CN113652258A - Aromatic hydrocarbon production system and method for preventing metal catalytic coking - Google Patents

Aromatic hydrocarbon production system and method for preventing metal catalytic coking Download PDF

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Publication number
CN113652258A
CN113652258A CN202110858877.4A CN202110858877A CN113652258A CN 113652258 A CN113652258 A CN 113652258A CN 202110858877 A CN202110858877 A CN 202110858877A CN 113652258 A CN113652258 A CN 113652258A
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reforming
reactor
coking
feeding
pipeline
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CN113652258B (en
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顾大利
仲俊威
王纪龙
王军伟
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Ningbo Zhongjin Petrochemical Co ltd
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Ningbo Zhongjin Petrochemical Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G35/00—Reforming naphtha
    • C10G35/04—Catalytic reforming
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G35/00—Reforming naphtha
    • C10G35/24—Controlling or regulating of reforming operations
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/30—Aromatics
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Abstract

The invention relates to the technical field of aromatic hydrocarbon production, and discloses an aromatic hydrocarbon production system and method for preventing metal catalytic coking, wherein the system comprises a feeding unit, a heating furnace, a reforming reactor and a gas-liquid separator which are sequentially connected through a feeding pipeline, and a gas-phase injection unit which is connected with the feeding pipeline between the feeding unit and the heating furnace through an injection pipeline; the gas-phase injection unit comprises a coking inhibitor feeding device and a nitrogen pipeline which are respectively connected with an injection pipeline, and the injection pipeline is communicated with a feeding pipeline between the feeding unit and the heating furnace. According to the invention, the gas-phase agent injection unit is arranged in the system, and a coking inhibitor can be injected into the system through the gas-phase agent injection unit before the material is fed into the reforming reactor, so that the surfaces of metal components in the reforming reactor and the heating furnace are passivated, and the phenomenon of metal catalytic coking can be effectively avoided in the production process.

Description

Aromatic hydrocarbon production system and method for preventing metal catalytic coking
Technical Field
The invention relates to the technical field of aromatic hydrocarbon production, in particular to an aromatic hydrocarbon production system and method for preventing metal catalytic coking.
Background
Naphtha catalytic reforming is one of the main methods for producing aromatic hydrocarbons, and can convert naphtha with low octane number into dyes with high octane number or aromatic hydrocarbon products such as benzene, toluene, xylene and the like. Naphtha catalytic reforming is mainly divided into two modes of semi-regeneration and continuous regeneration according to the regeneration mode of a catalyst, and both the two modes use a metal catalyst. In the reaction system for producing aromatic hydrocarbon by catalytic reforming of naphtha in the prior art, a furnace tube of a heating furnace, the inner wall of a reactor and internal components are generally made of metal materials, and if the dehydrogenation activity of metal ions of the metal ions is not inhibited, the metal ions are in contact with hydrocarbon in the production process to generate stronger dehydrocarbonization reaction, so that a large amount of coking is generated in the reactor, and the internal components of the reactor are damaged in severe cases.
In order to inhibit the catalytic coking of the metal of the reforming device, the current common practice is to add a coking inhibitor during feeding so as to passivate the inner walls of the reactor and the heating furnace and inhibit the catalytic activity of the metal. For example, the publication No. CN101423774B of "a passivation method for initial reaction of continuous reforming device" disclosed in Chinese patent literature includes loading a reforming catalyst into a continuous reforming device, raising the temperature of a reactor to 350-420 ℃ under hydrogen circulation, introducing raw oil, gradually raising the temperature of the reactor to 460-480 ℃, and injecting sulfide into the raw oil while feeding the oil, so that the sulfur content in the reforming feed is more than 0.5 μ g/g to 50 μ g/g.
Although the method for adding the coking inhibitor into the feeding materials can well inhibit metal catalytic coking during the stable operation of the device, the method is not enough to quickly and fully passivate the inner walls of the reactor and the heating furnace when the device is started for the first time or the catalyst is replaced by new catalyst, so that the phenomenon of metal catalytic coking still occurs in the production process after the passivation method is adopted.
Disclosure of Invention
The invention provides an aromatic hydrocarbon production system and method for preventing metal catalytic coking, aiming at overcoming the problems that when a device which is started for the first time or a new catalyst is replaced, the inner walls of a reactor and a heating furnace cannot be passivated quickly and sufficiently when a coking inhibitor is added into a feed material to inhibit the metal coking of a reforming device in the prior art, and the metal catalytic coking phenomenon can be avoided in the production process.
In order to achieve the purpose, the invention adopts the following technical scheme:
an aromatic hydrocarbon production system for preventing metal catalytic coking comprises a feeding unit, a heating furnace, a reforming reactor and a gas-liquid separator which are sequentially connected through a feeding pipeline, and a gas-phase agent injection unit which is connected with the feeding pipeline between the feeding unit and the heating furnace through an agent injection pipeline; the gas-phase injection unit comprises a coking inhibitor feeding device and a nitrogen pipeline which are respectively connected with an injection pipeline, and the injection pipeline is communicated with a feeding pipeline between the feeding unit and the heating furnace.
According to the invention, the gas-phase agent injection unit communicated with the feeding pipeline is arranged in the system, a coking inhibitor can be injected into the system through the gas-phase agent injection unit before the material is fed into the reforming reactor, and the coking inhibitor is used for passivating the surfaces of metal components in the heating furnace tube, the inner wall of the reforming reactor, the catalyst and other systems in the heating furnace, so that the phenomenon of metal catalytic coking in the reforming reactor and the heating furnace in the production process is avoided.
