Fluidized bed apparatus and process for the co-production of aromatics and olefins by coupling naphtha with methanol

Abstract

This application discloses a fluidized-bed apparatus and method for co-producing aromatic hydrocarbons and olefins by coupling naphtha with methanol. Using this apparatus, naphtha and methanol are converted into a product gas primarily composed of aromatic hydrocarbons and low-carbon olefins through the action of a catalyst. This method can convert linear and branched aliphatic hydrocarbons to aromatic hydrocarbons with high selectivity, while increasing the production of paraxylene through the methylation of aromatic hydrocarbons, which can reach up to 75 wt% in a xylene mixture. The aromatization reactor for naphtha and methanol coupling in this application increases paraxylene production by controlling the progress of the stepwise reactions (naphtha → benzene, toluene → paraxylene). Furthermore, the methylation of benzene, toluene, and methanol provides the heat required for the aromatization reaction by coupling naphtha with methanol on-site, achieving autothermal equilibrium.

Description

[Technical Field]

[0001] The present application relates to a fluidized bed reactor and a method for using the same, and more particularly to a fluidized bed reactor for co-producing aromatics and olefins by coupling naphtha with methanol and a method therefor, which belong to the chemical industry technical field. [Background technology]

[0002] Aromatic compounds (benzene, toluene, and dimethylbenzene, collectively known as BTX) are important organic chemical raw materials, and among them, dimethylbenzene (PX) is the most notable aromatic compound. It is primarily used in the production of polyesters such as terephthalic acid (PTA), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polypropylene terephthalate (PTT). In recent years, China's production and consumption of dimethylbenzene have been steadily increasing. In 2021, China's total PX imports were approximately 13.65 million tons, with an external dependency rate of approximately 38%.

[0003] Naphtha catalytic reforming is the primary route for producing aromatic compounds. Naphtha has a highly complex composition. It is not only the primary feedstock for catalytic reforming but also the primary feedstock for thermal cracking to produce ethylene. Its composition plays a crucial role in the economic efficiency of the plant. Generally, a high aromatic potential content and a suitable distillation range are favorable for catalytic reforming. Meanwhile, naphtha with a high content of linear and branched aliphatic hydrocarbons and a low content of cycloalkanes and aromatic compounds is suitable for ethylene production by thermal cracking. To effectively utilize naphtha resources and improve economic efficiency, it is usually necessary to first separate the linear and branched aliphatic hydrocarbons from the cycloalkanes and aromatic compounds in naphtha. The former is used as a feedstock for ethylene production, and the latter is used as a feedstock for the catalytic reforming plant.

[0004] Naphtha fractions have a relatively broad distillation range, making it difficult to efficiently separate linear and branched aliphatic hydrocarbons from cycloalkanes and aromatic compounds using conventional separation methods. Furthermore, catalytic reforming technology also faces challenges in converting linear and branched aliphatic hydrocarbons to aromatic compounds. The naphtha feedstock used in catalytic reforming typically requires distillation to remove light fractions with boiling points below 60°C to increase the aromatic potential of the catalytic reforming feedstock. However, fractions with boiling points above 60°C still contain large amounts of linear and branched aliphatic hydrocarbons that are difficult to convert to aromatic compounds. Therefore, highly selective conversion of linear and branched aliphatic hydrocarbons to aromatic compounds remains a key focus and challenge in the development of technologies for producing aromatic compounds from naphtha.

[0005] Due to thermodynamic equilibrium limitations, the paraxylene content of the xylene mixture produced in naphtha catalytic reforming units is only about 24%. It is necessary to further increase the paraxylene production volume through the isomerization-separation process. Therefore, increasing the paraxylene content in the xylene mixture is an important means of reducing the energy consumption for paraxylene production. Summary of the Invention [Problem to be solved by the invention]

[0006] Naphtha molecules contain only a small amount of methyl groups (methyl groups / benzene rings = ~1.3 (molar ratio)), and due to its molecular structure, catalytic reforming / aromatics combined units inevitably produce large amounts of benzene as a by-product.

[0007] Methanol aromatization is an emerging process for producing aromatic compounds. However, due to the excess hydrogen atoms in the methanol molecule relative to the aromatic compounds, the process of producing aromatic compounds from methanol inevitably produces large amounts of paraffins and hydrogen as by-products. Based on the molecular structure and reaction mechanism, it is clear that methanol can provide methyl groups to aromatic compounds, thereby increasing the production of toluene and xylene. This provides a new technological approach to producing aromatic compounds by coupling naphtha and methanol. [Means for solving the problem]

[0008] The present application provides a fluidized bed apparatus and a method for simultaneously producing aromatic hydrocarbons and olefins by coupling naphtha and methanol using naphtha and methanol as raw materials, with the aim of producing aromatic hydrocarbons with para-xylene as the main target product.

[0009] According to one aspect of the present application, a fluidized bed apparatus for the co-production of aromatics and olefins by coupling naphtha with methanol is provided, including a naphtha and methanol aromatization reactor, a regenerator, and a light hydrocarbon aromatization reactor.

[0010] A fluidized bed apparatus for co-producing aromatics and olefins by coupling naphtha with methanol, comprising: a naphtha-methanol coupling aromatization reactor; a regenerator; and a light hydrocarbon aromatization reactor; The naphtha-methanol coupling aromatization reactor is connected to a regenerator through a spent agent transport pipe I, and the regenerator is connected to the naphtha-methanol coupling aromatization reactor through a regenerant transport pipe; The naphtha and methanol coupling aromatization reaction zone is provided with a naphtha-methanol coupling reactor distributor, the naphtha-methanol coupling reactor distributor includes n sub-distributors, which are arranged in order from bottom to top from a first sub-distributor to an n-th sub-distributor, where 2≦n≦10, the first sub-distributor is used to pass naphtha raw material, and the second sub-distributor to the n-th sub-distributor are used to pass methanol raw material; The light hydrocarbon aromatization reactor comprises a lift tube reactor, the lift tube reactor being connected to a bed reactor; The regenerator is connected to the lift tube reactor through a regenerator slide valve II, and the bed reactor is connected to the regenerator through a spent agent transport pipe II.

[0011] Alternatively, a gas-solid separation section is provided in the upper part of the aromatization reactor by coupling of naphtha and methanol, and a product gas transport pipe I is provided in the gas-solid separation section; and a naphtha-methanol coupling aromatization reaction section is provided in the lower part of the aromatization reactor by coupling of naphtha and methanol; The reactor housing for aromatization by coupling of naphtha and methanol is further provided with a gas-solid separator I, a gas-solid separator II, and a gas collecting chamber I, the gas collecting chamber I being located at the top of the gas-solid separation section, the gas collecting chamber I being connected to a product gas transport pipe I, and the gas outlets of the gas-solid separator I and the gas-solid separator II being connected to the gas collecting chamber I; The catalyst outlet end of the gas-solid separation device I is located above the open end of the stripper I inlet pipe, the inlet of the gas-solid separation device II is connected to the regenerator, and the catalyst outlet end of the gas-solid separation device II is located above the open end of the stripper I inlet pipe and between the first sub-distributor and the second sub-distributor.

[0012] Optionally, a stripper I is provided below the naphtha-methanol coupling aromatization reaction section, and the naphtha-methanol coupling aromatization reaction section is connected to a spent agent transport pipe I via the stripper I.

[0013] Optionally, the stripper I is connected to a spent agent transport pipe I via a spent slide valve I.

[0014] Optionally, the gas-solid separation device I uses one or more sets of gas-solid cyclone separators, each set of gas-solid cyclone separators including one first-class gas-solid cyclone separator and one second-class gas-solid cyclone separator.

[0015] Optionally, the gas-solid separation device II uses one or more sets of gas-solid cyclone separators, each set of gas-solid cyclone separators including one first-class gas-solid cyclone separator and one second-class gas-solid cyclone separator.

[0016] Optionally, a gas-solid separation section of the regenerator is provided at the top of the regenerator, and an exhaust gas transport pipe is provided in the gas-solid separation section of the regenerator; A regeneration section is provided at the bottom of the regenerator, and the outlet of the spent catalyst transport pipe I and the spent catalyst transport pipe II are used to input the spent catalyst into the regeneration section. A regenerator distributor is provided at the bottom of the regenerator to allow the regeneration gas to pass through. The regenerant transport pipe transports the regenerated catalyst in the regeneration section to the naphtha aromatics reactor, and the regeneration slide valve II transports the regenerated catalyst to the lift pipe reactor.

[0017] Optionally, a regenerator gas-solid separation device and a regenerator gas collection chamber are further provided in the regenerator housing, the regenerator gas collection chamber is located at the top of the regenerator gas-solid separation section, the gas outlet of the regenerator gas-solid separation device is connected to the regenerator gas collection chamber, and the regenerator gas collection chamber is connected to an exhaust gas transport pipe.

[0018] Optionally, a regenerator stripper is provided below the regeneration section, and the regeneration section is connected to the regeneration slide valve I and the regeneration slide valve II via the regenerator stripper.

[0019] Optionally, the regeneration slide valve I is connected to the naphtha aromatics reactor through a regenerant transport pipe, and the regeneration slide valve II is connected to the lift pipe reactor.

