performance.
  • the inventors of the present application have found through technical research that there is a technical bias in the above recognition.
  • the inventive discovery of the present application is that the methanol-to-olefin reaction, the deactivation catalyst of the methanol-to-olefin catalyst and the catalytic performance of the fully regenerated catalyst are not satisfactory, but the incompletely regenerated catalyst which retains a certain amount of carbon has better catalytic activity. It can greatly improve the selectivity of the initial low-carbon olefins and ensure the highest selectivity of the catalyst low-carbon olefins, thereby improving the overall selectivity of the low-carbon olefins.
  • the method for partially regenerating a methanol to olefin catalyst characterized in that the method comprises placing a deactivated methanol-to-olefin catalyst in a regenerator for partial regeneration reaction to obtain a regenerated catalyst;
  • At least a portion of the regenerated catalyst has a carbon deposition amount of more than 1%.
  • At least a part of the regenerated catalyst has a carbon deposition amount of 1.7% to 6%.
  • the lower limit of the carbon deposition amount of the regenerated catalyst obtained after the partial regeneration reaction in the regenerator is selected from the group consisting of 1%, 1.5%, 1.7%, 1.76%, 2%, 2.94%, 3%, 3.89%, 4 %, the upper limit is selected from 2%, 2.94%, 3%, 3.89%, 4%, 4.82%, 5.16%, 5.95%, 6%.
  • the amount of carbon accumulated in the regenerated catalyst obtained after the partial regeneration reaction in the regenerator is 2% to 6%.
  • ⁇ is the carbon content of the catalyst in terms of mass percentage
  • m 250 ° C is the mass of the catalyst when the temperature is raised to 250 ° C
  • m 900 ° C is the mass of the catalyst when the temperature is raised to 900 ° C. The heating process is completed in air.
  • water vapor is introduced into the regenerator.
  • the regeneration reaction is a reaction between the carbonaceous material on the deactivated catalyst and O 2 . Since it is equivalent to the combustion reaction of the carbonaceous material, it is difficult to control the degree of the combustion reaction, and it is difficult to obtain incompleteness.
  • the catalyst is regenerated; and the catalytic activity of the carbonaceous material on the catalyst which is not completely oxidized to CO 2 after the O 2 reaction is not high, and the selectivity for ethylene and propylene in the MTO reaction is also low.
  • an air regenerating catalyst even if the degree of reaction is controlled, is not completely regenerated, since oxygen first reacts with hydrogen in the carbon deposit to gradually convert carbon deposits into heavy components, and heavy carbon deposits react with methanol to olefins. Without catalytic performance, partial regeneration of the catalyst by air charring will cause a large change in the carbon residue properties of the catalyst. The cocatalytic effect of the regenerated catalyst during the reaction is weakened, and the selectivity of the low carbon olefin cannot reach the maximum.
  • water vapor is introduced into the regenerator without using the regeneration gas containing oxygen.
  • the regeneration reaction in the technical solution of the present application is the reaction of the carbonaceous material on the deactivated catalyst with H 2 O. .
  • the water vapor selectively reacts with the carbonaceous material, so that the properties of the carbon residue can be effectively controlled by the regeneration temperature and time, thereby further ensuring the selectivity of the low-carbon olefin in the reaction.
  • the catalyst is brought into contact with water vapor under an inert gas atmosphere, and the influence of air on the performance of the catalyst can be avoided.
  • the contact time of the water vapor introduced into the regenerator with the deactivated methanol olefin catalyst is from 10 min to 40 min.
  • the space velocity of the water vapor introduced into the regenerator is 4h -1 to 8h -1 .
  • the partial regeneration reaction is carried out at 600 ° C to 750 ° C;
  • the partial regeneration reaction is carried out at a temperature of from 710 °C to 750 °C.
  • the carbon content of the deactivated methanol to olefin catalyst is from 7% to 12%.
  • an inert gas is also introduced into the regenerator.
  • the inert gas is selected from at least one of nitrogen, helium, argon, and helium.
  • the volume fraction of oxygen in the gas phase in the regenerator is ⁇ 1%.
  • the methanol-to-olefin catalyst is subjected to a methanol-to-olefin reaction in a fluidized bed reactor, and the deactivated methanol-to-olefin catalyst is sent to a regenerator for partial regeneration reaction to obtain a regenerated catalyst as an incompletely regenerated catalyst. Incompletely regenerated catalyst It is recycled back to the fluidized bed reactor.
  • the incompletely regenerated catalyst refers to a regenerated catalyst in which a carbon deposit on the catalyst is not completely removed after the catalyst is regenerated, and a part of the carbon deposit remains on the catalyst. It may also be referred to as a partially regenerated catalyst.
  • the catalyst is a molecular sieve catalyst.
  • the methanol to olefin catalyst is a fluidized bed catalyst.
  • the catalyst is a silicoaluminophosphate molecular sieve (abbreviated as SAPO molecular sieve) catalyst.
  • SAPO molecular sieve silicoaluminophosphate molecular sieve
  • the reactor is a fluidized bed reactor.
  • an inert gas is introduced into the reactor for purging before the water vapor is introduced.
  • the inert gas is selected from at least one of argon or nitrogen.
  • a methanol to olefin process wherein the methanol to olefin reaction is carried out in a fluidized bed using a methanol to olefin catalyst, characterized in that at least a portion of the carbon content of the regenerated catalyst More than 1%.
  • the amount of carbon deposited by the regenerated catalyst is from 2% to 6%.
  • the regenerated catalyst is obtained by at least one of the above-described methods of partially regenerating methanol to an olefin catalyst.
  • the carbonization in the catalyst is partially regenerated by gasification, and the gasification products are mainly CO and H 2 , which can be recycled and reused, thereby improving the utilization ratio of methanol carbon atoms;
  • the MTO reaction of the partially regenerated catalyst with water vapor can greatly improve the selectivity of the initial low-carbon olefin and ensure the highest selectivity, thereby improving the overall selectivity of the low-carbon olefin.