In the initial operation stage of the system, because the activity of the catalyst in the reforming reactor is high and the surfaces of metal components in the heating furnace and the reforming reactor are not passivated, metal catalytic coking is easy to occur after direct feeding, when the system operates, the liquid coking inhibitor in the coking inhibitor feeding device is injected into a feeding pipeline through an injection pipeline under the carrying and diluting effects of nitrogen and is mixed with circulating hydrogen entering the feeding pipeline through a feeding unit, so that the coking inhibitor and the circulating hydrogen sequentially pass through the heating furnace and the reforming reactor along the feeding pipeline to passivate the surface of the metal component in the coking inhibitor feeding device in advance, and the metal catalytic coking can be avoided after feeding; and (4) feeding the passivated material into a gas-liquid separator for gas-liquid separation, and continuously feeding the separated recycle hydrogen into a feeding unit for recycling. After the metal components in the system are passivated, a mixture of naphtha and recycle hydrogen is introduced into the system through the feeding unit, the naphtha is subjected to catalytic reforming reaction under the action of a catalyst in a reforming reactor, a liquid aromatic hydrocarbon product is obtained after separation of a gas-liquid separator, and the gaseous recycle hydrogen continuously enters the feeding unit for recycling.
Preferably, the reforming reactor comprises a first reforming reactor, a second reforming reactor, a third reforming reactor and a fourth reforming reactor which are connected in series, and each reforming reactor is provided with a feeding hole and a discharging hole; a first hearth, a second hearth, a third hearth and a fourth hearth which are connected in parallel are arranged in the heating furnace, and heating furnace tubes are respectively arranged in the hearths; two ends of a heating furnace tube in the first hearth are respectively connected with a feeding unit and a feeding port of the reforming first reactor through feeding pipelines; two ends of the heating furnace tube in the second hearth are respectively connected with a discharge hole of the reforming first reactor and a feed hole of the reforming second reactor through feed pipelines; two ends of a heating furnace tube in the third hearth are respectively connected with a discharge hole of the reforming second reactor and a feed hole of the reforming third reactor through feed pipelines; two ends of a heating furnace tube in the fourth hearth are respectively connected with a discharge hole of the reforming third reactor and a feed hole of the reforming fourth reactor through feed pipelines; and a discharge hole of the reforming fourth reactor is connected with the gas-liquid separator through a feed pipeline.
The invention arranges four reforming reactors in series in the system, so that the reactant naphtha sequentially passes through the four reforming reactors to react, thereby ensuring the yield of the produced aromatic hydrocarbon. Meanwhile, four parallel hearths are arranged in the heating furnace, reactants pass through the heating furnace tubes in the corresponding hearths before entering each reforming reactor to heat the reactants, so that the temperature of the reactants meets the reaction requirement, and the normal operation of the system and the yield of products are ensured.
Preferably, a booster pump is arranged on the agent injection pipeline between the coking inhibitor feeding device and the feeding pipeline.
Preferably, the agent injection pipeline and the nitrogen pipeline are respectively provided with a control valve.
Preferably, the catalyst is a platinum-based catalyst.
Preferably, the coking inhibitor is selected from one or more of sulfur-containing compounds, phosphorus-containing compounds and sulfur-phosphorus compounds.
Preferably, the preparation method of the coking inhibitor comprises the following steps:
(1) adding maleic anhydride, dimethyl hydroxymethyl phosphate and gamma-glycidyl ether oxypropyl trimethoxy silane into a solvent, uniformly stirring, adding a first catalyst, reacting for 8-10 hours at 140-160 ℃, and removing the solvent to obtain a first reaction product;
(2) dissolving ethylenediamine in a solvent to obtain an ethylenediamine solution, adding dichloromethylthio phosphine into the ethylenediamine solution at the temperature of 0-20 ℃ under the protection of nitrogen, stirring for 20-30 min, heating to 40-45 ℃, carrying out heat preservation reaction for 10-15 h, and removing the solvent to obtain a second reaction product;
(3) and mixing the first reaction product and the second reaction product under the protection of nitrogen at 40-45 ℃, adding a second catalyst, stirring for 20-30 min, heating to 60-80 ℃, introducing nitrogen, and reacting for 20-30 h to obtain the coking inhibitor.
At present, a coking inhibitor used in catalytic reforming reaction is mainly a sulfur-containing or phosphorus-containing compound, and a decomposition product of the sulfur-containing or phosphorus-containing compound at high temperature can be adsorbed on the surface of metal to form a layer of protective film, so that the generation and growth of metal catalytic coke are inhibited, and the coking rate is reduced. However, the prior sulfur-containing or phosphorus-containing compound has effective passivation effect on the metal surface and generally has poor coking inhibition effect. In order to improve the passivation effect of a coking inhibitor on the metal surface, the invention firstly uses maleic anhydride to react with hydroxyl in dimethyl hydroxymethyl phosphate and epoxy group in gamma-glycidyl ether oxypropyl trimethoxy silane to obtain phosphate group and siloxane group modified maleic acid ester through the step (1); then, through the step (2), reacting ethylenediamine with dichloromethyl thiophosphine to obtain a diaminophospho intermediate; and finally, performing Michael addition reaction by using the amino group of the diaminophosulfuron intermediate and the modified maleic acid ester in the step (3) to finally obtain the sulfur-containing phosphorus compound with modified siloxane group in the molecular chain.