[0020] Optionally, the regenerator gas-solid separation device uses one or more sets of gas-solid cyclone separators, each set of gas-solid cyclone separators including one first-grade gas-solid cyclone separator and one second-grade gas-solid cyclone separator.

[0021] Optionally, a gas-solid separation zone of the bed reactor is provided at the top of the bed reactor, and a product gas transport pipe II is provided in the gas-solid separation zone of the bed reactor; A light hydrocarbon aromatization reaction zone is provided at the bottom of the bed reactor, and a bed reactor distributor is provided at the bottom of the light hydrocarbon aromatization reaction zone, and the bed reactor distributor is used to pass the bed reactor raw material. The upper end of the lift tube reactor penetrates the bottom of the bed reactor and is inserted axially into the bed reactor; The regeneration slide valve II inputs catalyst into the feed inlet end of the lift tube reactor.

[0022] Optionally, the gas-solid separation section of the bed reactor is provided with a gas-solid separator III and a gas collection chamber II, the gas outlet of the gas-solid separator III is connected to the gas collection chamber II, the catalyst outlet of the gas-solid separator III is located in the light hydrocarbon aromatization reaction section, and the gas collection chamber II is connected to the product gas transport pipe II outside the bed reactor.

[0023] Alternatively, the light hydrocarbon aromatization reaction zone is connected to a stripper II, and the bed reactor is connected to a spent agent transport pipe II through the stripper II.

[0024] Optionally, the stripper II is connected to a spent agent transport pipe II via a spent slide valve II.

[0025] Optionally, the gas-solid separator III is a gas-solid cyclone separator, and the catalyst outlet of the gas-solid separator III is located above the outlet end of the lift tube reactor.

[0026] The present application also proposes a method for co-producing aromatic hydrocarbons and olefins by coupling naphtha and methanol, using the apparatus according to any one of claims 1 to 4 and a metal zeolite bifunctional catalyst as the catalyst.

[0027] A feedstock containing naphtha is fed from the first sub-distributor to an aromatization reactor by coupling naphtha and methanol, a feedstock containing methanol is fed from the second to nth sub-distributors to an aromatization reactor by coupling naphtha and methanol, a lift tube reactor feedstock containing low carbon paraffins is fed to the lift tube reactor, a bed reactor feedstock is fed to the bed reactor, and a regeneration gas is fed to the regenerator.

[0028] The naphtha-methanol coupling aromatization reactor and the bed reactor output product gas, and the spent catalyst is input to the regenerator through the spent agent transport pipe I and the spent agent transport pipe II. The spent catalyst is reacted with the regeneration gas in the regenerator to be regenerated, and then transported to the naphtha-methanol coupling aromatization reactor and the lift tube reactor, and the regenerator discharges exhaust gas.

[0029] Alternatively, the catalyst is a metal-modified HZSM-5 zeolite molecular sieve, and the metal used for the metal modification is at least one selected from La, Zn, Ga, Fe, Mo, and Cr; The metal modification method includes immersing HZSM-5 zeolite molecular sieve in a metal salt solution, drying, and calcining to obtain the metal-modified HZSM-5 zeolite molecular sieve.

[0030] Optionally, the naphtha is at least one selected from direct coal liquefaction naphtha, indirect coal liquefaction naphtha, straight-run naphtha, and hydrocracked naphtha.

[0031] Optionally, the naphtha-containing feedstock further comprises unreacted naphtha separated from the product gas stream, the unreacted naphtha being C4-C 12 These include straight-chain, branched aliphatic hydrocarbons and naphthenes.

[0032] Optionally, the reaction conditions for the aromatization reaction section by coupling naphtha and methanol are: gas superficial linear velocity 0.5-2.0 m / s, reaction temperature 500-600 °C, reaction pressure 100-500 kPa, bed density 150-700 kg / m 3 is.

[0033] Optionally, the gas apparent linear velocity is independently selected from any value of 0.5 m / s, 0.6 m / s, 0.7 m / s, 0.8 m / s, 0.9 m / s, 1.0 m / s, 1.1 m / s, 1.2 m / s, 1.3 m / s, 1.4 m / s, 1.5 m / s, 1.6 m / s, 1.7 m / s, 1.8 m / s, 1.9 m / s, 2.0 m / s, or a range of any two values.

[0034] Optionally, the reaction temperature is independently selected from any value or range of any two values ​​of 500°C, 520°C, 530°C, 540°C, 550°C, 560°C, 570°C, 580°C, 590°C, 600°C.

[0035] Alternatively, the reaction pressure is independently selected from any value or range of any two values ​​of 100 kPa, 125 kPa, 150 kPa, 175 kPa, 200 kPa, 225 kPa, 250 kPa, 275 kPa, 300 kPa, 325 kPa, 350 kPa, 375 kPa, 400 kPa, 425 kPa, 450 kPa, 475 kPa, 500 kPa.

[0036] Optionally, the bed density is 150 kg / m 3 , 200 kg / m 3 , 250 kg / m 3 , 300 kg / m 3 , 350 kg / m 3 , 400 kg / m 3 , 450 kg / m 3 , 500 kg / m 3 , 550 kg / m 3 , 600 kg / m 3 , 650 kg / m 3 , 700 kg / m 3 Independently select any value or range of any two values.

[0037] Optionally, the carbon content in the regenerated catalyst is 0.5 wt % or less.

[0038] Optionally, the regeneration gas is at least one selected from oxygen, air, and oxygen-enriched air.

[0039] Optionally, the reaction conditions in the regeneration zone are: gas superficial linear velocity 0.5-2.0 m / s, regeneration temperature 600-750 °C, regeneration pressure 100-500 kPa, bed density 150-700 kg / m 3 is.

[0040] Optionally, the gas apparent linear velocity is independently selected from any value of 0.5 m / s, 0.6 m / s, 0.7 m / s, 0.8 m / s, 0.9 m / s, 1.0 m / s, 1.1 m / s, 1.2 m / s, 1.3 m / s, 1.4 m / s, 1.5 m / s, 1.6 m / s, 1.7 m / s, 1.8 m / s, 1.9 m / s, 2.0 m / s, or a range of any two values.

[0041] Optionally, the regeneration temperature is independently selected from any value or range of any two values ​​of 600°C, 615°C, 630°C, 645°C, 670°C, 685°C, 700°C, 715°C, 730°C, 745°C, 750°C.

[0042] Optionally, the regeneration pressure is independently selected from any value or range of any two values ​​of 100 kPa, 125 kPa, 150 kPa, 175 kPa, 200 kPa, 225 kPa, 250 kPa, 275 kPa, 300 kPa, 325 kPa, 350 kPa, 375 kPa, 400 kPa, 425 kPa, 450 kPa, 475 kPa, 500 kPa.

[0043] Optionally, the bed density is 150 kg / m 3 , 200 kg / m 3 , 250 kg / m 3 , 300 kg / m 3 , 350 kg / m 3 , 400 kg / m 3 , 450 kg / m3 , 500 kg / m 3 , 550 kg / m 3 , 600 kg / m 3 , 650 kg / m 3 , 700 kg / m 3 Independently select any value or range of any two values.

[0044] Optionally, the lift tube reactor feed further comprises steam, the steam content being 0-80 wt%.

[0045] Optionally, the low carbon paraffins in the lift tube reactor feed are separated from the product gas stream.

[0046] Optionally, the reaction conditions of the lift tube reactor are: gas superficial linear velocity 3.0-10.0 m / s, temperature 580-700°C, pressure 100-500 kPa, bed density 50-150 kg / m 3 is.

[0047] Optionally, the gas apparent linear velocity is independently selected from any value or range of any two values ​​of 3.0 m / s, 3.5 m / s, 4.0 m / s, 4.5 m / s, 5.0 m / s, 5.5 m / s, 6.0 m / s, 6.5 m / s, 7.0 m / s, 7.5 m / s, 8.0 m / s, 8.5 m / s, 9.0 m / s, 9.5 m / s, 10.0 m / s.

[0048] Optionally, the temperature is independently selected from any value or range of any two values ​​of 580°C, 590°C, 600°C, 610°C, 620°C, 630°C, 640°C, 650°C, 660°C, 670°C, 680°C, 690°C, 700°C.

[0049] Optionally, the pressure is independently selected from any value or range of any two values ​​of 100 kPa, 125 kPa, 150 kPa, 175 kPa, 200 kPa, 225 kPa, 250 kPa, 275 kPa, 300 kPa, 325 kPa, 350 kPa, 375 kPa, 400 kPa, 425 kPa, 450 kPa, 475 kPa, 500 kPa.

[0050] Optionally, the bed density is 50 kg / m 3 , 60 kg / m 3 , 70 kg / m 3 , 80 kg / m 3 , 90kg / m 3 , 100 kg / m 3 , 110 kg / m 3 , 120 kg / m 3 , 130 kg / m 3 , 140 kg / m 3 , 150 kg / m 3 Independently select any value or range of any two values.

[0051] Optionally, the bed reactor feed is obtained separately from the product gas stream.

