技术领域technical field
本发明涉及一种不存在氢的情况下烃油的催化转化方法，更具体地说，涉及一种轻质烃油催化转化生产低碳烯烃的方法。The invention relates to a method for catalytic conversion of hydrocarbon oil in the absence of hydrogen, in particular to a method for catalytic conversion of light hydrocarbon oil to produce light olefins.
背景技术Background technique
乙烯是石油化学工业最重要的基础原料之一，通过乙烯聚合、与苯的烷基化以及与水、氧、卤素的加成反应，可以得到一系列极有价值的衍生物。世界乙烯工业继续保持着稳步发展的态势。目前，世界上约98％的乙烯来自于管式炉蒸汽裂解技术，在乙烯生产原料中，石脑油占46％，乙烷占34％。Ethylene is one of the most important basic raw materials in the petrochemical industry. Through ethylene polymerization, alkylation with benzene, and addition reaction with water, oxygen, and halogen, a series of extremely valuable derivatives can be obtained. The world ethylene industry continues to maintain a steady development trend. At present, about 98% of the world's ethylene comes from tube furnace steam cracking technology. Among the raw materials for ethylene production, naphtha accounts for 46% and ethane accounts for 34%.
丙烯是最重要的烯烃之一，用量仅次于乙烯。丙烯最大用量的衍生物是聚丙烯，占全球丙烯用量的61％。2005年，全球大约62％丙烯来自蒸汽裂解制乙烯的联产，34％丙烯来自炼厂催化裂化装置副产，还有4％丙烯来自丙烷脱氢和乙烯-丁烯易位反应。Propylene is one of the most important olefins, second only to ethylene in consumption. The derivative of propylene with the largest amount is polypropylene, which accounts for 61% of the global propylene consumption. In 2005, about 62% of the world's propylene came from the co-production of steam cracking to ethylene, 34% of the propylene came from the by-product of the catalytic cracking unit of the refinery, and 4% of the propylene came from the propane dehydrogenation and ethylene-butene metathesis reaction.
目前，蒸汽裂解技术已日臻完善，并且是大量消耗能源的过程，又受使用而高温材质的局限，进一步改进的潜力已很小。烃类蒸汽裂解生产的乙烯和丙烯的产量很大，微小收率的提高以及微小的原料和能源的节省都将带来可观的经济效益。为了提高裂解过程烯烃的选择性，降低裂解反应温度，进一步增加乙烯和丙烯的收率，通过提高原料的多样性，开发了多种新的乙烯生产技术，如催化裂解制低碳烯烃技术、甲烷氧化偶联技术、乙烷氧化脱氢技术、天然气经甲醇或二甲醚制烯烃技术等，其中催化裂解制烯烃技术与蒸汽裂解技术相比，具有能降低裂解温度，提高乙烯和丙烯收率和裂解反应选择性、节省能量的优点，从而成为极具吸引力的技术。At present, steam cracking technology has been perfected day by day, and it is a process that consumes a lot of energy, and is limited by the high-temperature materials used, so the potential for further improvement is very small. The output of ethylene and propylene produced by steam cracking of hydrocarbons is large, and the slight increase in yield and the small saving of raw materials and energy will bring considerable economic benefits. In order to improve the selectivity of olefins in the cracking process, reduce the cracking reaction temperature, and further increase the yield of ethylene and propylene, by increasing the diversity of raw materials, a variety of new ethylene production technologies have been developed, such as catalytic cracking technology for producing low-carbon olefins, methane Oxidative coupling technology, ethane oxidative dehydrogenation technology, natural gas through methanol or dimethyl ether to olefins technology, etc. Among them, the catalytic cracking olefins technology has the advantages of lowering the cracking temperature and increasing the yield of ethylene and propylene compared with the steam cracking technology. The selectivity of the cleavage reaction and the advantages of saving energy make it an attractive technology.
CN1406253A公开一种流化床催化裂化过程制备丙烯的方法，将石脑油流引入到由反应区、汽提区、催化剂再生区和分馏区组成的工艺装置中。使石脑油原料在反应区与催化剂接触，所述催化剂含有约10～50重％的平均孔径低于约0.7nm的结晶沸石，并且反应条件包括：温度约500～650℃，烃分压为10～40psia。反应区上部实现油气与催化剂分离，并使催化剂颗粒通过汽提区，然后进入催化剂再生区。在汽提区用蒸汽汽提挥发物，催化剂颗粒送到催化剂再生区，在此将催化剂上的焦炭焚烧掉，然后催化剂循环到反应区。从反应区得到的顶产品被送到分馏区，在此回收C3产品流，而富C4和/或C5烯烃的物流循环到汽提区。CN1406253A discloses a method for preparing propylene through a fluidized catalytic cracking process. The naphtha stream is introduced into a process unit composed of a reaction zone, a stripping zone, a catalyst regeneration zone and a fractionation zone. The naphtha feedstock is contacted in a reaction zone with a catalyst comprising about 10 to 50% by weight of crystalline zeolites having an average pore size of less than about 0.7 nm, and the reaction conditions include a temperature of about 500 to 650°C and a hydrocarbon partial pressure of 10～40psia. The upper part of the reaction zone realizes the separation of oil and gas from the catalyst, and the catalyst particles pass through the stripping zone, and then enter the catalyst regeneration zone. The volatiles are stripped with steam in the stripping zone, the catalyst particles are sent to the catalyst regeneration zone where the coke on the catalyst is burned off, and the catalyst is recycled to the reaction zone. The overhead product from the reaction zone is sent to the fractionation zone where a C3 product stream is recovered, while the C4 and/or C5 olefin-rich stream is recycled to the stripping zone.