When the sulfur-containing phosphorus compound with modified siloxane groups in the molecular chain prepared by the method is used as a coking inhibitor, the sulfur-phosphorus component can effectively form a protective film on the metal surface to passivate the metal surface; meanwhile, the siloxane groups can effectively improve the anti-adhesion property of the metal surface and reduce the adhesion between the metal surface and the carbon particles, thereby further reducing the carbon deposition amount on the metal surface and effectively avoiding the metal catalytic coking phenomenon in the reaction process.
Preferably, the ratio of the amount of the maleic anhydride to the total amount of the dimethyl hydroxymethyl phosphate and the gamma-glycidoxypropyltrimethoxysilane in the step (1) is 1:2 to 2.4, and the ratio of the amount of the dimethyl hydroxymethyl phosphate to the gamma-glycidoxypropyltrimethoxysilane is 2 to 3: 1; the first catalyst is selected from one or more of p-toluenesulfonic acid, sodium methoxide and triethylamine, and the dosage of the first catalyst is 0.01-0.05% of the total mass of reactants.
Although the silicone silicon group is introduced into the coking inhibitor to be beneficial to improving the inhibition effect of the silicone silicon group on metal catalytic coking, the excessive addition of the silicon element can cause catalyst deactivation and influence the yield of the product. According to the invention, by controlling the addition of each reactant, the catalyst can not be deactivated while the coking inhibitor can effectively inhibit metal catalytic coking.
Preferably, the ratio of the amounts of dichloromethylthiophosphine and ethylenediamine added in step (2) is 1:2 to 2.2.
Preferably, the mass ratio of the first reaction product to the second reaction product in the step (3) is 2-2.2: 1; the second catalyst is sodium methoxide, and the addition amount of the second catalyst is 0.03-0.05% of the total mass of the reactants.
The invention also provides an aromatic hydrocarbon production method using the production system, which comprises the following steps:
(1) filling a catalyst into the reforming reactor;
(2) introducing hydrogen into the system in a circulating manner through a feeding unit;
(3) heating the temperature of a feed inlet of a reforming reactor to 450-500 ℃, diluting a coking inhibitor with nitrogen through a gas-phase injection unit, mixing the diluted coking inhibitor with hydrogen, introducing the mixture into a system, and passivating metal in the system;
(4) stopping introducing the coking inhibitor and the nitrogen after the passivation is finished, introducing naphtha into the system through the feeding unit while keeping circularly introducing the hydrogen, and performing a reforming reaction to obtain an aromatic hydrocarbon product.
Preferably, the concentration of the coking inhibitor introduced in the step (3) in the gas is 15-25 x 10-6L/L, and the time for introducing the coking inhibitor is 2-3 h. Although components such as S, P, Si in the coking inhibitor can inhibit metal catalytic coking, excessive addition of the components can also affect the activity of the catalyst, so the addition amount of the coking inhibitor needs to be strictly controlled, and the activity of the catalyst is ensured while the metal surface in the system is effectively passivated.
Preferably, when the reforming reaction is carried out in the step (4), the temperature of the feed inlet of the reforming reactor is 525-535 ℃, and the liquid hourly space velocity is 1.2-2.0 h-1。
Therefore, the invention has the following beneficial effects:
(1) a gas-phase agent injection unit communicated with a feeding pipeline is arranged in the system, a coking inhibitor can be injected into the system through the gas-phase agent injection unit before the material is fed into the reforming reactor, and the surfaces of metal components in the heating furnace tube in the heating furnace, the inner wall of the reforming reactor and other systems are passivated through the coking inhibitor, so that the phenomenon of metal catalytic coking in the reforming reactor and the heating furnace in the production process is avoided;
(2) a sulfur-containing phosphorus compound with modified siloxane groups in a molecular chain is used as a coking inhibitor, and sulfur and phosphorus components can effectively form a protective film on the surface of metal to passivate the surface of the metal; meanwhile, the siloxane groups can effectively improve the anti-adhesion property of the metal surface and reduce the adhesion between the metal surface and the carbon particles, thereby further reducing the carbon deposition amount on the metal surface and effectively avoiding the metal catalytic coking phenomenon in the reaction process.
Drawings
Fig. 1 is a schematic view of the connection structure of the present invention.
In the figure: 1 feeding unit, 2 heating furnace, 2-1 first hearth, 2-2 second hearth, 2-3 third hearth, 2-4 fourth hearth, 3-1 reforming first reactor, 3-2 reforming second reactor, 3-3 reforming third reactor, 3-4 reforming fourth reactor, 4 gas-liquid separator, 5 coking inhibitor feeding device, 6 nitrogen pipeline, 7 feeding pipeline, 8 injection pipeline, 9 heating furnace tube, 10 booster pump, 11 control valve.
Detailed Description
The invention is further described with reference to the following detailed description and accompanying drawings.
In the present invention, all the raw materials are commercially available or commonly used in the industry, and the methods in the following examples are conventional in the art unless otherwise specified.
