WO2009067858A1 - A predeactivation method and a deactivation method during initial reaction for a continuous reforming apparatus - Google Patents

A predeactivation method and a deactivation method during initial reaction for a continuous reforming apparatus Download PDF

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Publication number
WO2009067858A1
WO2009067858A1 PCT/CN2008/001819 CN2008001819W WO2009067858A1 WO 2009067858 A1 WO2009067858 A1 WO 2009067858A1 CN 2008001819 W CN2008001819 W CN 2008001819W WO 2009067858 A1 WO2009067858 A1 WO 2009067858A1
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Prior art keywords
reforming
gas
hydrogen
reaction
reactor
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PCT/CN2008/001819
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English (en)
French (fr)
Inventor
Jieguang Wang
Aizeng Ma
Jianqiang Ren
Changqing Ji
Xinkuan Zhang
Hengfang Chen
Yajun Zhao
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China Petroleum & Chemical Corporation
Research Institute Of Petroleum Processing, Sinopec
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Priority claimed from CN200710176571A external-priority patent/CN101423774B/zh
Priority claimed from CN 200710178229 external-priority patent/CN101445746B/zh
Application filed by China Petroleum & Chemical Corporation, Research Institute Of Petroleum Processing, Sinopec filed Critical China Petroleum & Chemical Corporation
Priority to EP08854893.8A priority Critical patent/EP2210929B1/en
Priority to US12/740,458 priority patent/US8475650B2/en
Priority to RU2010119051/04A priority patent/RU2470065C2/ru
Publication of WO2009067858A1 publication Critical patent/WO2009067858A1/zh

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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
    • C10G35/06—Catalytic reforming characterised by the catalyst used
    • C10G35/085—Catalytic reforming characterised by the catalyst used containing platinum group metals or compounds thereof
    • C10G35/09—Bimetallic catalysts in which at least one of the metals is a platinum group metal
    • 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
    • C10G35/06—Catalytic reforming characterised by the catalyst used
    • C10G35/065—Catalytic reforming characterised by the catalyst used containing crystalline zeolitic molecular sieves, other than aluminosilicates
    • 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
    • C10G35/22—Starting-up 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
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/207—Acid gases, e.g. H2S, COS, SO2, HCN
    • 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
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/30—Physical properties of feedstocks or products
    • C10G2300/305—Octane number, e.g. motor octane number [MON], research octane number [RON]
    • 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
    • C10G2300/70—Catalyst aspects
    • C10G2300/705—Passivation
    • 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
    • C10G2400/02—Gasoline
    • 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