CN101279881A公开了一种催化裂解石脑油生产乙烯和丙烯的方法，该发明通过采用以C4～C10烃组成的石脑油为原料，原料烃汽化后，先与惰性气体混合，其中惰性气体与石脑油的摩尔比大于0～5.0∶1，在反应温度为580～750℃，反应压力(以表压计)大于0～0.5MPa，重量空速0.5～3h-1，水/石脑油重量比0～5∶1的条件下，原料混合气与催化剂接触反应生成乙烯和丙烯，其中所用催化剂选自ZSM-5/丝光沸石共生分子筛、ZSM-5/β沸石共生分子筛或ZSM-5/Y沸石共生分子筛中至少一种的技术方案，主要解决石脑油催化裂解制乙烯丙烯反应中催化剂因结焦导致的寿命较短、须耗用大量水蒸气的问题。CN101279881A discloses a method for catalytically cracking naphtha to produce ethylene and propylene. The invention adopts naphtha composed of C4-C10 hydrocarbons as a raw material. After the raw material hydrocarbon is vaporized, it is first mixed with an inert gas. The molar ratio of naphtha is greater than 0-5.0:1, the reaction temperature is 580-750°C, the reaction pressure (in gauge pressure) is greater than 0-0.5MPa, the weight space velocity is 0.5-3h-1 , the water/naphtha weight Under the condition of ratio 0～5:1, the mixed gas of raw material is contacted with catalyst to generate ethylene and propylene, wherein the catalyst used is selected from ZSM-5/mordenite symbiotic molecular sieve, ZSM-5/beta zeolite symbiotic molecular sieve or ZSM-5/Y The technical solution of at least one of the zeolite symbiotic molecular sieves mainly solves the problems of short catalyst life due to coking and the consumption of a large amount of water vapor in the reaction of naphtha catalytic cracking to ethylene propylene.
CN1958731A公开了一种催化热裂解制取低碳烯烃方法。将包含石脑油、轻柴油和加氢尾油的石油烃裂解原料，通过上下串联的两个装填不同催化剂a和b的催化剂床层，进行催化裂解反应，得到低碳数烯烃。优选采用双反应器双催化剂床层工艺，将两段固定床反应器串联；或者采用单反应器双催化剂床层工艺，在同一固定床反应器中装填两催化剂床层。该发明的方法可以提高原料的转化率，并且提高反应的选择性，增加目的产物(乙烯和丙烯)的收率。CN1958731A discloses a method for preparing low-carbon olefins by catalytic thermal cracking. Petroleum hydrocarbon cracking raw materials including naphtha, light diesel oil and hydrogenated tail oil are subjected to catalytic cracking reaction through two catalyst beds loaded with different catalysts a and b in series up and down to obtain low carbon number olefins. It is preferred to adopt the dual-reactor dual-catalyst bed process, and connect two fixed-bed reactors in series; or adopt the single-reactor dual-catalyst bed process, and fill two catalyst beds in the same fixed-bed reactor. The method of the invention can increase the conversion rate of raw materials, increase the selectivity of the reaction, and increase the yield of target products (ethylene and propylene).
CN1566272A公开一种利用轻质石油馏分催化转化生产乙烯和丙烯的方法，是将富含烯烃的轻质石油馏分在主反应区内与热的五元环高硅沸石催化剂接触、并在催化转化条件下反应；分离反应产物和待生催化剂；反应产物由主反应区引出后进一步分离为富含乙烯、丙烯的C4以下馏分和C4及C4以上馏分；待生催化剂经汽提后进入再生器，在含氧气体存在下烧焦再生；热的再生催化剂先进入预反应区内与来自主反应区的上述C4及C4以上馏分接触、反应，所生成的油剂混合物返回主反应区循环使用。CN1566272A discloses a method for producing ethylene and propylene by catalytic conversion of light petroleum fractions, which is to contact the light petroleum fractions rich in olefins with a hot five-membered ring silicalite catalyst in the main reaction zone, and under catalytic conversion conditions Down reaction; separation of reaction product and raw catalyst; the reaction product is further separated into fractions below C4 and fractions above C4 and above C4 rich in ethylene and propylene after being drawn out from the main reaction zone; the raw catalyst enters the regenerator after being stripped, and is Coke regeneration in the presence of oxygen-containing gas; the hot regenerated catalyst first enters the pre-reaction zone to contact and react with the above-mentioned C4 and above C4 fractions from the main reaction zone, and the resulting oil mixture returns to the main reaction zone for recycling.
由于催化裂解工艺的裂化反应转化率高，反应温度高，裂化反应热大，在反应方面需要的热量较常规催化裂化或其它催化转化方法要多，自身裂化生成的焦炭往往不能满足反应-再生系统自身热平衡的需求。上述现有技术提出了通过催化裂化反应过程将石油烃原料转化为低碳烯烃的方法和催化剂，但未能解决轻质烃油裂化过程中反应热不足的问题。Due to the high conversion rate of the cracking reaction of the catalytic cracking process, the high reaction temperature, and the high heat of the cracking reaction, the heat required for the reaction is more than that of conventional catalytic cracking or other catalytic conversion methods, and the coke generated by its own cracking often cannot meet the requirements of the reaction-regeneration system. own heat balance needs. The above-mentioned prior art proposes methods and catalysts for converting petroleum hydrocarbon raw materials into light olefins through a catalytic cracking reaction process, but fails to solve the problem of insufficient reaction heat in the cracking process of light hydrocarbon oils.
发明内容Contents of the invention
本发明的目的是提供一种节省能耗、选择性好的轻质烃油催化裂化生产低碳烯烃，即乙烯和丙烯的方法。The purpose of the present invention is to provide a method for producing light olefins, namely ethylene and propylene, by catalytic cracking of light hydrocarbon oil with low energy consumption and good selectivity.