As shown in fig. 1, an aromatic hydrocarbon production system for preventing metal-catalyzed coking used in the examples and comparative examples of the present invention comprises a feed unit 1, a heating furnace 2, a reforming reactor and a gas-liquid separator 4 connected in this order by a feed line 7, and a gas-phase injection unit connected to the feed line between the feed unit and the heating furnace by an injection line 8.
The reforming reactor comprises a first reforming reactor 3-1, a second reforming reactor 3-2, a third reforming reactor 3-3 and a fourth reforming reactor 3-4 which are connected in series, a feed inlet and a discharge outlet are respectively arranged on each reforming reactor, and a catalyst is arranged in each reforming reactor; a first hearth 2-1, a second hearth 2-2, a third hearth 2-3 and a fourth hearth 2-4 which are connected in parallel are arranged in the heating furnace, and U-shaped heating furnace tubes 9 are respectively arranged in each hearth. Two ends of a heating furnace tube in the first hearth are respectively connected with a feeding unit and a feeding port of the reforming first reactor through feeding pipelines; two ends of a heating furnace tube in the second hearth are respectively connected with a discharge hole of the reforming first reactor and a feed hole of the reforming second reactor through feed pipelines; two ends of a heating furnace tube in the third hearth are respectively connected with a discharge hole of the reforming second reactor and a feed hole of the reforming third reactor through feed pipelines; two ends of a heating furnace tube in the fourth hearth are respectively connected with a discharge hole of the reforming third reactor and a feed hole of the reforming fourth reactor through feed pipelines; and a discharge hole of the reforming fourth reactor is connected with the gas-liquid separator through a feed pipeline.
The gas-phase injection unit comprises a coking inhibitor feeding device 5 and a nitrogen pipeline 6 which are respectively connected with an injection pipeline, and the injection pipeline is communicated with a feeding pipeline between the feeding unit and the heating furnace; a coking inhibitor is arranged in the coking inhibitor feeding device; a booster pump 10 is arranged on an injection pipeline between the coking inhibitor feeding device and the feeding pipeline, and control valves 11 are respectively arranged on the injection pipeline and the nitrogen pipeline.
Example 1:
a process for producing aromatic hydrocarbons comprising the steps of:
(1) filling a commercially available reforming catalyst into the reforming reactor;
(2) introducing hydrogen into the system by a feeding unit in a circulating manner, wherein the circulating gas flow is 4 multiplied by 104Nm3/h；
(3) Heating the temperature of the feed inlet of each reforming reactor to 480 ℃, diluting a coking inhibitor with nitrogen by a gas-phase injection unit, mixing the diluted coking inhibitor with hydrogen, introducing the mixture into a system, and passivating the metal in the system; the coking inhibitor adopts dimethyl disulfide, and the content of the coking inhibitor in the circulating gas is 20 multiplied by 10-6L/L, wherein the time for introducing the coking inhibitor is 2.5 hours;
(4) stopping introducing the coking inhibitor and the nitrogen after the passivation is finished, introducing naphtha into the system through the feeding unit while keeping circularly introducing the hydrogen, and performing a reforming reaction to obtain an aromatic hydrocarbon product; during the reforming reaction, the temperature of the feed inlet of each reforming reactor is 528 ℃, and the liquid hourly space velocity is 1.45h-1。
Example 2:
a process for producing aromatic hydrocarbons comprising the steps of:
(1) filling a commercially available reforming catalyst into the reforming reactor;
(2) introducing hydrogen into the system by a feeding unit in a circulating manner, wherein the circulating gas flow is 4 multiplied by 104Nm3/h；
(3) Feeding each reforming reactor intoThe temperature of the material inlet is increased to 480 ℃, a coking inhibitor is diluted by nitrogen through a gas phase injection unit and then mixed with hydrogen to be introduced into the system, and the metal in the system is passivated; the content of coking inhibitor in the circulating gas is 20 × 10-6L/L, wherein the time for introducing the coking inhibitor is 2.5 hours;
(4) stopping introducing the coking inhibitor and the nitrogen after the passivation is finished, introducing naphtha into the system through the feeding unit while keeping circularly introducing the hydrogen, and performing a reforming reaction to obtain an aromatic hydrocarbon product; during the reforming reaction, the temperature of the feed inlet of each reforming reactor is 528 ℃, and the liquid hourly space velocity is 1.45h-1。
The preparation method of the coking inhibitor comprises the following steps:
A) adding maleic anhydride, dimethyl hydroxymethyl phosphate and gamma-glycidoxypropyltrimethoxysilane into xylene, wherein the ratio of the amount of the maleic anhydride to the total amount of dimethyl hydroxymethyl phosphate and gamma-glycidoxypropyltrimethoxysilane is 1:2.1, and the ratio of the amount of dimethyl hydroxymethyl phosphate to the amount of gamma-glycidoxypropyltrimethoxysilane is 2: 1; after stirring uniformly, adding a sodium methoxide catalyst, wherein the adding amount of the sodium methoxide catalyst is 0.03 percent of the total mass of reactants, reacting for 9 hours at 150 ℃, and removing the solvent under reduced pressure to obtain a first reaction product;
B) dissolving ethylenediamine in dichloromethane to obtain an ethylenediamine solution, adding dichloromethyl thiophosphine with the mass ratio of the dichloromethyl thiophosphine to the ethylenediamine being 1:2.1 into the ethylenediamine solution at 10 ℃ under the protection of nitrogen, stirring for 25min, heating to 42 ℃, keeping the temperature, reacting for 12h, and removing the solvent to obtain a second reaction product;
C) mixing a first reaction product and a second reaction product with the mass ratio of 2.1:1 at 42 ℃ under the protection of nitrogen, adding a sodium methoxide catalyst accounting for 0.04% of the total mass of reactants, stirring for 25min, heating to 70 ℃, introducing nitrogen to react for 24h, and obtaining the coking inhibitor.