  • the selectivity of the initial low carbon olefin of the fully regenerated catalyst is 62.57%, and the selectivity of the initial low carbon olefin of the partially regenerated catalyst of the present process can be controlled within the range of 63% to 83%.
  • the MTO reaction is carried out by partially regenerating the catalyst with steam.
  • the methanol of the reactant is nearly completely converted, and the conversion rate is the same as that of the fresh agent.
  • the methanol conversion rate of the partially regenerated catalyst in the method is close to 100%.
  • Fig. 1 is a view showing the results of performance test of a partially regenerated catalyst in an embodiment of the present invention.
  • FIG. 2 is a schematic view showing the results of performance test of a partially regenerated catalyst in one embodiment of the present invention.
  • Fig. 3 is a schematic view showing the results of performance test of a partially regenerated catalyst in an embodiment of the present invention.
  • Fig. 4 is a view showing the results of performance test of a partially regenerated catalyst in an embodiment of the present invention.
  • Fig. 5 is a view showing the results of performance test of a partially regenerated catalyst in an embodiment of the present invention.
  • Fig. 6 is a view showing the results of performance test of a partially regenerated catalyst in one embodiment of the present invention.
  • the methanol-to-olefin catalyst SAPO-34 used commercially in the present application was purchased from Zhengda Energy Materials (Dalian) Co., Ltd.
  • the carbon deposition amount of the catalyst is determined as follows:
  • the catalyst was heated to 250 ° C in air, the recording mass was m 250 ° C ; the catalyst was heated to 900 ° C in air, and the recording mass was m 900 ° C ; then the carbon deposition amount of the catalyst was determined by the following formula I:
  • a nitrogen gas with a flow rate of 100 mL/min is introduced into the reactor to set a temperature of the reactor heating furnace; when the temperature is raised to 700 ° C, the nitrogen gas is continuously purged for 10 minutes, and then water vapor is introduced, and the mass thereof is empty. The speed is 6h -1 and the temperature is 15min.
  • the steam is vaporized, a small amount of catalyst is taken, and the carbon deposition amount is measured. The carbon deposition amount is 5.95%.
  • the temperature is increased, the regeneration is stopped, the regeneration gas is switched to nitrogen gas, and the temperature of the furnace is lowered to 490 ° C for 20 minutes.
  • fresh agent means a methanol-to-olefin catalyst which has not been used in the examples, that is, the first use of a methanol-to-olefin catalyst.
  • a nitrogen gas with a flow rate of 100 mL/min is introduced into the reactor to set a temperature of the reactor heating furnace; when the temperature is raised to 700 ° C, the nitrogen gas is continuously purged for 10 minutes, and then water vapor is introduced, and the mass thereof is empty. The speed is 6h -1 and the temperature is 30min.
  • the steam is vaporized, a small amount of catalyst is taken, and the carbon deposition amount is measured. The carbon deposition amount is 4.82%.
  • the temperature is increased, the regeneration is stopped, the regeneration gas is switched to nitrogen gas, and the temperature of the furnace is lowered to 490 ° C for 20 minutes.
  • fresh agent means a methanol-to-olefin catalyst which has not been used in the examples, that is, the first use of a methanol-to-olefin catalyst.
  • a nitrogen gas purge flow rate of 100 mL/min was introduced into the reactor to set the temperature of the reactor heating furnace; when the temperature was raised to 750 ° C, the nitrogen gas was continuously purged for 10 minutes, and then water vapor was introduced, and the mass thereof was empty. The speed is 6h -1 and the temperature is 10min.
  • the steam is vaporized, a small amount of catalyst is taken, and the carbon deposition amount is measured. The carbon deposition amount is 5.16%.
  • the regeneration is stopped, the regeneration gas is switched to nitrogen gas, and the temperature of the furnace is lowered to 490 ° C for 20 minutes.
  • fresh agent means a methanol-to-olefin catalyst which has not been used in the examples, that is, the first use of a methanol-to-olefin catalyst.
  • a nitrogen gas purge flow rate of 100 mL/min was introduced into the reactor to set the temperature of the reactor heating furnace; when the temperature was raised to 750 ° C, the nitrogen gas was continuously purged for 10 minutes, and then water vapor was introduced, and the mass thereof was empty. The speed is 6h -1 and the temperature is 20min.
  • the steam is vaporized, a small amount of catalyst is taken, and the carbon deposition amount is measured. The carbon deposition amount is 3.89%.
  • the temperature is increased, the regeneration is stopped, the regeneration gas is switched to nitrogen gas, and the temperature of the furnace is lowered to 490 ° C for 20 minutes.
  • the "fresh agent" in the figure means a methanol-to-olefin catalyst which has not been used in the examples, i.e., the first use of a methanol-to-olefin catalyst.
  • a nitrogen gas purge flow rate of 100 mL/min was introduced into the reactor to set the temperature of the reactor heating furnace; when the temperature was raised to 750 ° C, the nitrogen gas was continuously purged for 10 minutes, and then water vapor was introduced, and the mass thereof was empty. The speed is 6h -1 and the temperature is 30min.
  • a small amount of catalyst is taken to measure the carbon deposition amount, and the carbon deposition amount is 2.94%.
  • the temperature is increased, the regeneration is stopped, the regeneration gas is switched to nitrogen gas, and the temperature of the furnace is lowered to 490 ° C for 20 minutes.
  • fresh agent means a methanol-to-olefin catalyst which has not been used in the examples, that is, the first use of a methanol-to-olefin catalyst.
  • a nitrogen gas purge flow rate of 100 mL/min was introduced into the reactor to set the temperature of the reactor heating furnace; when the temperature was raised to 750 ° C, the nitrogen gas was continuously purged for 10 minutes, and then water vapor was introduced, and the mass thereof was empty. The speed is 6h -1 and the temperature is 40min.
  • the steam is vaporized, a small amount of catalyst is taken, and the carbon deposition amount is measured. The carbon deposition amount is 1.76%.
  • the temperature is programmed to be stopped, the regeneration is stopped, the regeneration gas is switched to nitrogen gas, and the temperature of the furnace is lowered to 490 ° C for 20 minutes.
  • fresh agent means a methanol-to-olefin catalyst which has not been used in the examples, that is, the first use of a methanol-to-olefin catalyst.