一种带换热的轻质烃油催化转化方法，包括：A method for catalytic conversion of light hydrocarbon oil with heat exchange, comprising:
轻质烃油原料与来自提升管反应器的高温反应油气换热到200-550℃后，进入提升管反应器底部，与再生催化剂接触进行催化裂解反应同时向上流动，提升管反应器出口的反应油气和待生催化剂进入旋风分离器进行气固分离，分离出的反应油气引出装置，与轻质原料油换热后进一步分离得到乙烯、丙烯、C2～C3烷烃、C4烃馏份及其他产物；分离出的待生催化剂经汽提后进入催化剂再生器中，含氧气体与来自催化剂再生器的高温烟气换热到200-400℃后引入催化剂再生器，待生催化剂与氧气接触烧焦再生，恢复活性的再生催化剂返回反应器中循环使用，所述的提升管反应器设置于催化剂再生器内部并贯穿催化剂再生器，所述的提升管反应器出口连通旋风分离器，旋风分离器的气相出口经集气室连通后续分离系统，旋风分离器固相出口经汽提段连通催化剂再生器内部，所述的汽提段上部不设置沉降器。The light hydrocarbon oil raw material and the high-temperature reaction oil gas from the riser reactor exchange heat to 200-550°C, enter the bottom of the riser reactor, contact with the regenerated catalyst for catalytic cracking reaction and flow upward at the same time, the reaction at the outlet of the riser reactor Oil gas and raw catalyst enter the cyclone separator for gas-solid separation, and the separated reaction oil gas extraction device is further separated after heat exchange with light raw material oil to obtain ethylene, propylene, C2-C3 alkanes, C4 hydrocarbon fractions and other products; The separated raw catalyst enters the catalyst regenerator after being stripped, and the oxygen-containing gas exchanges heat with the high-temperature flue gas from the catalyst regenerator to 200-400°C and then is introduced into the catalyst regenerator, and the raw catalyst contacts with oxygen and burns for regeneration The regenerated catalyst that recovers activity returns to the reactor for recycling. The riser reactor is arranged inside the catalyst regenerator and runs through the catalyst regenerator. The outlet of the riser reactor is connected to the cyclone separator, and the gas phase of the cyclone separator is The outlet is connected to the subsequent separation system through the gas collection chamber, and the solid phase outlet of the cyclone separator is connected to the inside of the catalyst regenerator through the stripping section, and no settler is arranged on the upper part of the stripping section.
本发明提供的方法中，所述的提升管反应器的操作条件为：反应温度为500～750℃、优选540～720℃、更优选560～700℃，反应时间为1～10秒、优选2～6秒、更优选2～4秒，表观压力为0.05～1.0MPa，剂油比为1～100、优选10～50、更优选20～40。In the method provided by the present invention, the operating conditions of the riser reactor are: the reaction temperature is 500-750°C, preferably 540-720°C, more preferably 560-700°C, and the reaction time is 1-10 seconds, preferably 2 ~6 seconds, more preferably 2~4 seconds, the superficial pressure is 0.05~1.0 MPa, the agent-oil ratio is 1~100, preferably 10~50, more preferably 20~40.
本发明提供的轻质烃油催化转化生产低碳烯烃的方法的有益效果为：The beneficial effect of the method for producing light olefins by catalytic conversion of light hydrocarbon oil provided by the invention is:
1)、采用提升管反应器置于催化剂再生器内的结构，缩减了提升管反应器与再生器的散热总表面积，降低了提升管反应器的散热能耗，减少了补充燃料量，节省能量，同时，内置的提升管反应器还可从再生器获得热量，减缓了轻质石油烃裂解生焦不足而带来的热平衡问题。1) The structure in which the riser reactor is placed in the catalyst regenerator reduces the total heat dissipation surface area of the riser reactor and the regenerator, reduces the heat dissipation energy consumption of the riser reactor, reduces the amount of supplementary fuel, and saves energy , At the same time, the built-in riser reactor can also obtain heat from the regenerator, which alleviates the heat balance problem caused by insufficient coke generation in the cracking of light petroleum hydrocarbons.
2)、取消了传统的催化裂化装置的沉降器，采用旋风分离器固相出口直接与汽提段连通的密封式结构，缩短了油气和催化剂的接触时间，快速导出油气，减少了油气停留时间，从而避免了由于催化剂与反应产物接触时间过长而引起的非选择性反应，提高了低碳烯烃产率，其中乙烯产率可达24.35重％，丙烯产率达25.91重％。2) The settler of the traditional catalytic cracking unit is canceled, and the sealed structure of the solid phase outlet of the cyclone separator directly connected to the stripping section is adopted, which shortens the contact time between oil gas and catalyst, quickly exports oil gas, and reduces oil gas residence time , thereby avoiding the non-selective reaction caused by the contact time between the catalyst and the reaction product being too long, and improving the yield of light olefins, wherein the yield of ethylene can reach 24.35% by weight, and the yield of propylene can reach 25.91% by weight.
3)、反应器与再生器一体化，将反应器置于再生器内，结构简单且紧凑，大大节省了设备费用和建设投资。3) The reactor and the regenerator are integrated, and the reactor is placed in the regenerator, which has a simple and compact structure, which greatly saves equipment costs and construction investment.
4)、高温的反应油气与低温的原料换热，高温的烟气与低温主风换热，既为反应系统带入更多的热量，又充分利用了热源，节省的能量。4) High-temperature reaction oil gas exchanges heat with low-temperature raw materials, and high-temperature flue gas exchanges heat with low-temperature main air, which not only brings more heat into the reaction system, but also makes full use of heat sources and saves energy.
附图说明Description of drawings
附图为本发明提供的轻质烃油催化转化生产低碳烯烃的方法流程示意图。The accompanying drawing is a schematic flow chart of the method for producing light olefins by catalytic conversion of light hydrocarbon oil provided by the present invention.
其中：1-提升管反应器，2-旋风分离器，3-催化剂再生器，4-再生催化剂脱气罐，9-汽提蒸汽入口，10-待生催化剂立管、11-旋风分离器气相出口管，12-集气室，13-再生催化剂斜管，5、6、7、8、14、15、16、17、18、19、20、21-管线，33-塞阀，34-中心套筒，35-催化剂导向板。Among them: 1-riser reactor, 2-cyclone separator, 3-catalyst regenerator, 4-regenerated catalyst degassing tank, 9-stripping steam inlet, 10-standby catalyst standpipe, 11-cyclone separator gas phase Outlet pipe, 12-gas collection chamber, 13-regenerated catalyst inclined pipe, 5, 6, 7, 8, 14, 15, 16, 17, 18, 19, 20, 21-pipeline, 33-plug valve, 34-center Sleeve, 35 - Catalyst guide plate.