[0052] Optionally, the bed reactor feed comprises unreacted naphtha separated from the product gas stream, the unreacted naphtha being C4-C 12 These include straight-chain, branched aliphatic hydrocarbons and naphthenes.

[0053] Optionally, the bed reactor feed comprises C3, C4 and C5 hydrocarbons.

[0054] Optionally, the bed reactor feed comprises C4 and C5 hydrocarbons.

[0055] Optionally, the reaction conditions of the light hydrocarbon aromatization reaction zone are: gas superficial linear velocity of 0.5-2.0 m / s, reaction temperature of 550-665°C, reaction pressure of 100-500 kPa, bed density of 150-700 kg / m 3 is.

[0056] Optionally, the gas apparent linear velocity is independently selected from any value of 0.5 m / s, 0.6 m / s, 0.7 m / s, 0.8 m / s, 0.9 m / s, 1.0 m / s, 1.1 m / s, 1.2 m / s, 1.3 m / s, 1.4 m / s, 1.5 m / s, 1.6 m / s, 1.7 m / s, 1.8 m / s, 1.9 m / s, 2.0 m / s, or a range of any two values.

[0057] Optionally, the reaction temperature is independently selected from any value or range of any two values ​​of 550°C, 560°C, 570°C, 580°C, 590°C, 600°C, 610°C, 620°C, 630°C, 640°C, 650°C, 660°C, 665°C.

[0058] Alternatively, the reaction pressure is independently selected from any value or range of any two values ​​of 100 kPa, 125 kPa, 150 kPa, 175 kPa, 200 kPa, 225 kPa, 250 kPa, 275 kPa, 300 kPa, 325 kPa, 350 kPa, 375 kPa, 400 kPa, 425 kPa, 450 kPa, 475 kPa, 500 kPa.

[0059] Optionally, the bed density is 150 kg / m 3 , 200 kg / m 3 , 250 kg / m 3 , 300 kg / m 3 , 350 kg / m 3 , 400 kg / m 3 , 450 kg / m 3 , 500 kg / m 3 , 550 kg / m 3 , 600 kg / m 3 , 650 kg / m 3 , 700 kg / m 3 Independently select any value or range of any two values.

[0060] Alternatively, naphtha enters the reaction zone from the first sub-distributor of the distributor of the naphtha and methanol coupling aromatization reactor, and contacts with the catalyst from the regenerator to produce a product gas stream containing BTX, low-carbon olefins, hydrogen, low-carbon alkanes, combustible gases, heavy aromatic hydrocarbons, and unconverted naphtha. The catalyst from the regenerator enters the gas-solid separation device II for gas-solid separation, and the catalyst from which the gas has been removed moves between the first sub-distributor and the second sub-distributor. Methanol enters the reaction zone from the second sub-distributor to the n-th sub-distributor of the distributor of the naphtha and methanol coupling aromatization reactor, respectively, and benzene in the product gas stream is separated. The catalyst from the regenerator is converted into a catalytic converter by condensation in the aromatization reaction section of naphtha and methanol. The product gas flow enters the gas-solid separator I to remove the catalytic converter therein, then enters the gas collection chamber I and passes through the product gas transport pipe I to enter the downstream process. The catalytic converter from the aromatization reaction section of naphtha and methanol enters the stripper I through the open end of the stripper inlet pipe I to be stripped, and after stripping, passes through the spent slide valve I and the spent agent transport pipe I to enter the downstream section.

[0061] The regeneration gas is sent to the regeneration section of the regenerator through the distributor of the regenerator and contacts the pre-regeneration catalyst from the naphtha and methanol coupling aromatization reactor and the pre-regeneration catalyst from the light hydrocarbon aromatization reactor. The coke on the pre-regeneration catalyst reacts with the regeneration gas to produce smoke, and the pre-regeneration catalyst is transformed into a regenerated catalyst.

[0062] The raw material of the lift tube reactor is fed into the inlet end of the lift tube reactor and reacts with the regenerated catalyst from the regenerator. The raw material of the lift tube reactor is converted into a stream containing components such as BTX, low-carbon olefins, and H2 through the action of the catalyst, and then enters the lower part of the light hydrocarbon aromatization reaction zone of the bed reactor through the outlet end of the lift tube reactor.

[0063] The feedstock of the bed reactor is sent to the light hydrocarbon aromatization reaction zone through the distributor of the bed reactor, and contacts with the catalyst from the lift tube reactor to produce light hydrocarbon aromatization product gas containing components such as BTX, low carbon olefins, and H2, and the catalyst is transformed into a catalytic converter.

[0064] Optionally, the product gas stream enters a gas-solid separator I to remove interposed spent catalyst, and then enters a gas collection chamber I and enters downstream processes via product gas delivery line I.

[0065] The spent catalyst from the aromatics reaction section of the naphtha-methanol coupling enters the stripper I through the open end of the stripper I inlet pipe and undergoes stripping treatment. After stripping treatment, it enters the downstream section through the spent catalyst transport pipe I and the spent catalyst slide valve I.

[0066] Specifically, the downstream section is a regenerator.

[0067] The low carbon olefins refer to ethylene and propylene.

[0068] The low carbon alkanes refer to ethane and propane.

[0069] The combustible gases include methane and CO.

[0070] The heavy aromatic compounds refer to aromatic compounds having 9 or more carbon atoms in the molecule.

[0071] Optionally, the method includes the following: the spent catalyst in the aromatics reaction zone produced by coupling naphtha and methanol passes through a stripper I, a spent slide valve I and a spent agent transport pipe I in order into a regenerator, where it contacts and reacts with regeneration gas to obtain exhaust gas and regenerated catalyst.

[0072] Optionally, the method includes the following: the spent catalyst in the light hydrocarbon aromatization reaction zone passes through a stripper II, a spent slide valve II and a spent agent transport pipe II in order into a regenerator, and contacts and reacts with the regeneration gas to obtain exhaust gas and regenerated catalyst.

[0073] The exhaust gas enters the regenerator's gas-solid separator where entrained regenerated catalyst is removed, then enters the regenerator's gas collection chamber and passes through an exhaust gas transport pipe to downstream processes.

[0074] Alternatively, the regenerated catalyst passes through the regenerator stripper, the regenerator slide valve I and the regenerant transport pipe in order to enter the aromatics reactor by coupling naphtha and methanol.

[0075] Optionally, the regenerated catalyst passes through the regenerator stripper and regeneration slide valve II in sequence into the light hydrocarbon aromatization reactor.

[0076] The product gas of the light hydrocarbon aromatization enters a gas-solid separator III, where the entrained catalyst is removed, and then enters a gas collection chamber II and passes through a product gas transport pipe II into downstream processes.

[0077] The catalyst in the light hydrocarbon aromatization reaction zone enters the downstream region through Stripper II, spent slide valve II and spent agent transport line II.

[0078] Specifically, the downstream region is a regenerator.

[0079] The C3, C4, and C5 hydrocarbons refer to hydrocarbons having 3, 4, and 5 carbon atoms.

[0080] The C4 and C5 hydrocarbons refer to hydrocarbons having 4 and 5 carbon atoms.

[0081] The naphtha components in this application are C4-C 12 These include straight-chain, branched aliphatic hydrocarbons, cyclic alkanes and aromatic compounds.

[0082] The aromatic compounds in this application refer to benzene, toluene, and xylene, collectively referred to as BTX.

[0083] In the method described in this application, the aromatic potential content of the naphtha feedstock is 0-80 wt%, the naphtha turnover rate is 70-95 wt%, and the methanol conversion rate in one pass is about 100 wt%. The unconverted naphtha is separated from the product gas and returned to the naphtha-methanol coupling aromatics reactor as feedstock. A portion of the low-carbon alkanes is separated from the product gas and returned to the lift tube reactor of the light hydrocarbon aromatization reactor as feedstock. C3, C4, and C5 hydrocarbons are separated from the product gas and returned to the bed reactor of the light hydrocarbon aromatization reactor as feedstock. The final product composition is as follows: 60-72 wt% BTX, 8-15 wt% low-carbon olefins, 3-7 wt% hydrogen, 3-7 wt% low-carbon alkanes, 4-6 wt% combustible gas, 4-8 wt% heavy aromatics, and 0.5-1 wt% coke. The content of paraxylene in the mixed xylene in the product is 60-75 wt%. [Effects of the Invention]