Example 3:
a process for producing aromatic hydrocarbons comprising the steps of:
(1) filling a commercial platinum-rhenium reforming catalyst into a reforming reactor;
(2) through a feeding unitIntroducing hydrogen into the system in a circulating manner, wherein the flow rate of the circulating gas is 5 multiplied by 104Nm3/h；
(3) Heating the temperature of the feed inlet of each reforming reactor to 450 ℃, diluting a coking inhibitor with nitrogen by a gas-phase injection unit, mixing the diluted coking inhibitor with hydrogen, introducing the mixture into a system, and passivating the metal in the system; the content of coking inhibitor in the circulating gas is 15 × 10-6L/L, wherein the time for introducing the coking inhibitor is 3 hours;
(4) stopping introducing the coking inhibitor and the nitrogen after the passivation is finished, introducing naphtha into the system through the feeding unit while keeping circularly introducing the hydrogen, and performing a reforming reaction to obtain an aromatic hydrocarbon product; during the reforming reaction, the temperature of the feed inlet of each reforming reactor is 525 ℃, and the liquid hourly space velocity is 1.2h-1。
The preparation method of the coking inhibitor comprises the following steps:
A) adding maleic anhydride, dimethyl hydroxymethyl phosphate and gamma-glycidoxypropyltrimethoxysilane into xylene, wherein the ratio of the amount of the maleic anhydride to the total amount of dimethyl hydroxymethyl phosphate and gamma-glycidoxypropyltrimethoxysilane is 1:2.4, and the ratio of the amount of dimethyl hydroxymethyl phosphate to the amount of gamma-glycidoxypropyltrimethoxysilane is 3: 1; stirring uniformly, adding a sodium methoxide catalyst, wherein the adding amount of the sodium methoxide catalyst is 0.01 percent of the total mass of reactants, reacting for 10 hours at 140 ℃, and removing the solvent under reduced pressure to obtain a first reaction product;
B) dissolving ethylenediamine in dichloromethane to obtain an ethylenediamine solution, adding dichloromethyl thiophosphine with the mass ratio of the dichloromethyl thiophosphine to the ethylenediamine being 1:2 into the ethylenediamine solution at 0 ℃ under the protection of nitrogen, stirring for 20min, heating to 40 ℃, keeping the temperature and reacting for 15h, and removing the solvent to obtain a second reaction product;
C) mixing a first reaction product and a second reaction product with the mass ratio of 2:1 at 40 ℃ under the protection of nitrogen, adding a sodium methoxide catalyst accounting for 0.03% of the total mass of reactants, stirring for 20min, heating to 60 ℃, introducing nitrogen to react for 30h, and obtaining the coking inhibitor.
Example 4:
a process for producing aromatic hydrocarbons comprising the steps of:
(1) filling a commercial platinum-rhenium reforming catalyst into a reforming reactor;
(2) introducing hydrogen into the system by a feeding unit in a circulating manner, wherein the circulating gas flow is 5 multiplied by 104Nm3/h；
(3) Heating the temperature of the feed inlet of each reforming reactor to 500 ℃, diluting a coking inhibitor with nitrogen by a gas-phase injection unit, mixing the diluted coking inhibitor with hydrogen, introducing the mixture into a system, and passivating the metal in the system; the content of coking inhibitor in the circulating gas is 25 × 10-6L/L, wherein the time for introducing the coking inhibitor is 2 hours;
(4) stopping introducing the coking inhibitor and the nitrogen after the passivation is finished, introducing naphtha into the system through the feeding unit while keeping circularly introducing the hydrogen, and performing a reforming reaction to obtain an aromatic hydrocarbon product; during the reforming reaction, the temperature of the feed inlet of each reforming reactor is 535 ℃, and the liquid hourly space velocity is 2.0h-1。
The preparation method of the coking inhibitor comprises the following steps:
A) adding maleic anhydride, dimethyl hydroxymethyl phosphate and gamma-glycidoxypropyltrimethoxysilane into xylene, wherein the ratio of the amount of the maleic anhydride to the total amount of dimethyl hydroxymethyl phosphate and gamma-glycidoxypropyltrimethoxysilane is 1:2.4, and the ratio of the amount of dimethyl hydroxymethyl phosphate to the amount of gamma-glycidoxypropyltrimethoxysilane is 3: 1; after stirring uniformly, adding a sodium methoxide catalyst, wherein the adding amount of the sodium methoxide is 0.05 percent of the total mass of reactants, reacting for 8 hours at 160 ℃, and removing the solvent under reduced pressure to obtain a first reaction product;
B) dissolving ethylenediamine in dichloromethane to obtain an ethylenediamine solution, adding dichloromethyl thiophosphine with the mass ratio of the dichloromethyl thiophosphine to the ethylenediamine being 1:2.2 into the ethylenediamine solution at the temperature of 20 ℃ under the protection of nitrogen, stirring for 30min, heating to 45 ℃, keeping the temperature and reacting for 10h, and removing the solvent to obtain a second reaction product;
C) mixing a first reaction product and a second reaction product with the mass ratio of 2.2:1 at 45 ℃ under the protection of nitrogen, adding a sodium methoxide catalyst accounting for 0.05 percent of the total mass of reactants, stirring for 30min, heating to 80 ℃, introducing nitrogen to react for 20h, and obtaining the coking inhibitor.