具体实施方式Detailed ways
以下具体说明本发明提供的方法的具体实施方式，但本发明并不因此而受到任何限制：The specific embodiment of the method provided by the invention is described below in detail, but the present invention is not thereby subject to any limitation:
富含中孔沸石的再生催化剂进入提升管反应器的预提升段，在预提升介质的作用下向上流动，轻质烃油原料与来自提升管反应器的高温反应油气换热到200-550℃后，与雾化蒸汽一起注入提升管反应器下部，与再生催化剂接触进行催化裂解反应同时向上流动；反应后物流经提升管反应器出口进入旋风分离器进行气固分离，分离出的反应油气引出装置，与轻质原料油换热后进一步分离得到乙烯、丙烯、C2～C3烷烃、C4烃馏份、汽油馏份和柴油馏分；分离出的带炭的待生催化剂直接进入旋风分离器下端的汽提段，经汽提后进入催化剂再生器中，含氧气体与来自催化剂再生器的高温烟气换热到200-400℃后引入催化剂再生器，待生催化剂与氧气接触烧焦再生，恢复活性的再生催化剂返回提升管反应器中循环使用；The regenerated catalyst rich in medium pore zeolite enters the pre-lift section of the riser reactor, and flows upward under the action of the pre-lift medium, and the light hydrocarbon oil raw material exchanges heat with the high-temperature reaction oil gas from the riser reactor to 200-550°C Finally, it is injected into the lower part of the riser reactor together with the atomized steam, and it is in contact with the regenerated catalyst for catalytic cracking reaction and flows upward at the same time; the post-reaction stream enters the cyclone separator through the outlet of the riser reactor for gas-solid separation, and the separated reaction oil gas is drawn out After exchanging heat with light feedstock oil, it can be further separated to obtain ethylene, propylene, C2-C3 alkanes, C4 hydrocarbon fractions, gasoline fractions and diesel fractions; the separated charcoal-bearing catalyst directly enters the cyclone separator at the lower end The stripping section enters the catalyst regenerator after stripping, and the oxygen-containing gas exchanges heat with the high-temperature flue gas from the catalyst regenerator to 200-400°C and then enters the catalyst regenerator. The active regenerated catalyst is returned to the riser reactor for recycling;
所述的提升管反应器设置于催化剂再生器内部并贯穿催化剂再生器，所述的提升管反应器出口直接连通旋风分离器，旋风分离器的气相出口经集气室连通后续分离系统，旋风分离器固相出口直接经汽提段连通催化剂再生器内部，所述的汽提段上部不设置沉降器。The riser reactor is arranged inside the catalyst regenerator and runs through the catalyst regenerator, the outlet of the riser reactor is directly connected to the cyclone separator, and the gas phase outlet of the cyclone separator is connected to the subsequent separation system through the gas collection chamber, and the cyclone separates The solid phase outlet of the regenerator is directly connected to the inside of the catalyst regenerator through the stripping section, and the upper part of the stripping section is not provided with a settler.
本发明提供的方法中，所述的提升管反应器的操作条件为：反应温度为500～750℃、优选540～720℃、更优选560～700℃，反应时间为1～10秒、优选2～6秒、更优选2～4秒，表观压力为0.05～1.0MPa，剂油比为1～100、优选10～50、更优选20～40，水蒸汽与原料油的重量比为0.05～1.0。In the method provided by the present invention, the operating conditions of the riser reactor are: the reaction temperature is 500-750°C, preferably 540-720°C, more preferably 560-700°C, and the reaction time is 1-10 seconds, preferably 2 ～6 seconds, more preferably 2～4 seconds, superficial pressure is 0.05～1.0MPa, agent-oil ratio is 1～100, preferably 10～50, more preferably 20～40, the weight ratio of water vapor and raw material oil is 0.05～ 1.0.
本发明提供的方法中，所述的轻质烃油原料为馏程为25-204℃的烃馏份。可以选自催化裂解汽油、催化裂化汽油、直馏石脑油、焦化汽油、热裂解汽油、热裂化汽油和加氢汽油中的一种或几种。In the method provided by the present invention, the light hydrocarbon oil raw material is a hydrocarbon fraction with a distillation range of 25-204°C. It can be selected from one or more of catalytic cracking gasoline, catalytic cracking gasoline, straight-run naphtha, coker gasoline, thermal cracking gasoline, thermal cracking gasoline and hydrogenated gasoline.
本发明提供的方法中，轻质烃油原料先与来自提升管反应器的高温反应油气换热到200-550℃、优选250-500℃、更优选300-480℃后引入提升管反应器中，可以采用列管式换热器等换热设备，或者将高温反应油气与轻质烃油原料直接接触换热，本发明对此没有限制。换热后的轻质烃油原料进入提升管反应器内的方式，可以在一个进料位置将全部所述轻质烃油原料油引入反应器内，或在至少两个不同的进料位置将所述轻质烃油原料按照相同或不同的比例引入反应器内。In the method provided by the present invention, the light hydrocarbon oil raw material first exchanges heat with the high-temperature reaction oil gas from the riser reactor to 200-550°C, preferably 250-500°C, more preferably 300-480°C, and then introduces it into the riser reactor , heat exchange equipment such as shell and tube heat exchangers can be used, or the high-temperature reaction oil gas and light hydrocarbon oil raw materials can be directly contacted for heat exchange, which is not limited in the present invention. The way that the light hydrocarbon oil feedstock after heat exchange enters the riser reactor can introduce all of the light hydrocarbon oil feedstock oil into the reactor at one feed position, or introduce The light hydrocarbon oil feedstock is introduced into the reactor in the same or different proportions.
本发明提供的方法中，所述的反应油气与轻质烃油原料换热后进入后续分离系统，进一步分离得到乙烯、丙烯、C2～C3烷烃、C4烃馏份、汽油馏份和柴油馏份。将干气和液化气经气体分离设备进一步分离得到乙烯、丙烯、C2～C3烷烃、C4烃馏份，从反应产物中分离乙烯和丙烯等方法与本领域常规技术方法相似，本发明对此没有限制。In the method provided by the present invention, the reaction oil gas and the light hydrocarbon oil raw material enter into the subsequent separation system after heat exchange, and further separate and obtain ethylene, propylene, C2-C3 alkanes, C4 hydrocarbon fractions, gasoline fractions and diesel fractions . Dry gas and liquefied gas are further separated by gas separation equipment to obtain ethylene, propylene, C2～C3 alkane, C4 hydrocarbon fractions, and methods such as separating ethylene and propylene from the reaction product are similar to the conventional technical methods in the art, and the present invention does not have this limit.
优选将分离出的C4烃馏份引入提升管反应器中进行回炼。其中，轻质烃油原料与C4烃馏份可以在相同的位置或不同的进料位置引入反应器内。在更优选的实施方案中，所述的返回提升管反应器的C4烃馏份在所述的轻质烃油原料进料位置之后引入反应器。The separated C4 hydrocarbon fraction is preferably introduced into a riser reactor for reclamation. Wherein, the light hydrocarbon oil raw material and the C4 hydrocarbon fraction can be introduced into the reactor at the same position or different feeding positions. In a more preferred embodiment, said C4 hydrocarbon fraction returned to the riser reactor is introduced into the reactor after said light hydrocarbon oil feedstock feed position.