[0084] (1) The method for producing aromatic compounds by coupling naphtha and methanol described in the present application can convert linear and branched aliphatic hydrocarbons into aromatic compounds with high selectivity, and therefore has a wide range of applicable raw materials, and aromatic compounds can be produced using naphtha with a low aromatic potential content as a raw material. (2) This application achieves the aromatization of low-carbon alkanes, C4 and C5 hydrocarbons by using a light hydrocarbon aromatization reactor and a bifunctional catalyst of metal-containing zeolite, thereby significantly improving the aromatic yield of the technology for producing aromatic compounds from naphtha. (3) The naphtha-methanol coupling aromatic hydrocarbon and olefin co-production apparatus of the present application is equipped with a naphtha-methanol coupling aromatization reactor, which is equipped with multiple sub-distributors and a gas-solid separation unit II. Naphtha enters the reaction zone through the first sub-distributor, and methanol enters the reaction zone from the second sub-distributor through the nth sub-distributor. The gas-solid separation unit II directly delivers the high-activity catalyst from the regenerator above the first sub-distributor. The naphtha-methanol coupling aromatization reactor is a fluidized bed reactor suitable for staged reactions. Naphtha is converted to benzene, toluene, etc. in the lower part of the reaction zone, then flows upward. In the middle and upper parts of the reaction zone, the benzene and toluene undergo methylation with methanol, further producing paraxylene, thereby achieving the production of the target product, paraxylene. The high-activity catalyst from the regenerator enters the lower part of the reaction zone directly, promoting the aromatization reaction of naphtha and improving naphtha conversion. The direct supply of methanol to the middle and upper parts of the reaction zone effectively shortens the residence time of paraxylene in the reaction zone, inhibiting paraxylene isomerization and improving the paraxylene content in xylene (reaching 75 wt% under optimal industrial conditions). At the same time, the energy consumption for paraxylene separation is significantly reduced. In summary, the methylation feedstock (methanol) is supplied in stages as the naphtha feedstock flows from bottom to top in the reactor, controlling the progress of the stepwise reactions (naphtha → benzene, toluene → paraxylene) and increasing paraxylene production. (4) The aromatization reaction of naphtha is a strongly endothermic reaction, absorbing 1.1 to 1.6 MJ of heat when 1 kg of naphtha is converted into aromatic hydrocarbons. On the other hand, the methylation reaction of methanol with aromatic hydrocarbons is a strongly exothermic reaction, releasing more than 2.0 MJ of heat when 1 kg of methanol is converted into methyl groups of aromatic hydrocarbons. Therefore, the reaction for producing paraxylene from benzene, toluene, and methanol supplies heat in situ to the aromatization reaction by coupling naphtha with methanol, achieving autothermal equilibrium. (5) The aromatic hydrocarbon and olefin co-production apparatus of the present application by coupling naphtha and methanol is equipped with an independent light hydrocarbon aromatization reactor. Because low-carbon alkanes are very stable, a higher reaction temperature is required. The temperature of the light hydrocarbon aromatization reactor is higher than that of the aromatization reactor by coupling naphtha and methanol, and low-carbon alkanes and C4 and C5 hydrocarbons undergo aromatization reactions in this independent reactor, thereby improving the reaction rate and aromatic hydrocarbon yield. [Brief explanation of the drawings]

[0085] [Figure 1] FIG. 1 illustrates a fluidized bed apparatus for the co-production of aromatics and olefins by coupling naphtha with methanol according to one embodiment of the present application. DETAILED DESCRIPTION OF THE INVENTION

[0086] The present application will be described in detail below with reference to embodiments, but is not limited to these embodiments.

[0087] Possible embodiments are described below. The present application provides a fluidized bed apparatus for co-producing aromatics and olefins by coupling naphtha with methanol. As shown in Figure 1, the apparatus includes a naphtha-methanol aromatization reactor 1, a regenerator 2, and a light hydrocarbon aromatization reactor 3.

[0088] The naphtha and methanol coupling aromatization reactor 1 includes: a naphtha and methanol coupling aromatization reactor housing 1-1, a naphtha and methanol coupling aromatization reactor distributor 1-2, a gas-solid separation device I1-3, a gas collection chamber I1-4, a product gas transport pipe I1-5, a stripper I1-6, a spent sliding valve I1-7, a spent agent transport pipe I1-8, and a gas-solid separation device II1-9.

[0089] The naphtha and methanol coupling aromatization reactor distributor 1-2 includes a first sub-distributor 1-2-1, a second sub-distributor 1-2-2, and a third sub-distributor 1-2-3.

[0090] The naphtha-methanol coupling aromatization reactor housing 1-1 includes an upper housing and a lower housing, the upper housing forming a gas-solid separation zone and the lower housing forming a reaction zone, and the housings are provided with an outlet for a regenerant transport pipe 2-8.

[0091] The reactor distributor 1-2 is installed in the aromatization reaction section by coupling naphtha and methanol. The distributor includes three sub-distributors, arranged in order from bottom to top, from the first sub-distributor 1-2-1 to the third sub-distributor 1-2-3. The first sub-distributor is used to introduce naphtha feedstock, and the second to third sub-distributors are used to introduce methanol feedstock.

[0092] The naphtha and methanol aromatization reactor housing 1-1 further includes a gas-solid separator I1-3, a gas-solid separator II1-9, and an air collection chamber I1-4. The air collection chamber I1-4 is located at the top of the housing, and the gas outlet of the gas-solid separator I1-3 is connected to the air collection chamber I1-4. The air collection chamber I1-4 is also connected to the product gas transport pipe I1-5, and the catalyst outlet of the gas-solid separator I1-3 is located above the open end of the inlet pipe of the stripper I1-6. The inlet of the gas-solid separator II1-9 is connected to the regenerator 2, its gas outlet is connected to the air collection chamber I1-4, and its catalyst outlet is located above the open end of the inlet pipe of the stripper I1-6 and between the first sub-distributor 1-2-1 and the second sub-distributor 1-2-2.

[0093] A stripper I1-6 is installed below the aromatization reaction zone by coupling naphtha and methanol. The inlet of the stripper I1-6 is located inside the housing 1-1, and the outlet is located outside the housing 1-1 and connected to the used sliding valve I1-7. The open end of the inlet of the stripper I1-6 is located above the first sub-distributor 1-2-1.

[0094] A spent slide valve I1-7 is installed below the stripper I1-6, the inlet of which is connected to the outlet of the stripper I1-6, and the outlet of which is connected to the inlet of a spent agent transport pipe I1-8.

[0095] The outlet of the spent catalyst transport pipe I1-8 is connected to the regenerator housing 2-1, and the spent catalyst slide valve I1-7 serves to control the amount of spent catalyst circulated.

[0096] In a preferred embodiment, the gas-solid separation device I1-3 uses one or more sets of gas-solid cyclone separators, each set including a first-grade gas-solid cyclone separator and a second-grade gas-solid cyclone separator.

[0097] In a preferred embodiment, the gas-solid separation device II1-9 also uses one or more sets of gas-solid cyclone separators, each set including a first-grade gas-solid cyclone separator and a second-grade gas-solid cyclone separator.

[0098] The regenerator 2 includes: a regenerator housing 2-1, a regenerator distributor 2-2, a regenerator gas-solid separator 2-3, a regenerator gas collection chamber 2-4, an exhaust gas transport pipe 2-5, a regenerator stripper 2-6, a regenerator slide valve I 2-7, a regenerant transport pipe 2-8, and a regenerator slide valve II 2-9.

[0099] The regenerator housing 2-1 includes an upper regenerator housing and a lower regenerator housing. The upper regenerator housing encloses the gas-solid separation region, and the lower regenerator housing encloses the regeneration region. The regenerator housing 2-1 is provided with outlets for the spent reagent transport pipes I1-8 and II3-11.

[0100] A regenerator distributor 2-2 is provided at the bottom of the regeneration zone, and this regenerator distributor 2-2 is used to introduce the regeneration gas.

[0101] The regenerator housing 2-1 also contains a regenerator gas-solid separator 2-3 and a regenerator gas collection chamber 2-4. The regenerator gas collection chamber 2-4 is located at the top of the inside of the regenerator housing 2-1. The gas outlet of the regenerator gas-solid separator 2-3 communicates with the regenerator gas collection chamber 2-4, which in turn communicates with an exhaust gas transport pipe 2-5. The catalyst outlet end of the regenerator gas-solid separator 2-3 is located above the open end of the inlet pipe of the regenerator stripper 2-6.

[0102] Below the regeneration zone, a regenerator stripper 2-6 is provided. The inlet of the regenerator stripper 2-6 is located inside the regenerator housing 2-1, and its outlet is located outside the regenerator housing 2-1 and connected to the regeneration slide valves I2-7 and II2-9. The open end of the inlet of the regenerator stripper 2-6 is located above the regenerator distributor 2-2.

[0103] The regenerating slide valve I2-7 is connected to the inlet of the regenerating agent transport pipe 2-8, the outlet of which is connected to the inlet of the gas-solid separator II1-9.

[0104] The regeneration slide valve I2-7 is used to control the circulation rate of the regenerated catalyst.

[0105] The regeneration slide valve II2-9 is also used to control the amount of regenerated catalyst circulated.

[0106] In a preferred embodiment, the regenerator gas-solid separator 2-3 employs one or more sets of gas-solid cyclone separators, each set of gas-solid cyclone separators including a first-class gas-solid cyclone separator and a second-class gas-solid cyclone separator.

[0107] The light hydrocarbon aromatization reactor 3 includes: a lift tube reactor inlet end 3-1, a lift tube reactor middle section 3-2, a lift tube reactor outlet end 3-3, a bed reactor housing 3-4, a bed reactor distributor 3-5, a gas-solid separator III 3-6, a gas collection chamber II 3-7, a product gas transport pipe II 3-8, a stripper II 3-9, a spent sliding valve II 3-10, and a spent agent transport pipe II 3-11.