Comparative example 1 (no pre-passivation before feeding):
a process for producing aromatic hydrocarbons comprising the steps of:
(1) filling a commercial platinum-rhenium reforming catalyst into a reforming reactor;
(2) introducing hydrogen into the system by a feeding unit in a circulating manner, wherein the circulating gas flow is 4 multiplied by 104Nm3/h；
(3) While keeping the cyclic introduction of hydrogen, introducing naphtha into the system through a feeding unit for carrying out reforming reaction to obtain an aromatic hydrocarbon product, wherein the temperature of a feeding port of each reforming reactor is 528 ℃ and the liquid hourly space velocity is 1.45h during the reforming reaction-1(ii) a While introducing naphtha, diluting the coking inhibitor with nitrogen by a gas phase injection unit, mixing the diluted coking inhibitor with hydrogen and naphtha, and introducing the mixture into a system, wherein the content of the coking inhibitor in the circulating gas is 20 multiplied by 10-6L/L, and the coking inhibitor adopts dimethyl disulfide.
Comparative example 2 (too high concentration of coke inhibitor fed):
a process for producing aromatic hydrocarbons comprising the steps of:
(1) filling a commercially available reforming catalyst into the reforming reactor;
(2) introducing hydrogen into the system by a feeding unit in a circulating manner, wherein the circulating gas flow is 4 multiplied by 104Nm3/h；
(3) Heating the temperature of the feed inlet of each reforming reactor to 480 ℃, diluting a coking inhibitor with nitrogen by a gas-phase injection unit, mixing the diluted coking inhibitor with hydrogen, introducing the mixture into a system, and passivating the metal in the system; the content of coking inhibitor in the circulating gas is 35 × 10-6L/L, wherein the time for introducing the coking inhibitor is 2.5 hours;
(4) stopping introducing the coking inhibitor and the nitrogen after the passivation is finished, introducing naphtha into the system through the feeding unit while keeping circularly introducing the hydrogen, and performing a reforming reaction to obtain an aromatic hydrocarbon product; during the reforming reaction, the temperature of the feed inlet of each reforming reactor is 528 ℃, and the liquid hourly space velocity is 1.45h-1。
The preparation method of the coking inhibitor is the same as that in the example 2.
Comparative example 3 (no phosphate groups introduced in the coking inhibitor):
the method for preparing the coking inhibitor used in comparative example 3 comprises the following steps:
A) adding maleic anhydride and gamma-glycidoxypropyltrimethoxysilane into xylene in a mass ratio of 1:2.1, uniformly stirring, adding a sodium methoxide catalyst, reacting at 150 ℃ for 9 hours, and removing the solvent under reduced pressure to obtain a first reaction product, wherein the addition amount of the sodium methoxide is 0.03 percent of the total mass of reactants;
B) dissolving ethylenediamine in dichloromethane to obtain an ethylenediamine solution, adding dichloromethyl thiophosphine with the mass ratio of the dichloromethyl thiophosphine to the ethylenediamine being 1:2.1 into the ethylenediamine solution at 10 ℃ under the protection of nitrogen, stirring for 25min, heating to 42 ℃, keeping the temperature, reacting for 12h, and removing the solvent to obtain a second reaction product;
C) mixing a first reaction product and a second reaction product with the mass ratio of 2.1:1 at 42 ℃ under the protection of nitrogen, adding a sodium methoxide catalyst accounting for 0.04% of the total mass of reactants, stirring for 25min, heating to 70 ℃, introducing nitrogen to react for 24h, and obtaining the coking inhibitor.
The rest is the same as in example 2.
Comparative example 4 (too many siloxane groups introduced in the coking inhibitor):
the method for preparing the coking inhibitor used in comparative example 4 comprises the following steps:
A) adding maleic anhydride, dimethyl hydroxymethyl phosphate and gamma-glycidoxypropyltrimethoxysilane into xylene, wherein the ratio of the amount of the maleic anhydride to the total amount of dimethyl hydroxymethyl phosphate and gamma-glycidoxypropyltrimethoxysilane is 1:2.1, and the ratio of the amount of dimethyl hydroxymethyl phosphate to the amount of gamma-glycidoxypropyltrimethoxysilane is 1: 1; after stirring uniformly, adding a sodium methoxide catalyst, wherein the adding amount of the sodium methoxide catalyst is 0.03 percent of the total mass of reactants, reacting for 9 hours at 150 ℃, and removing the solvent under reduced pressure to obtain a first reaction product;
B) dissolving ethylenediamine in dichloromethane to obtain an ethylenediamine solution, adding dichloromethyl thiophosphine with the mass ratio of the dichloromethyl thiophosphine to the ethylenediamine being 1:2.1 into the ethylenediamine solution at 10 ℃ under the protection of nitrogen, stirring for 25min, heating to 42 ℃, keeping the temperature, reacting for 12h, and removing the solvent to obtain a second reaction product;
C) mixing a first reaction product and a second reaction product with the mass ratio of 2.1:1 at 42 ℃ under the protection of nitrogen, adding a sodium methoxide catalyst accounting for 0.04% of the total mass of reactants, stirring for 25min, heating to 70 ℃, introducing nitrogen to react for 24h, and obtaining the coking inhibitor.