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Abstract

本申请公开了一种部分再生甲醇制烯烃催化剂的方法，所述方法包括将失活的甲醇制烯烃催化剂置于再生器中进行部分再生反应，得到再生催化剂；至少一部分所述再生催化剂的积碳量超过1％。本申请公开了一种甲醇制烯烃方法，所述甲醇制烯烃反应采用甲醇制烯烃催化剂在流化床中进行，其特征在于，至少一部分的所述再生催化剂的积碳量超过1％。

Description

部分再生甲醇制烯烃催化剂的方法和甲醇制烯烃方法 技术领域
本申请涉及一种部分再生甲醇制烯烃催化剂的方法和一种再生催化剂，属于化工催化剂领域。
背景技术
乙烯、丙烯是国民经济重要的基础原料，在石化和化学工业发展中占有重要的战略地位。我国乙烯生产原料主要以石脑油为主，其成本较高。工业上甲醇制烯烃技术从煤出发，利用SAPO类催化剂，采用流化床工艺，成功制备高选择性的低碳烯烃。但SAPO类催化剂在反应一段时间后，积碳导致失活，需要进行烧炭再生，以恢复催化剂的活性和选择性。在现有技术中，甲醇制烯烃催化剂的再生过程采用氮气与空气或水蒸气与空气的混合气作为再生进料气体，通过调节再生进料气中氮气或者水蒸气的量，防止再生过程出现“飞温”或者“尾燃”现象。但是，这种方法产生大量的温室气体CO2，不利于环境保护，而且降低了甲醇碳原子的利用率。
US06/286604提出一种空气与水蒸气混合再生催化剂方法，其中空气与水蒸气体积比为1:1，再生温度450℃-480℃。此方法中由于空气存在，烧炭速率很快，催化剂再生后效果与新鲜剂相当，并没有增加初始低碳烯烃的选择性，其作用相当于完全再生。
发明内容
根据本发明的一个方面，提供一种部分再生甲醇制烯烃催化剂的方法，该方法能够利用水蒸气气化失活催化剂中的部分积碳，快速高效地将失活的甲醇制烯烃催化剂部分再生，比完全彻底再生催化剂更有利于甲醇制烯烃反应。
现有技术中，本领域技术人员的普遍认识是：在MTO反应之前通过对新鲜SAPO-34分子筛催化剂进行改性和结构修饰，如金属杂原子改性、瓶中造船笼内修饰法等，来提高SAPO-34催化剂的催化 性能。其中瓶中造船笼内修饰法从烃池机理出发，在分子筛笼内形成一个体积较大的分子，既降低笼内的酸性中心数目，又缩小笼体积，从而缩短MTO反应诱导期和提高低碳烯烃选择性。文献中报道可以修饰笼的分子主要有PH3，SiH4、Si2H6和B2H6。但对于从失活催化剂部分再生的角度出发，通过残留积碳来修饰笼结构，鲜有文献报道和专利申请。结合目前工业生产中，失活催化剂需要尽可能的清除积碳，进行完全再生，才能获得更好的催化剂性能。但本申请发明人通过创造性的研究，发现上述认识存在技术偏见。本申请创造性的发现，对于甲醇制烯烃反应，甲醇制烯烃催化剂的失活催化剂和完全再生催化剂的催化性能均不理想，反倒是保留一定积碳量的不完全再生催化剂具有更好的催化活性，能够大幅度提高初始低碳烯烃的选择性，并保证催化剂低碳烯烃的最高选择性，从而提高低碳烯烃的整体选择性。
所述的部分再生甲醇制烯烃催化剂的方法，其特征在于，所述方法包括将失活的甲醇制烯烃催化剂置于再生器中进行部分再生反应，得到再生催化剂；
至少一部分所述再生催化剂的积碳量超过1％。
进一步优选地，再生器中进行部分再生反应后得到的所述再生催化剂中，至少一部分所述再生催化剂的积碳量为1.7％～6％。
优选地，再生器中进行部分再生反应后得到的所述再生催化剂的积碳量范围下限选自1％、1.5％、1.7％、1.76％、2％、2.94％、3％、3.89％、4％，上限选自2％、2.94％、3％、3.89％、4％、4.82％、5.16％、5.95％、6％。
进一步优选地，再生器中进行部分再生反应后得到的所述再生催化剂的积碳量为2％～6％。