本发明提供的方法中，所述的催化剂再生器中，汽提段下部连接的待生催化剂立管外设置中心套筒，所述的中心套筒上端外缘设置有倾斜向下的催化剂导向板，所述的待生催化剂立管下部设置塞阀，塞阀阀头与待生立管正中对齐。汽提后的待生催化剂由汽提段经待生立管下来，经塞阀调节流量后进入中心套筒，在中心套筒底部输送风的输送下，沿中心套筒上升，通过中心套筒上端的催化剂导向板进入再生器内催化剂密相床中上部。催化剂再生器下部设置所述的中心套筒和塞阀可以防止催化剂再生器中的含氧气体进入汽提段，同时塞阀可控制待生催化剂流量。In the method provided by the present invention, in the catalyst regenerator, a central sleeve is arranged outside the standby catalyst standpipe connected to the lower part of the stripping section, and the outer edge of the upper end of the central sleeve is provided with a catalyst guide plate inclined downward. , the lower part of the standpipe of the standby catalyst is provided with a plug valve, and the valve head of the stopcock is aligned with the center of the standpipe of the standby catalyst. The raw catalyst after stripping comes down from the stripping section through the standby standpipe, and enters the central sleeve after adjusting the flow rate through the plug valve. Under the conveying wind at the bottom of the central sleeve, it rises along the central sleeve and passes through the central sleeve The catalyst guide plate at the upper end enters the middle and upper part of the catalyst dense-phase bed in the regenerator. The central sleeve and plug valve are arranged at the lower part of the catalyst regenerator to prevent the oxygen-containing gas in the catalyst regenerator from entering the stripping section, and the plug valve can control the flow rate of the catalyst to be regenerated.
本发明提供的方法中，催化剂再生器的底部引入含氧气体，所述的含氧气体与来自催化剂再生器的高温烟气换热到200-400℃后引入催化剂再生器，待生催化剂与氧气接触烧焦再生，催化剂烧焦再生后生成的烟气在催化剂再生器上部气固分离，例如经旋风分离器气固分离后，分离出的再生烟气排出催化剂再生器，与含氧气体换热后进入后续处理系统进一步处理。可以采用列管式换热器实现含氧气体和再生烟气的换热。In the method provided by the present invention, the bottom of the catalyst regenerator introduces oxygen-containing gas, and the oxygen-containing gas exchanges heat with the high-temperature flue gas from the catalyst regenerator to 200-400 ° C and then introduces the catalyst regenerator, and the catalyst to be regenerated is mixed with oxygen Contact coke regeneration, the flue gas generated after catalyst coke regeneration is separated from gas to solid in the upper part of the catalyst regenerator, for example, after gas-solid separation in a cyclone separator, the separated regenerated flue gas is discharged out of the catalyst regenerator to exchange heat with oxygen-containing gas Then enter the follow-up processing system for further processing. A tube-and-tube heat exchanger can be used to exchange heat between oxygen-containing gas and regenerated flue gas.
本发明提供的方法中，所述的催化剂再生器中烧焦再生的再生催化剂先进入脱气罐中，脱除含氧气体后引入提升管反应器底部循环使用，脱气罐上部脱除的含氧气体返回催化剂再生器中，以避免大量再生烟气进入提升管反应器，最后到吸收稳定系统、气压机，增加不必要的能量消耗。In the method provided by the present invention, the regenerated catalyst burnt and regenerated in the catalyst regenerator first enters the degassing tank, and after the oxygen-containing gas is removed, it is introduced into the bottom of the riser reactor for recycling. Oxygen gas is returned to the catalyst regenerator to avoid a large amount of regenerated flue gas entering the riser reactor, and finally to the absorption stabilization system and air compressor, increasing unnecessary energy consumption.
本发明提供的方法中，优选的方案是在脱气罐底部引入汽提介质，进一步脱除脱气罐中的再生催化剂所吸附的烟气。所述的汽提介质可以是轻烃、水蒸气或氮气，优选炼油厂干气或水蒸气。更优选的方案中，引入脱气罐底部的汽提介质为轻烃，例如采用炼油厂的干气。用量为轻质烃油总量的3-10重％。In the method provided by the present invention, the preferred solution is to introduce a stripping medium at the bottom of the degassing tank to further remove the flue gas adsorbed by the regenerated catalyst in the degassing tank. The stripping medium can be light hydrocarbon, water vapor or nitrogen, preferably refinery dry gas or water vapor. In a more preferred solution, the stripping medium introduced into the bottom of the degassing tank is light hydrocarbon, such as dry gas from an oil refinery. The dosage is 3-10% by weight of the total amount of light hydrocarbon oil.
本发明提供的方法中，优选向催化剂再生器中喷入燃料以补充能量，所述的燃料为气体燃料和/液体燃料，优选为流化催化裂化或流化催化裂解过程的原料油或柴油馏分或其它液体燃料。In the method provided by the present invention, fuel is preferably injected into the catalyst regenerator to supplement energy, and the fuel is gaseous fuel and/liquid fuel, preferably feed oil or diesel oil fraction of fluidized catalytic cracking or fluidized catalytic cracking process or other liquid fuels.
本发明提供的方法中，进入提升管反应器底部的所述预提升介质为本领域技术人员熟知的各种预提升介质，如水蒸气、炼油厂干气、轻质烷烃、轻质烯烃中的一种或几种。预提升介质的作用是使催化剂加速上升，在提升管反应器底部形成密度均匀的催化剂活塞流。预提升介质的用量为本领域的技术人员所公知，一般来说，预提升介质的用量占烃油总量的1～30重％，优选2～15重％。In the method provided by the present invention, the pre-lift medium entering the bottom of the riser reactor is various pre-lift media well known to those skilled in the art, such as one of water vapor, refinery dry gas, light alkanes, and light olefins. species or several. The role of the pre-lift medium is to accelerate the rise of the catalyst to form a catalyst plug flow with uniform density at the bottom of the riser reactor. The amount of the pre-lift medium is well known to those skilled in the art. Generally speaking, the amount of the pre-lift medium accounts for 1-30 wt%, preferably 2-15 wt%, of the total amount of hydrocarbon oil.