[0108] The bed reactor housing 3-4 includes an upper bed reactor housing and a lower bed reactor housing. The upper bed reactor housing surrounds the gas-solid separation zone, and the lower bed reactor housing surrounds the light hydrocarbon aromatization reaction zone. A bed reactor distributor 3-5 is installed at the bottom inside the light hydrocarbon aromatization reaction zone. The upper section of the lift tube reactor penetrates the bottom of the bed reactor and is axially inserted into the bed reactor, and the outlet end 3-3 of the lift tube reactor is located at the bottom inside the light hydrocarbon aromatization reaction zone.

[0109] The gas-solid separation zone of the bed reactor is equipped with a gas-solid separator III3-6 and a gas collection chamber II3-7. The gas outlet of the gas-solid separator III3-6 is connected to the gas collection chamber II3-7, and the catalyst outlet of the gas-solid separator III3-6 is located in the light hydrocarbon aromatization reaction zone. The gas collection chamber II3-7 is connected to the product gas transport pipe II3-8 outside the bed reactor.

[0110] The stripper II3-9 and the spent sliding valve II3-10 are provided outside the bed reactor housing. The inlet of the stripper II3-9 is located in the lower bed reactor housing, and its outlet is connected to the inlet of the spent sliding valve II3-10. The outlet of the spent sliding valve II3-10 is connected to the inlet of the spent agent transport pipe II3-11, and the outlet of the spent agent transport pipe II3-11 is connected to the regenerator housing 2-1.

[0111] In a preferred embodiment, the gas-solid separator III3-6 is a gas-solid cyclone separator, and the catalyst outlet of the gas-solid separator III3-6 is located above the outlet end 3-3 of the lift tube reactor.

[0112] In a preferred embodiment, a gas collection chamber II3-7 is provided at the top inside the bed reactor.

[0113] In a preferred embodiment, the bed reactor distributor 3-5 is used to introduce the bed reactor feed.

[0114] In a preferred embodiment, the lift tube reactor inlet end 3-1 is piped to a regeneration slide valve II 2-9.

[0115] In a preferred embodiment, the lift tube reactor inlet end 3-1 is used to introduce catalyst and lift tube reactor feed.

[0116] The present application provides a process for the co-production of aromatic hydrocarbons and olefins by coupling naphtha with methanol using the above-described apparatus and a metal zeolite bifunctional catalyst.

[0117] Optionally, the catalyst employs a metal-modified HZSM-5 zeolite molecular sieve, wherein the metal used for the metal modification is selected from at least one of La, Zn, Ga, Fe, Mo, and Cr.

[0118] The method of metal modification involves soaking the HZSM-5 zeolite molecular sieve in a metal salt solution, drying and calcining to obtain the metal-modified HZSM-5 zeolite molecular sieve.

[0119] The method comprises the steps of: Naphtha enters the reaction zone through the first sub-distributor 1-2-1 of the naphtha-methanol coupling aromatization reactor distributor 1-2 and contacts the catalyst from regenerator 2 to produce a product gas stream containing BTX, low-carbon olefins, hydrogen, low-carbon alkanes, combustible gases, heavy aromatic hydrocarbons, and unconverted naphtha. The catalyst from regenerator 2 enters gas-solid separation unit II 1-9, where the degassed catalyst enters between the first sub-distributor 1-2-1 and the second sub-distributor 1-2-2. Methanol enters the reaction zone through the second sub-distributor 1-2-2 to the third sub-distributor 1-2-3 of distributor 1-2 and undergoes a methylation reaction with benzene and toluene in the product gas stream to produce paraxylene. The catalyst from regenerator 2 is concentrated in the reaction zone and converted into spent catalyst. The product gas flow enters the gas-solid separator I1-3, and after the accompanying spent catalyst is removed, it enters the gas collection chamber I1-4 and is sent to the downstream process through the product gas transport pipe I1-5. The spent catalyst in the reaction zone enters the stripper I1-6 through the open end of its inlet pipe, is stripped, and is sent to the regenerator 2 through the spent catalyst slide valve I1-7 and the spent catalyst transport pipe I1-8.

[0120] The regeneration gas is supplied to the regeneration zone of the regenerator 2 through the regenerator distributor 2-2 and contacts the spent catalyst. This contact causes the coke on the spent catalyst to react with the regeneration gas, generating smoke and converting the spent catalyst into regenerated catalyst. The generated smoke is introduced into the regenerator gas-solid separator 2-3 to separate the accompanying regenerated catalyst, then flows into the regenerator gas collection chamber 2-4 and is sent to the downstream process through the exhaust gas transport pipe 2-5. The regenerated catalyst is sequentially passed through the regenerator stripper 2-6, the regeneration slide valve I2-7, and the regenerant transport pipe 2-8 and supplied to the naphtha-methanol coupling aromatization reactor 1. The regenerated catalyst is also supplied to the light hydrocarbon aromatization reactor 3 via the regenerator stripper 2-6 and the regeneration slide valve II2-9.

[0121] The lift tube reactor feedstock is fed to the lift tube reactor through the lift tube reactor inlet end 3-1 and reacts with the regenerated catalyst supplied from the regenerator. This reaction converts the lift tube reactor feedstock into a stream containing BTX, low-carbon olefins, H2, and other components. This stream is then introduced into the lower part of the light hydrocarbon aromatization reaction zone in the bed reactor through the lift tube reactor outlet end 3-3. Meanwhile, the bed reactor feedstock is fed to the light hydrocarbon aromatization reaction zone through the bed reactor distributor 3-5 and contacts the catalyst supplied from the lift tube reactor to produce a light hydrocarbon aromatization product gas containing BTX, low-carbon olefins, H2, and other components. The light hydrocarbon aromatization product gas is then introduced into the gas-solid separator III3-6 to separate the entrained catalyst, then flows into the gas collection chamber II3-7 and is sent to downstream processes through the product gas transport pipe II3-8. The catalyst in the light hydrocarbon aromatization reaction zone is sent to the regenerator 2 via a stripper II3-9, a spent slide valve II3-10, and a spent agent transport pipe II3-11.

[0122] The low carbon olefins refer to ethylene and propylene.

[0123] The low carbon alkanes refer to ethane and propane.

[0124] The combustible gases include methane and CO, among others.

[0125] The heavy aromatic hydrocarbons refer to aromatic hydrocarbons having 9 or more carbon atoms in the molecule.

[0126] In a preferred embodiment, the naphtha is at least one selected from direct coal liquefaction naphtha, indirect coal liquefaction naphtha, straight-run naphtha, and hydrocracked naphtha.

[0127] In a preferred embodiment, the naphtha further comprises unconverted naphtha separated from the product gas stream.

[0128] In a preferred embodiment, the process conditions in the aromatization reaction zone by coupling naphtha and methanol are a gas apparent linear velocity of 0.5 to 2.0 m / s, a reaction temperature of 500 to 600°C, a reaction pressure of 100 to 500 kPa, and a bed density of 150 to 700 kg / m 3 is.

[0129] In a preferred embodiment, the carbon content in the regenerated catalyst is 0.5 wt% or less.

[0130] In a preferred embodiment, the regeneration gas is at least one selected from oxygen, air, and oxygen-enriched air.

[0131] In a preferred embodiment, the process conditions in the regeneration zone are a gas apparent linear velocity of 0.5 to 2.0 m / s, a regeneration temperature of 600 to 750°C, a regeneration pressure of 100 to 500 kPa, and a bed density of 150 to 700 kg / m 3 is.

[0132] In a preferred embodiment, the lift tube reactor feed comprises steam and lower carbon alkanes separated from the product gas stream.

[0133] In a preferred embodiment, the steam content in the feedstock of the lift tube reactor is 0 to 80 wt%.

[0134] In a preferred embodiment, the process conditions of the lift tube reactor are: apparent linear velocity of gas of 3.0 to 10.0 m / s, temperature of 580 to 700°C, pressure of 100 to 500 kPa, and bed density of 50 to 150 kg / m 3 is.

[0135] In a preferred embodiment, the bed reactor feed further includes unreacted naphtha separated from the product gas stream, and the main component of the unreacted naphtha is C4 to C6. 12 straight-chain, branched aliphatic hydrocarbons, and naphthenes.

[0136] In a preferred embodiment, the bed reactor feed comprises C3, C4, and C5 hydrocarbons.

[0137] In a preferred embodiment, the bed reactor feed comprises C4 and C5 hydrocarbons.

[0138] In a preferred embodiment, the C3, C4, and C5 hydrocarbons are derived from C3, C4, and C5 hydrocarbons separated from a product gas stream.

[0139] In a preferred embodiment, the C4 and C5 hydrocarbons are derived from C4 and C5 hydrocarbons separated from a product gas stream.

[0140] The C3, C4, and C5 hydrocarbons refer to hydrocarbons having 3, 4, and 5 carbon atoms.

[0141] The C4 and C5 hydrocarbons refer to hydrocarbons having 4 and 5 carbon atoms.