本申请中，催化剂的积碳量ω的计算公式为如下式I所示：
积碳量ω＝(m250℃-m900℃)/m250℃×100％   式I
式I中，ω为以质量百分比计的催化剂的积碳量，m250℃为升温到250℃时催化剂的质量，m900℃为升温到900℃时催化剂的质量。所述升温过程在空气中完成。
优选地，所述部分再生反应中，向再生器中通入水蒸气。
若采用空气或氧气通入再生器中，再生反应为失活催化剂上的积碳物质与O2反应，由于其相当于是积碳物质的燃烧反应，不仅难以控制燃烧反应的程度，难以得到不完全再生催化剂；而且O2反应后未完全氧化为CO2的催化剂上的积碳物质的催化活性不高，进行MTO反应乙烯和丙烯选择性也较低。
具体而言，使用空气再生催化剂，即使控制了反应程度，未完全再生，由于氧气首先与积碳中的氢进行反应，使积碳逐渐向重组分转变，而重组分积碳对甲醇制烯烃反应无催化性能，所以通过空气烧炭对催化剂进行部分再生，会使催化剂残炭性质发生较大变化，再生催化剂在反应过程中共催化作用减弱，低碳烯烃选择性不能达到最大值。
作为本申请的一个优选的实施方式，向再生器中通入水蒸气，而不用含氧气的再生气，本申请的技术方案中的再生反应是失活催化剂上的积碳物质与H2O的反应。再生过程中，水蒸气有选择性地和积碳物质进行反应，使得残炭的性质可以通过再生温度和时间有效进行控制，从而进一步保证反应中低碳烯烃的选择性。本申请的技术方案中在惰性气体环境下使催化剂与水蒸气接触，可以避免空气对催化剂性能的影响。
进一步优选地，向再生器中通入的水蒸气与失活的甲醇制烯烃催化剂的接触时间为10min～40min。
进一步优选地，所述向再生器中通入水蒸气的空速为4h-1～8h-1。
优选地，所述部分再生反应在600℃～750℃的条件下进行；
进一步优选地，所述部分再生反应在710℃～750℃的条件下进行。
优选地，所述失活的甲醇制烯烃催化剂的积碳量为7％～12％。
优选地，还向再生器中通入非活性气体。
所述非活性气体选自氮气、氦气、氩气、氖气中的至少一种。
进一步优选地，所述部分再生反应中，所述再生器中的气相的氧气体积百分含量≤1％。
优选地，所述甲醇制烯烃催化剂在流化床反应器中进行甲醇制烯烃反应，将失活的甲醇制烯烃催化剂输送至再生器中进行部分再生反应，得到再生催化剂为不完全再生催化剂，将所述不完全再生催化剂 循环回所述流化床反应器。
本申请中，所述不完全再生催化剂，是指催化剂再生后，催化剂上的积碳不完全清除，催化剂上还保留部分积碳的再生催化剂。也可称为部分再生催化剂。
优选地，所述催化剂是分子筛催化剂。
优选地，所述甲醇制烯烃催化剂为流化床催化剂。
优选地，所述催化剂是磷酸硅铝分子筛(简写为SAPO分子筛)催化剂。
优选地，所述反应器是流化床反应器。
优选地，在通入水蒸气前先向反应器内通入惰性气体进行吹扫。优选地，所述惰性气体选自氩气或氮气中的至少一种。
根据本发明的另一个方面，提供了一种甲醇制烯烃方法，所述甲醇制烯烃反应采用甲醇制烯烃催化剂在流化床中进行，其特征在于，至少一部分的所述再生催化剂的积碳量超过1％。
优选地，所述再生催化剂的积碳量为2％～6％。
优选地，所述再生催化剂通过上述的部分再生甲醇制烯烃催化剂的方法中的至少一种得到。
本申请能产生的有益效果包括：
1)采用水蒸气作为再生气对催化剂中的积炭进行气化部分再生，其气化产物以CO、H2为主，可以循环再次利用，提高了甲醇碳原子的利用率；
2)由于水蒸气气化速率较慢，有利于催化剂残炭量的控制，水蒸气气化积碳反应需在催化剂活性位附近，从而有选择性地消除积炭；
3)用水蒸气部分再生的催化剂进行MTO反应，能够大幅度提高初始低碳烯烃的选择性，并保证其最高选择性，从而提高低碳烯烃的整体选择性。完全再生催化剂的初始低碳烯烃的选择性为62.57％，本方法部分再生催化剂的初始低碳烯烃的选择性可控制在63％-83％范围之内。