本发明提供的方法中，以催化剂的总重量计，所述催化剂含有：沸石1～60重％、无机氧化物5～99重％和粘土0～70重％，其中沸石作为活性组分，选自中孔沸石和任选的大孔沸石，中孔沸石占沸石总重量的50～100重％，优选70～100重％，大孔沸石占沸石总重量的0～50重％，优选0～30重％。In the method provided by the invention, based on the total weight of the catalyst, the catalyst contains: 1 to 60% by weight of zeolite, 5 to 99% by weight of inorganic oxide and 0 to 70% by weight of clay, wherein zeolite is selected as the active component From medium-pore zeolite and optional large-pore zeolite, medium-pore zeolite accounts for 50-100% by weight of the total weight of zeolite, preferably 70-100% by weight, and large-pore zeolite accounts for 0-50% by weight of the total weight of zeolite, preferably 0-100% by weight 30% by weight.
所述的中孔沸石选自具有MFI结构的沸石，例如ZSM-5沸石和/或ZRP沸石，也可对上述中孔沸石用磷等非金属元素和/或铁、钴、镍等过渡金属元素进行改性，有关ZRP更为详尽的描述参见US5232675，有关ZSM-5更为详尽的描述参见US3702886。所述的大孔沸石选自稀土Y(REY)、稀土氢Y(REHY)、不同方法得到的超稳Y沸石中的一种或几种。所述的无机氧化物作为粘接剂，选自二氧化硅(SiO2)和/或三氧化二铝(Al2O3)。所述的粘土作为基质(即载体)，选自高岭土和/或多水高岭土。The medium-pore zeolite is selected from zeolites with MFI structure, such as ZSM-5 zeolite and/or ZRP zeolite, and non-metallic elements such as phosphorus and/or transition metal elements such as iron, cobalt, and nickel can also be used for the above-mentioned medium-pore zeolite For modification, refer to US5232675 for a more detailed description of ZRP, and refer to US3702886 for a more detailed description of ZSM-5. The large-pore zeolite is selected from one or more of rare earth Y (REY), rare earth hydrogen Y (REHY), and ultrastable Y zeolites obtained by different methods. The inorganic oxide as a binder is selected from silicon dioxide (SiO2 ) and/or aluminum oxide (Al2 O3 ). The clay as a matrix (ie carrier) is selected from kaolin and/or Halloysite.
本发明提供的轻质烃油原料催化裂化生产低碳烯烃的方法还具有以下优点：The method for producing light olefins by catalytic cracking of light hydrocarbon oil feedstock provided by the invention also has the following advantages:
优选的方案中，在再生器中补充燃料，可以灵活调节再生器的温度，为整个反应系统补充热量。再生催化剂脱气罐底部注入置换介质，既可以进一步置换催化剂携带的烟气，又可以作为补充燃料加热催化剂，为装置提供更多的热量。In a preferred solution, fuel is supplemented in the regenerator, and the temperature of the regenerator can be flexibly adjusted to supplement heat for the entire reaction system. The replacement medium is injected into the bottom of the regenerated catalyst degassing tank, which can not only further replace the flue gas carried by the catalyst, but also serve as a supplementary fuel to heat the catalyst to provide more heat for the device.
采用本发明提供的方法，炼厂可以从石油烃最大限度生产乙烯和丙烯，从而实现炼厂概念的技术突破，从传统的燃料型和燃料-润滑油型炼厂生产模式向化工型转变，使炼厂从单一的炼油向化工原料及高附加值下游产品生产发展和延伸，既解决了石化原料短缺的问题，又提高了炼厂的经济效益。By adopting the method provided by the invention, the refinery can produce ethylene and propylene from petroleum hydrocarbons to the maximum extent, thereby realizing a technological breakthrough in the concept of the refinery, transforming the production mode of the traditional fuel type and fuel-lubricating oil type refinery into a chemical type, enabling The development and extension of the refinery from single oil refining to the production of chemical raw materials and high value-added downstream products not only solves the problem of shortage of petrochemical raw materials, but also improves the economic benefits of the refinery.
下面结合附图进一步说明本发明所提供的方法，但本发明并不因此而受到任何限制。The method provided by the present invention will be further described below in conjunction with the accompanying drawings, but the present invention is not limited thereto.
附图为本发明提供的轻质烃油原料生产低碳烯烃的催化转化方法的流程示意图。如附图所示，预提升介质经管线5由提升管反应器1底部进入，来自管线14的再生催化剂在预提升介质的提升作用下沿提升管向上加速运动，与来自管线21的高温反应油气换热到200-550℃的轻质烃油原料经管线7与来自管线6的雾化蒸汽混合后经喷嘴注入提升管反应器1中，与提升管反应器内的催化剂混合，原料油在热的催化剂上发生催化转化反应，并向上加速运动。提升管反应器出口的反应油气和积炭的待生催化剂进入旋风分离器2，旋风分离器可为两级，以提高气固分离效率，实现待生催化剂与反应产物油气的分离，反应产物油气经旋分器出口管11进入集气室12，集气室12中的反应产物油气经过管线21进入换热器中与轻质烃油原料换热后再引入后续分离系统进一步分离。The accompanying drawing is a schematic flow chart of the catalytic conversion method for producing light olefins from light hydrocarbon oil raw materials provided by the present invention. As shown in the figure, the pre-lift medium enters from the bottom of the riser reactor 1 through the pipeline 5, and the regenerated catalyst from the pipeline 14 accelerates upward along the riser under the lifting effect of the pre-lift medium, and reacts with the high-temperature oil gas from the pipeline 21. The light hydrocarbon oil raw material that has been heat-exchanged to 200-550 ° C is mixed with the atomized steam from the pipeline 6 through the pipeline 7, and then injected into the riser reactor 1 through the nozzle, and mixed with the catalyst in the riser reactor. The catalytic conversion reaction occurs on the catalyst and accelerates upward. The reaction oil gas at the outlet of the riser reactor and the coke-deposited catalyst enter the cyclone separator 2. The cyclone separator can be of two stages to improve the gas-solid separation efficiency, realize the separation of the catalyst and the reaction product oil gas, and the reaction product oil gas It enters the gas collection chamber 12 through the outlet pipe 11 of the cyclone, and the oil gas of the reaction product in the gas collection chamber 12 enters the heat exchanger through the pipeline 21 to exchange heat with the light hydrocarbon oil raw material and then introduces into the subsequent separation system for further separation.