[0142] In the embodiment described in this application, the aromatic potential content of the naphtha feedstock is 0-80 wt%, the naphtha turnover rate is 70-95 wt%, and the methanol conversion rate in one pass is about 100 wt%. The unconverted naphtha is separated from the product gas and returned to the naphtha-methanol coupling aromatics reactor as feedstock. A portion of the low-carbon alkanes is separated from the product gas and returned to the lift tube reactor of the light hydrocarbon aromatization reactor as feedstock. C3, C4, and C5 hydrocarbons are separated from the product gas and returned to the bed reactor of the light hydrocarbon aromatization reactor as feedstock. The final product composition is as follows: 60-72 wt% BTX, 8-15 wt% low-carbon olefins, 3-7 wt% hydrogen, 3-7 wt% low-carbon alkanes, 4-6 wt% combustible gas, 4-8 wt% heavy aromatics, and 0.5-1 wt% coke. The content of paraxylene in the mixed xylene in the product is 60-75 wt%.

[0143] The catalysts in the following examples are prepared by the following method: 100 g of HZSM-5 zeolite molecular sieve (manufactured by Minamidaikaigaku Catalyst Factory, Si / Al=15) was immersed in a 10 wt% aqueous zinc nitrate solution. The mass ratio (i.e., solid-liquid ratio) of the HZSM-5 zeolite molecular sieve to the zinc nitrate solution was 1 / 10, and the solution was immersed at 80°C for 6 hours. After immersion, the solution was drained, dried in an air atmosphere at 120°C for 4 hours, and then calcined in an air atmosphere at 550°C for 4 hours to obtain a [Zn]HZSM-5 molecular sieve sample. This sample was tableted, crushed, and sieved to obtain molded molecular sieve particles with a particle size of 40 to 60 mesh.

[0144] 100 g of [Zn]HZSM-5 molecular sieve sample was mixed with an amorphous binder containing aluminum or silicon, and then spray-dried and molded. The specific procedure was as follows:

[0145] [Zn]HZSM-5 molecular sieve sample, pseudoboehmite, silica sol, xanthan gum (biogum), and water were uniformly mixed, and the mixture was mixed, colloid milled, and degassed to obtain a slurry. The weight parts of each component in the slurry were as follows: [Zn]HZSM-535 parts by weight Al2O320 parts by weight SiO245 parts by weight H2O240 parts by weight Xanthan gum 1 part by weight

[0146] The resulting slurry is spray-dried and molded to obtain a microsphere sample with a particle size distribution of 20 to 100 μm. The microsphere sample is then calcined in a muffle furnace at 550°C for 3 hours to obtain a [Zn]HZSM-5 molded molecular sieve with an abrasion index of 1.2.

[0147] Example 1 In this embodiment, the device shown in FIG. 1 is used.

[0148] In this embodiment, the naphtha feedstock entering the naphtha-methanol coupling aromatization reactor is coal direct liquefaction naphtha, the aromatic potential content of which is 78 wt%.

[0149] The process conditions of the naphtha-methanol coupling aromatization reactor's naphtha-methanol coupling aromatization reaction zone are as follows: gas apparent linear velocity: 0.5 m / s, reaction temperature: 600°C, reaction pressure: 100 kPa, bed density: 700 kg / m 3 .

[0150] The regeneration gas is air.

[0151] The engineering conditions of the regeneration area of ​​the regenerator were as follows: gas apparent linear velocity 0.5 m / s, regeneration temperature 745°C, regeneration pressure 100 kPa, bed density 700 kg / m 3 .

[0152] The carbon content in the regenerated catalyst is 0.2 wt%.

[0153] The lift tube reactor feed is low carbon olefins separated from the product gas stream.

[0154] The engineering conditions of the lift tube reactor were as follows: gas apparent linear velocity 3.0 m / s, temperature 690°C, pressure 100 kPa, bed density 150 kg / m 3 .

[0155] The bed reactor feed comprises unreacted naphtha separated from the product gas stream, said unreacted naphtha being C4-C 12 These include straight-chain, branched aliphatic hydrocarbons and naphthenes.

[0156] The engineering conditions of the light hydrocarbon aromatization reaction area are as follows: gas apparent linear velocity is 0.5 m / s, reaction temperature is 665°C, reaction pressure is 100 kPa, and bed density is 700 kg / m 3 .

[0157] The single-stage conversion of naphtha feedstock entering the aromatization reactor by coupling naphtha with methanol is 60 wt%.

[0158] The product distribution is as follows: 72 wt% BTX, 8 wt% low-carbon olefins, 3 wt% hydrogen, 3.5 wt% low-carbon alkanes, 5 wt% combustible gases, 7.5 wt% heavy aromatics, and 1 wt% coke. The para-xylene content of the mixed xylenes in the product is 60 wt%.

[0159] Example 2 In this embodiment, the device shown in FIG. 1 is used.

[0160] In this embodiment, the naphtha feedstock entering the naphtha-methanol coupling aromatization reactor is indirect coal liquefaction naphtha, and its potential aromatic content is 0.1 wt%. The naphtha feedstock entering the naphtha-methanol coupling aromatization reactor also includes unconverted naphtha separated from the product gas stream.

[0161] The process conditions of the naphtha-methanol coupling aromatization reactor's naphtha-methanol coupling aromatization reaction zone are as follows: gas apparent linear velocity 2.0 m / s, reaction temperature 510°C, reaction pressure 500 kPa, bed density 150 kg / m 3 .

[0162] The regeneration gas is oxygen.

[0163] The engineering conditions of the regeneration area of ​​the regenerator were as follows: gas apparent linear velocity 2.0 m / s, regeneration temperature 610°C, regeneration pressure 500 kPa, bed density 150 kg / m 3 .

[0164] The carbon content in the regenerated catalyst is 0.1 wt%.

[0165] The lift tube reactor feed contains steam and low carbon olefins separated from the product gas stream, the steam content of which is 80 wt %.

[0166] The engineering conditions of the lift tube reactor were as follows: gas apparent linear velocity 10.0 m / s, temperature 580°C, pressure 500 kPa, bed density 50 kg / m 3 .

[0167] The bed reactor feed is C3, C4 and C5 hydrocarbons separated from the product gas stream.

[0168] The engineering conditions of the light hydrocarbon aromatization reaction area are as follows: gas apparent linear velocity is 2.0 m / s, reaction temperature is 550°C, reaction pressure is 500 kPa, and bed density is 150 kg / m 3 . The single-stage conversion of naphtha feedstock entering the aromatization reactor by coupling naphtha with methanol is 76 wt%.

[0169] The product distribution is as follows: 64 wt% BTX, 14 wt% low-carbon olefins, 5.3 wt% hydrogen, 3 wt% low-carbon alkanes, 5 wt% combustible gases, 8 wt% heavy aromatics, and 0.7 wt% coke. The para-xylene content of the mixed xylenes in the product is 73 wt%.

[0170] Example 3 In this embodiment, the device shown in FIG. 1 is used.

[0171] In this embodiment, the naphtha feedstock entering the naphtha-methanol coupling aromatization reactor is indirect coal liquefaction naphtha, and its aromatic potential content is 3 wt %. The naphtha feedstock entering the naphtha-methanol coupling aromatization reactor also includes unconverted naphtha separated from the product gas stream.

[0172] The process conditions of the naphtha-methanol coupling aromatization reactor's naphtha-methanol coupling aromatization reaction zone are as follows: gas apparent linear velocity 1.2 m / s, reaction temperature 550 °C, reaction pressure 120 kPa, bed density 260 kg / m 3 .

[0173] The regeneration gas is oxygen-enriched air.

[0174] The engineering conditions of the regeneration area of ​​the regenerator are as follows: gas apparent linear velocity 1.2 m / s, regeneration temperature 650 °C, regeneration pressure 120 kPa, bed density 260 kg / m 3 .

[0175] The carbon content in the regenerated catalyst is 0.3 wt%.

[0176] The lift tube reactor feed contains steam and low carbon olefins separated from the product gas stream, the steam content of which is 25 wt%.

[0177] The engineering conditions of the lift tube reactor were as follows: gas apparent linear velocity 7.0 m / s, temperature 630°C, pressure 120 kPa, bed density 80 kg / m 3 .

[0178] The bed reactor feed is C4 and C5 hydrocarbons separated from the product gas stream.

[0179] The engineering conditions of the light hydrocarbon aromatization reaction area are as follows: gas apparent linear velocity is 1.2 m / s, reaction temperature is 580 °C, reaction pressure is 120 kPa, bed density is 260 kg / m 3 .

[0180] The single-stage conversion of naphtha feedstock entering the aromatization reactor by coupling naphtha with methanol is 80 wt%.

[0181] The product distribution is as follows: 60 wt% BTX, 15 wt% low-carbon olefins, 7 wt% hydrogen, 7 wt% low-carbon alkanes, 5 wt% combustible gases, 5.5 wt% heavy aromatics, and 0.5 wt% coke. The para-xylene content of the mixed xylenes in the product is 75 wt%.

[0182] Example 4 In this embodiment, the device shown in FIG. 1 is used.

[0183] In this embodiment, the naphtha feedstock entering the naphtha-methanol coupled aromatization reactor is straight-run naphtha, with a potential aromatics content of 46 wt %, and the naphtha feedstock entering the naphtha-methanol coupled aromatization reactor also includes unconverted naphtha separated from the product gas stream.