4)用水蒸气部分再生的催化剂进行MTO反应，反应物甲醇接近完全转化，转化率与新鲜剂相同，本方法部分再生催化剂的甲醇转化率接近100％。
附图说明
图1为本发明的一个实施方式中部分再生催化剂的性能测试结果示意图。
图2为本发明的一个实施方式中部分再生催化剂的性能测试结果示意图。
图3为本发明的一个实施方式中部分再生催化剂的性能测试结果示意图。
图4为本发明的一个实施方式中部分再生催化剂的性能测试结果示意图。
图5为本发明的一个实施方式中部分再生催化剂的性能测试结果示意图。
图6为本发明的一个实施方式中部分再生催化剂的性能测试结果示意图。
具体实施方式
下面结合实施例详述本申请，但本申请并不局限于这些实施例。
本申请中商业所用甲醇制烯烃催化剂SAPO-34购买自正大能源材料(大连)有限公司。
催化剂的积碳量测定方法如下：
将催化剂在空气中升温至250℃，记录质量为m250℃；再将催化剂在空气中升温至900℃，记录质量为m900℃；则催化剂的积碳量有下式I确定：
积碳量ω＝(m250℃-m900℃)/m250℃×100％   式I
实施例1
将4g商业所用甲醇制烯烃催化剂SAPO-34装填到固定流化床反 应器中，进行甲醇制烯烃的反应，反应原料为浓度80wt％的甲醇水溶液，反应温度为490℃，压力为0.1MPa，空速为2.1h-1。催化剂失活后，测定失活催化剂的积碳量，为9.18％。
催化剂失活后，向反应器内通入流量100mL/min的氮气气体吹扫，设置反应器加热炉温度；待温度升至700℃时，氮气继续吹扫10min，然后通入水蒸气，其质量空速为6h-1，恒温15min。当水蒸气气化结束后取少量催化剂，进行积碳量测定，积碳量为5.95％，待程序升温结束停止再生，将再生气切换成氮气气体，加热炉温度降至490℃时保持20min，待温度稳定后通入浓度为80wt％的甲醇水溶液，空速为2.1h-1，压力为0.1MPa开始甲醇制烯烃评价反应，再生后催化剂的甲醇转化率和烯烃的选择性见图1。图中“新鲜剂”是指实施例中没有使用过的甲醇制烯烃催化剂，即首次用于甲醇制烯烃催化剂。
实施例2
将4g商业所用甲醇制烯烃催化剂SAPO-34装填到固定流化床反应器中，进行甲醇制烯烃的反应，反应原料为浓度80wt％的甲醇水溶液，反应温度为490℃，压力为0.1MPa，空速为2.1h-1。催化剂失活后，测定失活催化剂的积碳量，为11.88％。
催化剂失活后，向反应器内通入流量100mL/min的氮气气体吹扫，设置反应器加热炉温度；待温度升至700℃时，氮气继续吹扫10min，然后通入水蒸气，其质量空速为6h-1，恒温30min。当水蒸气气化结束后取少量催化剂，进行积碳量测定，积碳量为4.82％，待程序升温结束停止再生，将再生气切换成氮气气体，加热炉温度降至490℃时保持20min，待温度稳定后通入浓度为80wt％的甲醇水溶液，空速为2.1h-1，压力为0.1MPa开始甲醇制烯烃评价反应，再生后催化剂的甲醇转化率和烯烃的选择性见图2。图中“新鲜剂”是指实施例中没有使用过的甲醇制烯烃催化剂，即首次用于甲醇制烯烃催化剂。
实施例3
将4g商业所用甲醇制烯烃催化剂SAPO-34装填到固定流化床反应器中，进行甲醇制烯烃的反应，反应原料为浓度80wt％的甲醇水溶液，反应温度为490℃，压力为0.1MPa，空速为2.1h-1。催化剂失活后，测定失活催化剂的积碳量，为7.08％