经旋风分离器2下部与汽提段密闭链接，分离出的待生催化剂直接进入汽提段，与来自管线9的汽提蒸汽接触汽提脱除待生催化剂上吸附的油气。从待生催化剂中汽提出的反应油气经旋风分离器2后进入集气室12。汽提后的待生催化剂经待生催化剂立管10下来，经设置于待生催化剂立管10底部的塞阀33调节流量后，进入设置于待生催化剂立管15外部的中心套管34中并折向上方，再沿中心套管34上部外缘的催化剂导向板35返到催化剂再生器中，含有氧气的主风与来自催化剂再生器的高温烟气换热到200-400℃后，经管线8进入再生器底部，烧去待生催化剂上的焦炭，使待生催化剂恢复活性。再生后的催化剂经再生斜管13进入脱气罐4，脱气罐下部可经管线19引入汽提介质，进一步脱除再生催化剂中的烟气。脱气后的再生催化剂经管线14循环到提升管反应器1底部，脱气罐上部的气体经管线15返回再生器3中。再生烟气经旋风分离器17的出口管线18送至换热器B与主风换热，或先经烟气轮机回收部分能量，再送至换热器B与引入再生器的含氧气体换热。在装置生焦不足时，可以通过管线20向再生器喷入燃料油。The lower part of the cyclone separator 2 is connected to the stripping section in a sealed manner, and the separated raw catalyst directly enters the stripping section, where it is contacted with the stripping steam from the pipeline 9 to remove the oil gas adsorbed on the raw catalyst. The reaction oil gas stripped from the spent catalyst enters the gas collection chamber 12 after passing through the cyclone separator 2 . The stripped standby catalyst comes down through the standby catalyst standpipe 10, and after the flow is adjusted by the plug valve 33 arranged at the bottom of the standby catalyst standpipe 10, it enters the central casing 34 arranged outside the standby catalyst standpipe 15 And folded upwards, and then return to the catalyst regenerator along the catalyst guide plate 35 on the upper outer edge of the central sleeve 34, the main wind containing oxygen and the high-temperature flue gas from the catalyst regenerator exchange heat to 200-400 ° C, and then Pipeline 8 enters the bottom of the regenerator to burn off the coke on the spent catalyst and restore the activity of the spent catalyst. The regenerated catalyst enters the degassing tank 4 through the regeneration inclined pipe 13, and the lower part of the degassing tank can be introduced into the stripping medium through the pipeline 19 to further remove the flue gas in the regenerated catalyst. The degassed regenerated catalyst is circulated to the bottom of the riser reactor 1 through the pipeline 14, and the gas in the upper part of the degassing tank is returned to the regenerator 3 through the pipeline 15. The regenerated flue gas is sent to the heat exchanger B through the outlet pipeline 18 of the cyclone separator 17 to exchange heat with the main air, or to recover part of the energy through the flue gas turbine, and then sent to the heat exchanger B to exchange heat with the oxygen-containing gas introduced into the regenerator . When the device is insufficient for coking, fuel oil can be injected into the regenerator through the pipeline 20 .
集气室12中的反应油气经过管线21进入换热器与轻质烃油原料换热，然后进入后续的分离系统中进一步分离得到的催化裂解氢气、甲烷和乙烯，经进一步分离得到目的产物乙烯；乙烷、丙烷、丙烯和C4烃馏份、汽油馏份和柴油馏份；C4烃馏份部分或全部返回提升管反应器中继续反应，C4烃馏份可以与轻质烃油原料混合经管线7注入提升管反应器1中，也可以分别注入提升管反应器1中。The reaction oil gas in the gas collection chamber 12 enters the heat exchanger through the pipeline 21 to exchange heat with the light hydrocarbon oil raw material, and then enters the subsequent separation system to further separate the catalytic cracking hydrogen, methane and ethylene, and obtain the target product ethylene after further separation ; Ethane, propane, propylene and C4 hydrocarbon cuts, gasoline cuts and diesel oil cuts; C4 hydrocarbon cuts are partially or completely returned to the riser reactor to continue the reaction, and C4 hydrocarbon cuts can be mixed with light hydrocarbon oil raw materials The pipeline 7 is injected into the riser reactor 1, and may also be injected into the riser reactor 1 separately.
下面的实施例将对本方法予以进一步的说明，但并不因此而限制本发明。The following examples will further illustrate this method, but do not limit the present invention thereby.
实施例中所用的原料为直馏石脑油，其性质如表1所示。The raw material used in the embodiment is straight-run naphtha, and its properties are as shown in Table 1.
实施例中所用的催化裂解催化剂制备方法简述如下：The catalytic cracking catalyst preparation method used in the embodiment is briefly described as follows:
1)将20gNH4Cl溶于1000g水中，向此溶液中加入100g(干基)晶化产品ZRP-1沸石(齐鲁石化公司催化剂厂生产，SiO2/Al2O3＝30，稀土含量RE2O3＝2.0重％)，在90℃交换0.5h后，过滤得滤饼；加入4.0gH3PO4(浓度85％)与4.5gFe(NO3)3溶于90g水中，与滤饼混合浸渍烘干；接着在550℃温度下焙烧处理2小时得到含磷和铁的MFI结构中孔沸石，其元素分析化学组成为1) Dissolve 20g NH4 Cl in 1000g water, add 100g (dry basis) crystallization product ZRP-1 zeolite (produced by Qilu Petrochemical Company Catalyst Factory, SiO2 /Al2 O3 =30, rare earth content RE2 to this solution O3 =2.0 wt%), exchanged at 90°C for 0.5h, filtered to obtain a filter cake; add 4.0g H3 PO4 (concentration 85%) and 4.5g Fe(NO3 )3 to dissolve in 90g water, mix with the filter cake and impregnate Drying; followed by roasting treatment at 550°C for 2 hours to obtain a phosphorus- and iron-containing MFI structure mesoporous zeolite, whose elemental analysis chemical composition is
0.1Na2O·5.1Al2O3·2.4P2O5·1.5Fe2O3·3.8RE2O3·88.1SiO2。0.1Na2 O 5.1Al2 O3 2.4P2 O5 1.5Fe2 O3 3.8RE2 O3 88.1SiO2 .