The rest is the same as in example 2.
Comparative example 5 (no siloxane groups introduced in the coking inhibitor):
the method for preparing the coking inhibitor used in comparative example 5 comprises the following steps:
A) adding maleic anhydride and dimethyl hydroxymethyl phosphate with the mass ratio of 1:2.1 into xylene, uniformly stirring, adding a sodium methoxide catalyst, reacting at 150 ℃ for 9 hours, and removing a solvent under reduced pressure to obtain a first reaction product, wherein the addition amount of the sodium methoxide catalyst is 0.03 percent of the total mass of reactants;
B) dissolving ethylenediamine in dichloromethane to obtain an ethylenediamine solution, adding dichloromethyl thiophosphine with the mass ratio of the dichloromethyl thiophosphine to the ethylenediamine being 1:2.1 into the ethylenediamine solution at 10 ℃ under the protection of nitrogen, stirring for 25min, heating to 42 ℃, keeping the temperature, reacting for 12h, and removing the solvent to obtain a second reaction product;
C) mixing a first reaction product and a second reaction product with the mass ratio of 2.1:1 at 42 ℃ under the protection of nitrogen, adding a sodium methoxide catalyst accounting for 0.04% of the total mass of reactants, stirring for 25min, heating to 70 ℃, introducing nitrogen to react for 24h, and obtaining the coking inhibitor.
The rest is the same as in example 2.
Comparative example 6 (direct blending of the reactants as a coking inhibitor):
the coking inhibitor in comparative example 6 employs a mixture of dimethyl hydroxymethyl phosphate, gamma-glycidoxypropyltrimethoxysilane and dichloromethylthiophosphine in a mass ratio of 1.4:0.7:1, the remainder being the same as in example 2.
The reforming reactor in the above examples and comparative examples was tested for pressure drop and coking, product oil yield, and aromatic content in the product oil after 4 months of operation, and the results are shown in table 1.
Table 1: and testing the coking condition of the system.
Figure BDA0003185115070000101
As can be seen from table 1, in examples 1 to 4, when the system and the method of the present invention are used for aromatic hydrocarbon production, the yield of the product oil and the content of aromatic hydrocarbon in the product oil are high after the system is operated for 4 months, and the production requirements are met; the reforming reactor basically has no metal catalytic coking phenomenon, and the system can normally run. In addition, compared with the traditional fixed dimethyl disulfide coking inhibitor adopted in the embodiment 1, the coking inhibitor prepared in the invention adopted in the embodiments 2-4 has better inhibition effect on metal catalytic coking, and the pressure drop of the system after continuous operation is smaller.
In the comparative example 1, the metal components in the system are not pre-passivated by using a coking inhibitor before feeding, but the coking inhibitor is added in the feeding process, the pressure drop of the reforming reactor in the system operation process is increased, the pressure drop of the fourth reactor can reach over 67Kpa after 4 months, the coking in the third reactor and the fourth reactor is serious, the system needs to be shut down and repaired, and the product yield is also influenced.
In comparative example 2, when the concentration of the coking inhibitor introduced during pre-passivation is too high, the yield of the product oil and the content of aromatic hydrocarbon in the product oil during system operation are both remarkably reduced, probably because S, P, Si element in the product oil can cause the reduction of the activity of the catalyst when the concentration of the coking inhibitor is too high. In the comparative example 3, phosphate groups are not introduced into the coking inhibitor, and compared with the coking inhibitor in the example 2, the passivation effect of the coking inhibitor on metal is obviously reduced, so that the coking phenomenon in the system operation process cannot be effectively avoided. Too much siloxane groups introduced during the preparation of the coking inhibitor in comparative example 4 may affect the catalyst activity, resulting in product yield. In the comparative example 5, siloxane groups are not introduced into the coking inhibitor, which also influences the passivation effect of the coking inhibitor on metals, and the coking phenomenon in the system operation process can not be effectively avoided. In comparative example 6, the coking inhibiting effect of example 2 could not be achieved by directly mixing hydroxymethyl dimethyl phosphate, gamma-glycidoxypropyltrimethoxysilane, and dichloromethylthiophosphine as the coking inhibitor.

Claims (10)

1. The aromatic hydrocarbon production system capable of preventing metal catalytic coking is characterized by comprising a feeding unit (1), a heating furnace (2), a reforming reactor and a gas-liquid separator (4) which are sequentially connected through a feeding pipeline (7), and a gas-phase injection unit which is connected with the feeding pipeline between the feeding unit and the heating furnace through an injection pipeline (8); the gas-phase injection unit comprises a coking inhibitor feeding device (5) and a nitrogen pipeline (6) which are respectively connected with an injection pipeline, and the injection pipeline is communicated with a feeding pipeline between the feeding unit and the heating furnace; a coking inhibitor is arranged in the coking inhibitor feeding device; the reforming reactor is internally provided with a catalyst.