[0184] The process conditions of the naphtha-methanol coupling aromatization reactor's naphtha-methanol coupling aromatization reaction zone are as follows: gas apparent linear velocity 1.8 m / s, reaction temperature 590 °C, reaction pressure 200 kPa, bed density 220 kg / m 3 .

[0185] The regeneration gas is air.

[0186] The engineering conditions of the regeneration area of ​​the regenerator are as follows: gas apparent linear velocity 1.8 m / s, regeneration temperature 700 °C, regeneration pressure 200 kPa, bed density 220 kg / m 3 .

[0187] The carbon content in the regenerated catalyst is 0.1 wt%.

[0188] The lift tube reactor feed contains steam and low carbon olefins separated from the product gas stream, wherein the steam content is 50 wt%.

[0189] The engineering conditions of the lift tube reactor were as follows: gas apparent linear velocity 5.0 m / s, temperature 660°C, pressure 200 kPa, bed density 110 kg / m 3 .

[0190] The bed reactor feed is C4 and C5 hydrocarbons separated from the product gas stream.

[0191] The engineering conditions of the light hydrocarbon aromatization reaction area are as follows: gas apparent linear velocity is 1.8 m / s, reaction temperature is 630 °C, reaction pressure is 200 kPa, and bed density is 220 kg / m 3 .

[0192] The single-stage conversion of naphtha feedstock entering the aromatization reactor by coupling naphtha with methanol is 71 wt%.

[0193] The product distribution is as follows: 67 wt% BTX, 13 wt% low-carbon olefins, 6 wt% hydrogen, 5 wt% low-carbon alkanes, 4 wt% combustible gases, 4.2 wt% heavy aromatics, and 0.8 wt% coke. The para-xylene content of the mixed xylenes in the product is 68 wt%.

[0194] Example 5 In this embodiment, the device shown in FIG. 1 is used.

[0195] In this embodiment, the naphtha feedstock entering the naphtha-methanol coupled aromatization reactor is hydrocracked naphtha, with a potential aromatics content of 64 wt %, and the naphtha feedstock entering the naphtha-methanol coupled aromatization reactor also includes unconverted naphtha separated from the product gas stream.

[0196] The process conditions of the naphtha-methanol coupling aromatization reactor's naphtha-methanol coupling aromatization reaction zone are as follows: gas apparent linear velocity 1.0 m / s, reaction temperature 580°C, reaction pressure 150 kPa, bed density 350 kg / m 3 .

[0197] The regeneration gas is air.

[0198] The engineering conditions of the regeneration area of ​​the regenerator were as follows: gas apparent linear velocity 1.0 m / s, regeneration temperature 680°C, regeneration pressure 150 kPa, bed density 350 kg / m 3 .

[0199] The carbon content in the regenerated catalyst is 0.5 wt%.

[0200] The lift tube reactor feed contains steam and low carbon olefins separated from the product gas stream, the steam content of which is 40 wt%.

[0201] The engineering conditions of the lift tube reactor were as follows: gas apparent linear velocity 7.0 m / s, temperature 650°C, pressure 150 kPa, bed density 80 kg / m 3 .

[0202] The bed reactor feed is C4 and C5 hydrocarbons separated from the product gas stream.

[0203] The engineering conditions of the light hydrocarbon aromatization reaction area are as follows: gas apparent linear velocity is 1.0 m / s, reaction temperature is 610°C, reaction pressure is 150 kPa, and bed density is 350 kg / m 3 .

[0204] The single-stage conversion of naphtha feedstock entering the aromatization reactor by coupling naphtha with methanol is 67 wt%.

[0205] The product distribution is as follows: 70 wt% BTX, 10 wt% low-carbon olefins, 5 wt% hydrogen, 3 wt% low-carbon alkanes, 6 wt% combustible gases, 5 wt% heavy aromatics, and 1.0 wt% coke. The para-xylene content of the mixed xylenes in the product is 64 wt%.

[0206] The above description is only a partial example of the present application and does not limit the present application in any way. In the present application, more preferred embodiments are disclosed as above, but they are not intended to limit the present application. Various variations and modifications made by a person skilled in the art using the technical content disclosed above without departing from the technical solution of the present application are all equivalent to equivalent embodiments, and all fall within the scope of the technical solution. [Explanation of symbols]

[0207] 1. Aromatization reactor by coupling naphtha and methanol 1-1 Aromatization reactor housing by coupling naphtha and methanol 1-2 Aromatization reactor distributor by coupling naphtha and methanol 1-3 Gas-solid separator I 1-4 Air collection chamber I 1-5 Produced gas transport pipe I 1-6 Stripper I 1-7 Used sliding valve I 1-8 Spent Agent Transport Pipe I 1-9 Gas-solid separator II 1-2-1 1st sub-distributor 1-2-2 Second sub-distributor 1-2-3 3rd sub-distributor 2 Regenerator 2-1 Regenerator housing 2-2 Regenerator distributor 2-3 Regenerator gas-solid separation device 2-4 Regenerator gas collection chamber 2-5 Exhaust gas transport pipe 2-6 Regenerator stripper 2-7 Regenerative Slide Valve I 2-8 Regenerant transport pipe 2-9 Regenerative Slide Valve II 3 Light hydrocarbon aromatization reactor 3-1 Lift tube reactor inlet end 3-2 Lift tube reactor center 3-3 Lift tube reactor outlet end 3-4 Bed Reactor Housing 3-5 Bed Reactor Distributor 3-6 Gas-solid separator III 3-7 Air collection chamber II 3-8 Produced Gas Transport Pipe II 3-9 Stripper II 3-10 Used sliding valve II 3-11 Spent Agent Transport Pipe II

Claims

1. A fluidized bed apparatus for co-producing aromatics and olefins by coupling naphtha with methanol, comprising: an aromatization reactor by coupling naphtha with methanol, a regenerator, and a light hydrocarbon aromatization reactor, The naphtha and methanol coupling aromatization reactor is connected to a regenerator through a spent agent transport pipe I; the regenerator is connected to the naphtha and methanol coupling aromatization reactor via a regenerant transport pipe; The aromatization reaction zone by coupling of naphtha and methanol is provided with a naphtha-methanol coupling reactor distributor; The naphtha-methanol coupling reactor distributor includes n sub-distributors, which are arranged in order from the first sub-distributor to the nth sub-distributor from bottom to top, where 2≦n≦10; the first sub-distributor is used to pass naphtha feedstock; the second sub-distributor to the n-th sub-distributor are used to pass a methanol raw material; The light hydrocarbon aromatization reactor comprises a lift tube reactor, the lift tube reactor being connected to a bed reactor; The regenerator is connected to the lift pipe reactor via a regenerator slide valve II; The apparatus is characterized in that the bed reactor is connected to the regenerator through a spent agent transport pipe II.

2. a gas-solid separation section is provided at the top of the aromatization reactor by coupling of naphtha and methanol; The gas-solid separation section is provided with a product gas transport pipe I, A naphtha-methanol coupling aromatization reaction section is provided in the lower part of the naphtha-methanol coupling aromatization reactor, The reactor housing for aromatization by coupling of naphtha and methanol is further provided with a gas-solid separation device I, a gas-solid separation device II, and a gas collection chamber I, the gas collection chamber I being located at the top of the gas-solid separation section, and the gas collection chamber I being connected to a product gas transport pipe I; The gas outlets of the gas-solid separator I and the gas-solid separator II communicate with the gas collecting chamber I; The catalyst outlet end of the gas-solid separation device I is located above the open end of the inlet pipe of the stripper I, The inlet of the gas-solid separation device II is connected to the regenerator, 2. The apparatus according to claim 1, wherein the catalyst outlet end of the gas-solid separation device II is located above the open end of the inlet pipe of the stripper I and between the first sub-distributor and the second sub-distributor.

3. a stripper I is provided below the aromatization reaction section by coupling of naphtha and methanol; 3. The apparatus according to claim 2, wherein the aromatization reaction zone by coupling of naphtha and methanol is connected to the spent reagent transport pipe I via a stripper I.

4. 4. The apparatus according to claim 3, wherein the stripper I is connected to a spent agent transport pipe I via a spent slide valve I.

5. 3. The apparatus according to claim 2, wherein the gas-solid separation device I uses one or more sets of gas-solid cyclone separators, and each set of gas-solid cyclone separators includes one first-class gas-solid cyclone separator and one second-class gas-solid cyclone separator.

6. 3. The apparatus according to claim 2, wherein the gas-solid separation device II uses one or more sets of gas-solid cyclone separators, and each set of gas-solid cyclone separators includes one first-class gas-solid cyclone separator and one second-class gas-solid cyclone separator.

7. A gas-solid separation section of the regenerator is provided at the top of the regenerator, and an exhaust gas transport pipe is provided in the gas-solid separation section of the regenerator; A regeneration section is provided at the bottom of the regenerator. The outlet of spent catalyst transport pipe I and the outlet of spent catalyst transport pipe II are used to feed spent catalyst into the regeneration section; A regenerator distributor is provided at the bottom of the regenerator to allow the regenerated gas to pass through. The regenerant transport pipe transports the regenerated catalyst in the regeneration zone to the naphtha aromatics reactor; 2. The apparatus of claim 1, wherein a regenerated slide valve II delivers regenerated catalyst to the lift tube reactor.