2)用250kg脱阳离子水将75.4kg多水高岭土(苏州瓷土公司工业产品，固含量71.6重％)打浆，再加入54.8kg拟薄水铝石(山东铝厂工业产品，固含量63重％)，用盐酸将其PH调至2～4，搅拌均匀，在60～70℃下静置老化1小时，保持PH为2～4，将温度降至60℃以下，加入41.5kg铝溶胶(齐鲁石化公司催化剂厂产品，Al2O3含量为21.7重％)，搅拌40分钟，得到混合浆液。2) Beat 75.4kg polyhydrate kaolin (industrial product of Suzhou China Clay Company, solid content 71.6% by weight) with 250kg decationized water, then add 54.8kg pseudoboehmite (industrial product of Shandong Aluminum Factory, solid content 63% by weight) , adjust the pH to 2-4 with hydrochloric acid, stir evenly, leave it to age at 60-70°C for 1 hour, keep the pH at 2-4, lower the temperature below 60°C, add 41.5kg of aluminum sol (Qilu Petrochemical The product of the company's catalyst factory, the content of Al2 O3 is 21.7% by weight), and stirred for 40 minutes to obtain a mixed slurry.
3)将步骤1)制备的含磷和铁的MFI结构中孔沸石(干基为22.5kg)以及DASY沸石(齐鲁石化公司催化剂厂工业产品，晶胞常数为2.445～2.448nm，干基为2.0kg)加入到步骤2)得到的混合浆液中，搅拌均匀，喷雾干燥成型，用磷酸二氢铵溶液(磷含量为1重％)洗涤，洗去游离Na+，干燥即得催化裂解催化剂样品，该催化剂的组成为18重％含磷和铁的MFI结构中孔沸石、2重％DASY沸石、28重％拟薄水铝石、7重％铝溶胶和余量高岭土。3) The phosphorus- and iron-containing MFI structure mesoporous zeolite (dry basis is 22.5 kg) prepared in step 1) and DASY zeolite (industrial product of Qilu Petrochemical Company Catalyst Factory, unit cell constant is 2.445-2.448nm, dry basis is 2.0 kg) was added to the mixed slurry obtained in step 2), stirred evenly, spray-dried and formed, washed with ammonium dihydrogen phosphate solution (phosphorus content is 1% by weight), washed away free Na+ , dried to obtain a catalytic cracking catalyst sample, The composition of the catalyst is 18% by weight of phosphorus and iron-containing MFI structure mesoporous zeolite, 2% by weight of DASY zeolite, 28% by weight of pseudo-boehmite, 7% by weight of aluminum sol and the balance of kaolin.
实施例Example
该实施例按照附图的流程进行试验，以直馏石脑油为原料，在提升管反应器的中型装置上进行试验，预热至250℃的原料油进入提升管底部，在反应温度675℃、反应时间2秒，催化裂解催化剂与原料油的重量比35，水蒸汽与原料油的重量比为0.45条件下进行裂化反应，反应产物和水蒸气以及待生催化剂从反应器出口进入下部和汽提段密闭连通的旋风分离器中，反应产物和催化剂快速分离，反应产物通过与原料换热后引入分离系统按馏程进行切割，从而得到干气、丙烯、C4烃馏份和汽油等馏分，其中C4烃馏份返回反应器进一步反应。待生催化剂由水蒸气汽提出待生催化剂上吸附的烃类产物，汽提后的待生催化剂进入到再生器，与加热到250℃的空气接触进行再生。再生后的催化剂进入脱气罐，并用水蒸气汽提以除去再生催化剂吸附和携带的非烃气体杂质。汽提后的再生催化剂再返回到提升管反应中循环使用。操作条件和产品分布列于表2。This embodiment is tested according to the flow chart of the accompanying drawing, with straight-run naphtha as raw material, the test is carried out on a medium-sized device of a riser reactor, and the raw material oil preheated to 250°C enters the bottom of the riser, and at a reaction temperature of 675°C , the reaction time is 2 seconds, the weight ratio of the catalytic cracking catalyst to the raw oil is 35, and the weight ratio of water vapor to the raw oil is 0.45 to carry out the cracking reaction. In the closed and connected cyclone separator in the lifting section, the reaction product and the catalyst are quickly separated, and the reaction product is introduced into the separation system to cut according to the distillation range after exchanging heat with the raw material, so as to obtain dry gas, propylene, C4 hydrocarbon fractions and gasoline and other fractions. Among them, the C4 hydrocarbon fraction returns to the reactor for further reaction. The spent catalyst is stripped of the hydrocarbon products adsorbed on the spent catalyst by water vapor, and the stripped spent catalyst enters the regenerator and is regenerated by contacting with air heated to 250°C. The regenerated catalyst enters the degassing tank and is stripped with steam to remove the non-hydrocarbon gas impurities adsorbed and carried by the regenerated catalyst. The regenerated catalyst after stripping is returned to the riser reaction for recycling. The operating conditions and product distribution are listed in Table 2.
从表2可以看出，乙烯产率可达24.35重％，丙烯产率可达25.91重％，丙烯/乙烯比约为1.06。It can be seen from Table 2 that the yield of ethylene can reach 24.35% by weight, the yield of propylene can reach 25.91% by weight, and the ratio of propylene/ethylene is about 1.06.
表1Table 1
表2Table 2
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110317854.9ACN103059923B (en) | 2011-10-18 | 2011-10-18 | A kind of Light hydrocarbon oil catalytic conversion method with heat exchange |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110317854.9ACN103059923B (en) | 2011-10-18 | 2011-10-18 | A kind of Light hydrocarbon oil catalytic conversion method with heat exchange |
| Publication Number | Publication Date |
|---|---|
| CN103059923A CN103059923A (en) | 2013-04-24 |
| CN103059923Btrue CN103059923B (en) | 2015-09-23 |
| Application Number | Title | Priority Date | Filing Date |
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| CN201110317854.9AActiveCN103059923B (en) | 2011-10-18 | 2011-10-18 | A kind of Light hydrocarbon oil catalytic conversion method with heat exchange |
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