2. The aromatic hydrocarbon production system for preventing metal catalytic coking according to claim 1, wherein the reforming reactor comprises a first reforming reactor (3-1), a second reforming reactor (3-2), a third reforming reactor (3-3) and a fourth reforming reactor (3-4) which are connected in series, and each reforming reactor is provided with a feeding hole and a discharging hole; a first hearth (2-1), a second hearth (2-2), a third hearth (2-3) and a fourth hearth (2-4) which are connected in parallel are arranged in the heating furnace, and a heating furnace tube (9) is respectively arranged in each hearth; two ends of a heating furnace tube in the first hearth are respectively connected with a feeding unit and a feeding port of the reforming first reactor through feeding pipelines; two ends of the heating furnace tube in the second hearth are respectively connected with a discharge hole of the reforming first reactor and a feed hole of the reforming second reactor through feed pipelines; two ends of a heating furnace tube in the third hearth are respectively connected with a discharge hole of the reforming second reactor and a feed hole of the reforming third reactor through feed pipelines; two ends of a heating furnace tube in the fourth hearth are respectively connected with a discharge hole of the reforming third reactor and a feed hole of the reforming fourth reactor through feed pipelines; and a discharge hole of the reforming fourth reactor is connected with the gas-liquid separator through a feed pipeline.
3. The aromatic hydrocarbon production system for preventing metal catalyzed coking as claimed in claim 1 or 2, wherein a booster pump (10) is arranged on the agent injection pipeline between the coking inhibitor feeding device and the feeding pipeline.
4. A system for the production of aromatics with prevention of metal-catalyzed coking as claimed in claim 1 or 2, wherein the agent injection line and the nitrogen gas line are provided with control valves (11), respectively.
5. An aromatics production system with protection against metal-catalyzed coking as claimed in claim 1 or claim 2, wherein the catalyst is a platinum-group catalyst.
6. The aromatic hydrocarbon production system for preventing metal catalyzed coking as claimed in claim 1 or 2, wherein the coking inhibitor is one or more selected from the group consisting of sulfur-containing compounds, phosphorus-containing compounds and sulfur-phosphorus compounds.
7. A method for producing aromatic hydrocarbons using the production system according to any one of claims 1 to 6, comprising the steps of:
(1) filling a catalyst into the reforming reactor;
(2) introducing hydrogen into the system in a circulating manner through a feeding unit;
(3) heating the temperature of a feed inlet of a reforming reactor to 450-500 ℃, diluting a coking inhibitor with nitrogen through a gas-phase injection unit, mixing the diluted coking inhibitor with hydrogen, introducing the mixture into a system, and passivating metal in the system;
(4) stopping introducing the coking inhibitor and the nitrogen after the passivation is finished, introducing naphtha into the system through the feeding unit while keeping circularly introducing the hydrogen, and performing a reforming reaction to obtain an aromatic hydrocarbon product.
8. According to the claimsThe aromatic hydrocarbon production method of claim 7 is characterized in that the content of the coking inhibitor introduced in the step (3) in the gas is 15-25 x 10-6L/L, and the time for introducing the coking inhibitor is 2-3 h.
9. A process for producing aromatic hydrocarbons according to claim 7, wherein the temperature of the feed port of the reforming reactor at the time of the reforming reaction in the step (4) is 525 to 535 ℃.
10. The method for producing aromatic hydrocarbons according to claim 7 or 9, wherein the liquid hourly space velocity during the reforming reaction in the step (4) is 1.2 to 2.0h-1。
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114749108A (en) * 2022-04-06 2022-07-15 盛虹炼化(连云港)有限公司 Online loading and unloading method and system for catalyst for fluidized bed residual oil hydrogenation process

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1430662A (en) * 2000-09-22 2003-07-16 菲利浦石油公司 Improved catalytic reforming process
CN101445746A (en) * 2007-11-28 2009-06-03 中国石油化工股份有限公司 Pre-passivation method for continuous reforming device
US20100282645A1 (en) * 2007-10-31 2010-11-11 China Petroleum & Chemical Corporation Pre-passivation process for a continuous reforming apparatus, and passivation process for a continuous reforming apparatus during the initial reacation
CN206454619U (en) * 2017-02-20 2017-09-01 宁波中金石化有限公司 It is a kind of to reduce the system that catalyst carries hydro carbons
CN107434981A (en) * 2016-05-26 2017-12-05 中石化广州工程有限公司 A kind of method of continuous reformer note sulphur

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1430662A (en) * 2000-09-22 2003-07-16 菲利浦石油公司 Improved catalytic reforming process
US20100282645A1 (en) * 2007-10-31 2010-11-11 China Petroleum & Chemical Corporation Pre-passivation process for a continuous reforming apparatus, and passivation process for a continuous reforming apparatus during the initial reacation
CN101445746A (en) * 2007-11-28 2009-06-03 中国石油化工股份有限公司 Pre-passivation method for continuous reforming device
CN107434981A (en) * 2016-05-26 2017-12-05 中石化广州工程有限公司 A kind of method of continuous reformer note sulphur
CN206454619U (en) * 2017-02-20 2017-09-01 宁波中金石化有限公司 It is a kind of to reduce the system that catalyst carries hydro carbons

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114749108A (en) * 2022-04-06 2022-07-15 盛虹炼化(连云港)有限公司 Online loading and unloading method and system for catalyst for fluidized bed residual oil hydrogenation process
CN114749108B (en) * 2022-04-06 2023-07-07 盛虹炼化(连云港)有限公司 Method and system for on-line loading and unloading catalyst for ebullated bed residuum hydrogenation process

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