8. The regenerator housing further includes a regenerator gas-solid separator and a regenerator gas collecting chamber; The regenerator gas collecting chamber is located at the top of the regenerator gas-solid separation section; a gas outlet of the regenerator gas-solid separation device communicating with the regenerator gas collection chamber; 8. The apparatus of claim 7, wherein the regenerator gas collection chamber communicates with an exhaust gas transport pipe.

9. A regenerator stripper is provided below the regenerator section, 8. The apparatus according to claim 7, wherein the regeneration section is connected to the regeneration slide valve I and the regeneration slide valve II via a regenerator stripper.

10. The regeneration slide valve I is connected to the naphtha aromatic reactor through a regenerant transport pipe; 10. The apparatus according to claim 9, wherein the regeneration slide valve II is connected to the lift pipe reactor.

11. 8. The apparatus according to claim 7, wherein the regenerator gas-solid separation device uses one or more sets of gas-solid cyclone separators, and each set of gas-solid cyclone separators includes one first-class gas-solid cyclone separator and one second-class gas-solid cyclone separator.

12. A gas-solid separation zone of the bed reactor is provided at the top of the bed reactor, The gas-solid separation section of the bed reactor is provided with a product gas transport pipe II; The lower part of the bed reactor is provided with a light hydrocarbon aromatization reaction zone, a bed reactor distributor is provided in the lower part of the light hydrocarbon aromatization reaction zone; The bed reactor distributor is used to pass the bed reactor feed, The upper end of the lift tube reactor penetrates the bottom of the bed reactor and is inserted into the bed reactor in the axial direction.

2. The apparatus of claim 1, wherein said regeneration slide valve II inputs catalyst into the feed inlet end of said lift tube reactor.

13. The gas-solid separation section of the bed reactor is provided with a gas-solid separator III and a gas collection chamber II; The gas outlet of the gas-solid separator III is in communication with the gas collecting chamber II; The catalyst outlet of the gas-solid separator III is located in the light hydrocarbon aromatization reaction zone; 13. The apparatus according to claim 12, wherein the gas collection chamber II is in communication with a product gas transport pipe II outside the bed reactor.

14. The light hydrocarbon aromatization reaction zone is connected to a stripper II; 14. The apparatus according to claim 13, wherein the bed reactor is connected to a spent agent transport pipe II via a stripper II.

15. 15. The apparatus according to claim 14, wherein the stripper II is connected to a spent agent transport pipe II via a spent slide valve II.

16. The gas-solid separation device III is a gas-solid cyclone separator; 14. The apparatus according to claim 13, wherein the catalyst outlet of the gas-solid separator III is located above the outlet end of the lift tube reactor.

17. 1. A process for the co-production of aromatics and olefins by coupling naphtha with methanol, comprising: The apparatus according to any one of claims 1 to 16 is used, and a metal zeolite bifunctional catalyst is used as the catalyst. A feedstock containing naphtha is fed from a first sub-distributor to an aromatization reactor by coupling naphtha and methanol, a feedstock containing methanol is fed from second to n sub-distributors to an aromatization reactor by coupling naphtha and methanol, a lift tube reactor feedstock containing low carbon paraffins is fed to the lift tube reactor, a bed reactor feedstock is fed to the bed reactor, and a regeneration gas is fed to a regenerator; The naphtha-methanol coupling aromatization reactor and the bed reactor output product gas, and a spent catalyst is input to a regenerator through a spent agent transport pipe I and a spent agent transport pipe II, the spent catalyst is reacted with a regeneration gas in the regenerator to be regenerated, and then transported to the naphtha-methanol coupling aromatization reactor and the lift tube reactor, and the regenerator discharges exhaust gas.

18. The catalyst is a metal-modified HZSM-5 zeolite molecular sieve, The metal used for the metal modification is at least one selected from La, Zn, Ga, Fe, Mo, and Cr, 18. The method of claim 17, wherein the metal modification method comprises immersing HZSM-5 zeolite molecular sieve in a metal salt solution, drying, and calcining to obtain the metal-modified HZSM-5 zeolite molecular sieve.

19. 18. The method according to claim 17, wherein the naphtha is at least one selected from the group consisting of direct coal liquefaction naphtha, indirect coal liquefaction naphtha, straight-run naphtha, and hydrocracked naphtha.

20. The naphtha-containing feedstock further comprises unreacted naphtha separated from the product gas stream, the unreacted naphtha being C ４ -C １２ 18. The process of claim 17, wherein the hydrocarbons comprise linear, branched, aliphatic hydrocarbons and naphthenes.

21. The reaction conditions for the aromatization reaction section by coupling naphtha and methanol are: gas apparent linear velocity 0.5-2.0 m / s, reaction temperature 500-600°C, reaction pressure 100-500 kPa, bed density 150-700 kg / m ３ 18. The method of claim 17, wherein:

22. 18. The method of claim 17, wherein the carbon content in the regenerated catalyst is 0.5 wt% or less.

23. 18. The method of claim 17, wherein the regeneration gas is at least one selected from oxygen, air, and oxygen-enriched air.

24. The reaction conditions in the regeneration section are: gas apparent linear velocity 0.5-2.0 m / s, regeneration temperature 600-750°C, regeneration pressure 100-500 kPa, bed density 150-700 kg / m ３ 18. The method of claim 17, wherein:

25. 18. The method of claim 17, wherein the lift tube reactor feed further comprises steam, the steam content being 0-80 wt%.

26. 18. The method of claim 17, wherein the low carbon paraffins in the lift tube reactor feed are separated from the product gas stream.

27. The reaction conditions of the lift tube reactor are: superficial linear gas velocity of 3.0-10.0 m / s, temperature of 580-700°C, pressure of 100-500 kPa, bed density of 50-150 kg / m ３ 18. The method of claim 17, wherein:

28. 18. The method of claim 17, wherein the bed reactor feed is obtained separately from the product gas stream.

29. The bed reactor feed comprises unreacted naphtha separated from the product gas stream, the unreacted naphtha being C ４ -C １２ 18. The process of claim 17, wherein the hydrocarbons comprise linear, branched, aliphatic hydrocarbons and naphthenes.

30. The bed reactor feed is C ３ , C ４ and C ５ 18. The method of claim 17, comprising a hydrocarbon.

31. The bed reactor feed is C ４ and C ５ 18. The method of claim 17, comprising a hydrocarbon.

32. The reaction conditions for the light hydrocarbon aromatization reaction zone are: gas superficial linear velocity of 0.5-2.0 m / s, reaction temperature of 550-665°C, reaction pressure of 100-500 kPa, bed density of 150-700 kg / m ３ 18. The method of claim 17, wherein:

33. The naphtha enters the reaction zone through a first sub-distributor of a distributor of the naphtha and methanol coupling aromatization reactor and contacts the catalyst from the regenerator to produce a product gas stream containing BTX, light olefins, hydrogen, light alkanes, combustible gases, heavy aromatic hydrocarbons, and unconverted naphtha. The catalyst from the regenerator enters the gas-solid separation device II and is separated into gas and solid. The catalyst from which the gas has been removed moves between the first sub-distributor and the second sub-distributor. Methanol enters the reaction zones of the naphtha-methanol coupling aromatization reactor from the second sub-distributor to the nth sub-distributor of the distributor, and undergoes a methylation reaction with benzene and toluene in the product gas stream to produce paraxylene. The catalyst from the regenerator is converted into a regenerated catalyst by being concentrated in the aromatization reaction zone of naphtha and methanol coupling. The product gas flow enters the gas-solid separator I to remove the intermediate catalyst therein, then enters the gas collection chamber I and passes through the product gas transport pipe I to enter the downstream process. The catalyst for aromatization reaction of the naphtha and methanol coupling enters the stripper I through the open end of the stripper I inlet pipe and is stripped. After stripping, it passes through the spent slide valve I and the spent agent transport pipe I into the downstream section. The regeneration gas is sent to the regeneration section of the regenerator through the distributor of the regenerator, and contacts with the auxiliary catalyst from the naphtha and methanol aromatization reactor and the auxiliary catalyst from the light hydrocarbon aromatization reactor. The coke on the catalyst reacts with the regeneration gas to produce smoke, and the catalyst changes into a regenerated catalyst. The raw material of the lift tube reactor is fed into the reactor from the inlet end of the lift tube reactor, and contacts and reacts with the regenerated catalyst from the regenerator. The feedstock in the lift tube reactor is converted into BTX, low carbon olefins, and H 2 After being converted into a stream containing components such as ethane, the stream passes through the outlet end of the lift tube reactor and enters the lower inner part of the light hydrocarbon aromatization reaction zone of the bed reactor; The feedstock of the bed reactor is sent to the light hydrocarbon aromatization reaction zone through the distributor of the bed reactor, and contacts the catalyst from the lift tube reactor to produce BTX, low carbon olefins and H 2 18. The method of claim 17, wherein the catalyst is converted to a catalytic converter while producing a light hydrocarbon aromatization product gas containing components such as:

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