催化剂失活后，向反应器内通入流量100mL/min的氮气气体吹扫，设置反应器加热炉温度；待温度升至750℃时，氮气继续吹扫10min，然后通入水蒸气，其质量空速为6h-1，恒温10min。当水蒸气气化结束后取少量催化剂，进行积碳量测定，积碳量为5.16％，待程序升温结束停止再生，将再生气切换成氮气气体，加热炉温度降至490℃时保持20min，待温度稳定后通入浓度为80wt％的甲醇水溶液，空速为2.1h-1，压力为0.1MPa开始甲醇制烯烃评价反应，再生后催化剂的甲醇转化率和烯烃的选择性见图3。图中“新鲜剂”是指实施例中没有使用过的甲醇制烯烃催化剂，即首次用于甲醇制烯烃催化剂。
实施例4
将4g商业所用甲醇制烯烃催化剂SAPO-34装填到固定流化床反应器中，进行甲醇制烯烃的反应，反应原料为浓度80wt％的甲醇水溶液，反应温度为490℃，压力为0.1MPa，空速为2.1h-1。催化剂失活后，测定失活催化剂的积碳量，为9.18％。
催化剂失活后，向反应器内通入流量100mL/min的氮气气体吹扫，设置反应器加热炉温度；待温度升至750℃时，氮气继续吹扫10min，然后通入水蒸气，其质量空速为6h-1，恒温20min。当水蒸气气化结束后取少量催化剂，进行积碳量测定，积碳量为3.89％，待程序升温结束停止再生，将再生气切换成氮气气体，加热炉温度降至490℃时保持20min，待温度稳定后通入浓度为80wt％的甲醇水溶液，空速为2.1h-1，压力为0.1MPa开始甲醇制烯烃评价反应，再生后催化剂的甲醇转化率和烯烃的选择性见图4。图中“新鲜剂”是指实施例中没有使用过的甲醇制烯烃催化剂，即首次用于甲醇制烯烃催化 剂。
实施例5
将4g商业所用甲醇制烯烃催化剂SAPO-34装填到固定流化床反应器中，进行甲醇制烯烃的反应，反应原料为浓度80wt％的甲醇水溶液，反应温度为490℃，压力为0.1MPa，空速为2.1h-1。催化剂失活后，测定失活催化剂的积碳量，为9.18％。
催化剂失活后，向反应器内通入流量100mL/min的氮气气体吹扫，设置反应器加热炉温度；待温度升至750℃时，氮气继续吹扫10min，然后通入水蒸气，其质量空速为6h-1，恒温30min。当水蒸气气化结束后取少量催化剂，进行积碳量测定，积碳量为2.94％，待程序升温结束停止再生，将再生气切换成氮气气体，加热炉温度降至490℃时保持20min，待温度稳定后通入浓度为80wt％的甲醇水溶液，空速为2.1h-1，压力为0.1MPa开始甲醇制烯烃评价反应，再生后催化剂的甲醇转化率和烯烃的选择性见图5。图中“新鲜剂”是指实施例中没有使用过的甲醇制烯烃催化剂，即首次用于甲醇制烯烃催化剂。
实施例6
将4g商业所用甲醇制烯烃催化剂SAPO-34装填到固定流化床反应器中，进行甲醇制烯烃的反应，反应原料为浓度80wt％的甲醇水溶液，反应温度为490℃，压力为0.1MPa，空速为2.1h-1。催化剂失活后，测定失活催化剂的积碳量，为9.18％。
催化剂失活后，向反应器内通入流量100mL/min的氮气气体吹扫，设置反应器加热炉温度；待温度升至750℃时，氮气继续吹扫10min，然后通入水蒸气，其质量空速为6h-1，恒温40min。当水蒸气气化结束后取少量催化剂，进行积碳量测定，积碳量为1.76％，待程序升温结束停止再生，将再生气切换成氮气气体，加热炉温度降至490℃时保持20min，待温度稳定后通入浓度为80wt％的甲醇水溶液，空速为2.1h-1，压力为0.1MPa开始甲醇制烯烃评价反应，再生后催 化剂的甲醇转化率和烯烃的选择性见图6。图中“新鲜剂”是指实施例中没有使用过的甲醇制烯烃催化剂，即首次用于甲醇制烯烃催化剂。
以上所述，仅是本申请的几个实施例，并非对本申请做任何形式的限制，虽然本申请以较佳实施例揭示如上，然而并非用以限制本申请，任何熟悉本专业的技术人员，在不脱离本申请技术方案的范围内，利用上述揭示的技术内容做出些许的变动或修饰均等同于等效实施案例，均属于技术方案范围内。

Claims (10)

  1. 一种部分再生甲醇制烯烃催化剂的方法，其特征在于，所述方法包括将失活的甲醇制烯烃催化剂置于再生器中进行部分再生反应，得到再生催化剂；
    至少一部分所述再生催化剂的积碳量超过1％。
  2. 根据权利要求1所述的部分再生甲醇制烯烃催化剂的方法，其特征在于，再生器中进行部分再生反应后得到的所述再生催化剂的积碳量为1.7％～6％。
  3. 根据权利要求1所述的部分再生甲醇制烯烃催化剂的方法，其特征在于，所述部分再生反应中，向再生器中通入水蒸气，水蒸气与失活的甲醇制烯烃催化剂的接触时间为10min～40min。
  4. 根据权利要求3所述的部分再生甲醇制烯烃催化剂的方法，其特征在于，所述向再生器中通入水蒸气的空速为4h-1～8h-1。
  5. 根据权利要求1所述的部分再生甲醇制烯烃催化剂的方法，其特征在于，所述部分再生反应在600℃～750℃的条件下进行；
    优选地，所述部分再生反应在710℃～750℃的条件下进行。
  6. 根据权利要求1所述的部分再生甲醇制烯烃催化剂的方法，其特征在于，所述失活的甲醇制烯烃催化剂的积碳量为7％～12％。
  7. 根据权利要求1所述的部分再生甲醇制烯烃催化剂的方法，其特征在于，还向再生器中通入非活性气体；
    所述非活性气体选自氮气、氦气、氩气、氖气中的至少一种；
    所述部分再生反应中，所述再生器中气相的氧气体积百分含量≤1％。
  8. 根据权利要求1所述的部分再生甲醇制烯烃催化剂的方法，其特征在于，所述甲醇制烯烃催化剂在流化床反应器中进行甲醇制烯烃反应，将失活的甲醇制烯烃催化剂输送至再生器中进行部分再生反应，得到再生催化剂为不完全再生催化剂，将所述不完全再生催化剂循环回所述流化床反应器；
    所述甲醇制烯烃催化剂含有磷酸硅铝分子筛；
    所述甲醇制烯烃催化剂为流化床催化剂。
  9. 一种甲醇制烯烃方法，所述甲醇制烯烃反应采用甲醇制烯烃催化剂在流化床中进行，其特征在于，至少一部分的所述再生催化剂的积碳量超过1％。
  10. 根据权利要求9所述的甲醇制烯烃方法，其特征在于，所述再生催化剂通过权利要求1至7任一项所述的部分再生甲醇制烯烃催化剂的方法中的至少一种得到。
PCT/CN2017/114567 2017-12-05 2017-12-05 部分再生甲醇制烯烃催化剂的方法和甲醇制烯烃方法 Ceased WO2019109237A1 (zh)

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PCT/CN2017/114567 WO2019109237A1 (zh) 2017-12-05 2017-12-05 部分再生甲醇制烯烃催化剂的方法和甲醇制烯烃方法
EP17934137.5A EP3721995A4 (en) 2017-12-05 2017-12-05 PROCESS FOR PARTIAL REGENERATION OF METHANOL TO OLEFIN CATALYST AND PROCESS FOR CONVERTING METHANOL TO OLEFIN
RU2020122179A RU2753348C1 (ru) 2017-12-05 2017-12-05 Способ частичной регенерации катализатора превращения метанола в олефин и способ превращения метанола в олефин
SG11202005199TA SG11202005199TA (en) 2017-12-05 2017-12-05 Method for partially regenerating methanol to olefin catalyst and methanol to olefin process

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2023528820A (ja) * 2020-10-16 2023-07-06 中国科学院大▲連▼化学物理研究所 再生装置、軽オレフィンを調製する装置およびその応用

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022077452A1 (zh) * 2020-10-16 2022-04-21 中国科学院大连化学物理研究所 流化床反应器、装置以及含氧化合物制备低碳烯烃的方法
CN115304442A (zh) * 2021-05-08 2022-11-08 国家能源投资集团有限责任公司 甲醇制c2-c3烯烃的方法和装置
CN117185308B (zh) * 2022-06-01 2025-10-31 中国石油化工股份有限公司 一种sapo-34分子筛及其制备方法和应用

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6286604B1 (en) 2000-05-09 2001-09-11 Ren-Sheng Ou Powerless automatic and/or manual fire-extinguishing device
CN101941875A (zh) * 2009-07-06 2011-01-12 中国石油化工股份有限公司上海石油化工研究院 增产低碳烯烃的方法
CN102276393A (zh) * 2010-06-11 2011-12-14 中国石油化工股份有限公司 甲醇制烯烃反应-再生系统中再生催化剂返回反应器的方法
CN102463138A (zh) * 2010-11-17 2012-05-23 中国石油化工股份有限公司 Sapo-34催化剂的两段再生方法
CN104672040A (zh) * 2013-12-03 2015-06-03 中国科学院大连化学物理研究所 一种含氧化合物制低碳烯烃的方法及其使用的设备

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6482999B2 (en) * 1999-02-17 2002-11-19 Exxonmobil Chemical Patents, Inc. Method for improving light olefin selectivity in an oxygenate conversion reaction
US7550403B2 (en) 2005-06-30 2009-06-23 Uop Llc Methods for recovering activity of molecular sieve catalysts
US20070037692A1 (en) 2005-08-10 2007-02-15 Beech James H Jr Method for stabilizing catalyst activity during MTO unit operation
EP2022565A1 (en) * 2007-07-06 2009-02-11 Casale Chemicals S.A. Process for preparing silicoaluminoposphate (SAPO) molecular sieves, catalysts containing said sieves and catalytic dehydration processes using said catalysts
CN101811072B (zh) * 2009-02-19 2011-12-21 中国石油化工股份有限公司 甲醇制烯烃反应过程中控制再生的方法
JP5499918B2 (ja) * 2009-06-05 2014-05-21 三菱化学株式会社 触媒の再生方法
CN101844089A (zh) * 2010-05-25 2010-09-29 兆威兴业有限公司 对甲醇或二甲醚制备低碳烯烃用催化剂部分再生的方法
RU2522576C1 (ru) * 2013-04-10 2014-07-20 Ассоциация делового сотрудничества в области передовых комплексных технологий "АСПЕКТ" Способ каталитического пиролиза хлористого метила
KR101494229B1 (ko) * 2013-05-01 2015-02-17 한국화학연구원 중간생성물의 실시간 모니터링을 통한 메탄올로부터 경질올레핀 제조용 순환유동층 공정의 효율적 운전
EP3078652B1 (en) 2013-12-03 2018-07-18 Dalian Institute Of Chemical Physics, Chinese Academy of Sciences Method for preparing a light olefin using an oxygen-containing compound

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6286604B1 (en) 2000-05-09 2001-09-11 Ren-Sheng Ou Powerless automatic and/or manual fire-extinguishing device
CN101941875A (zh) * 2009-07-06 2011-01-12 中国石油化工股份有限公司上海石油化工研究院 增产低碳烯烃的方法
CN102276393A (zh) * 2010-06-11 2011-12-14 中国石油化工股份有限公司 甲醇制烯烃反应-再生系统中再生催化剂返回反应器的方法
CN102463138A (zh) * 2010-11-17 2012-05-23 中国石油化工股份有限公司 Sapo-34催化剂的两段再生方法
CN104672040A (zh) * 2013-12-03 2015-06-03 中国科学院大连化学物理研究所 一种含氧化合物制低碳烯烃的方法及其使用的设备

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP3721995A4

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2023528820A (ja) * 2020-10-16 2023-07-06 中国科学院大▲連▼化学物理研究所 再生装置、軽オレフィンを調製する装置およびその応用
JP7393115B2 (ja) 2020-10-16 2023-12-06 中国科学院大▲連▼化学物理研究所 再生装置、軽オレフィンを調製する装置およびその応用
US12296324B2 (en) 2020-10-16 2025-05-13 Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences Regeneration device, device for preparing low-carbon olefins, and use thereof

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