Definitions

  • a passivation method for pre-passivation and initial reaction of a continuous reforming device is provided.
  • the invention relates to a method for pre-passivation and initial reaction passivation of a continuous reforming device, in particular to a passivation method of a reaction device before or during a feed reaction of a continuous reforming device.
  • the continuous regenerative catalytic reforming of naphtha is highly valued in the production of high-octane gasoline and aromatic hydrocarbons due to its high liquid recovery, high hydrogen yield and high aromatic yield.
  • the reforming catalyst used in the continuous reformer is a series of dual or polymetallic catalysts containing platinum tin, which is more sensitive to platinum-tin catalysts than platinum-only catalysts. Therefore, to ensure the normal operation of the catalytic reformer, there is a strict limit on the sulfur content in the reforming feedstock.
  • CN1234455C US Pat. No. 6,495,487 B1 and US Pat. No. 6,780,814, B2 disclose the use environment requirements of a platinum-tin multimetal reforming catalyst, and indicate that during normal operation of the continuous reforming reaction, the naphtha feedstock for reforming is subjected to catalytic desorption and adsorption. The way to remove sulfur from the oil to the lowest level, the best sulfur-free.
  • the platinum-tin series reforming catalyst requires the control index of the impurity content of the reforming raw material, and the sulfur content is generally controlled to be not more than 0.5 g/g.
  • Continuous reforming operation pressure is relatively low, reaction temperature is high, hydrogen/oil is relatively low, and the device is more likely to coke during the reaction.
  • continuous reforming has continued to increase in the direction of ultra-low pressure, low hydrogen/oil ratio, low space velocity, etc., and the tendency of the reactor and the heating furnace tube to coke is also increasing.
  • multiple sets of continuous reformers have been subjected to reactor wall coking. Coking can cause poor catalyst flow, damage to internal components of the reactor, and even equipment downtime, which can result in significant economic losses to the refinery.
  • Catalytic Reforming Process and Engineering (first edition, November 2006, China Petrochemical Press), pp. 522-534, analyzes the mechanism of coking in a continuous reformer: hydrocarbon molecules are adsorbed in a reducing atmosphere
  • the surface of the metal grains of the reactor wall is excessively dehydrogenated to form carbon atoms under the metal catalysis of the wall, and is dissolved or infiltrated into the grains or between the particles of the metal. Due to The deposition and growth of carbon separates the metal grains from the matrix, resulting in a filamentous carbon with metal iron particles at the front end. This carbon is obviously different from the carbon deposit on the catalyst, and has high catalytic dehydrogenation and hydrogenolysis activity.
  • the filamentous carbon becomes longer and thicker. Harden.
  • the development of filamentous carbon generally goes through several stages of development of soft carbon, soft bottom carbon and hard carbon. The longer the formation time, the more serious the consequences.
  • the circulation system may be blocked and cannot be circulated normally; in severe cases, the internal components of the reactor such as the scallop and the center tube may be damaged. If the generated coke enters the regeneration system, it will cause local over-temperature of the scorch zone of the regenerator and over-temperature of the oxychlorination zone to burn out the internal components of the regenerator. The degree of damage to the reactor and regenerator internal components becomes more severe as the operating time increases.
  • the continuous reforming operation is based on the refinery material balance, hydrogen balance and product requirements.
  • the severity of the reaction is increased quickly when the water in the gas is qualified.
  • the sulfur content of the reforming feed is controlled between 0.2 and 0.5 g/g, especially for new plants that are used for the first time, not enough to passivate the reactor and the furnace tube wall quickly and fully, and a considerable part of the continuous reformer After the passivation method described above, the coking of the reaction system still occurs during the operation. Therefore, how to effectively suppress the metal-catalyzed coking of the continuous reforming reactor and the heating furnace wall becomes an important subject of continuous reforming technicians.
  • CN1160435C discloses a method for inhibiting coke deposition in a pyrolysis furnace, which is used before introducing hydrocarbon feedstock into a thermal cracking furnace.
  • Sulfur and phosphorus containing compound treatment pyrolysis furnace the sulfur / phosphorus atomic ratio of at least 5, the addition of a sufficient amount of sulfur compounds in the phosphorus compound can form a uniform and effective on the surface of the pyrolysis furnace
  • the passivation layer is used to inhibit the deposition of coke.
  • CN85106828A discloses a method and a device for forming a surface of a metal part, and placing the metal part on a cathode disk of a reaction chamber in a vacuum furnace while being in a vacuum furnace
  • the solid sulfur is placed, and the solid stone is vaporized by heating.
  • the vaporized sulfur bombards the metal part on the cathode disk under the action of the electric field, thereby forming a vulcanized layer on the surface thereof.
  • CN 1126607C discloses a method for inhibiting and slowing the formation and deposition of coke in hydrocarbon pyrolysis, which pretreats a metal surface with a pretreatment agent before injection of the cracking feedstock into the cracking equipment with water vapor, pretreatment
  • the agent is one or a mixture of two or more of hydrogen, an organic sulfur compound, an organic phosphorus, and an organosulfur compound.
  • This method can passivate the metal surface of the cracker to inhibit and reduce coke formation and deposition during the cracking process and subsequent processing.
  • the reforming apparatus provided by the present invention has two passivation methods, one is pre-passivation before the reforming raw material enters the apparatus, and the other is a passivation method in which the reaction raw material enters the apparatus for initial reaction.
  • the pre-passivation method of the continuous reforming apparatus comprises charging a reforming catalyst in a continuous reforming unit, starting a gas circulation and raising the temperature of the reactor, and the reactor temperature is in the range of 100 to 650 ° C. Sulfide is injected into the gas inward, and the sulfur content in the control gas is 0.5 to: l00x l (T 6 L/L to passivate the device.
  • the passivation method for initial reaction of the continuous reforming apparatus comprises the following steps: (1) loading a reforming catalyst in a continuous reforming unit, starting a gas circulation and raising the temperature of the reactor, when the temperature of the reactor When the temperature is raised to 300 ⁇ 460 °C, the reforming feedstock oil is introduced into the reaction system, and the sulfide is introduced into the reaction system simultaneously or after the reforming feedstock oil is introduced, and the total sulfur amount in the introduction system is controlled.
  • the ratio of the reforming feedstock oil is between 0.5 g/g and 50 g/g, and when the hydrogen concentration in the recycle gas reaches 2. ( ⁇ L/L ⁇ 3 ( ⁇ L/L, the deuteration is introduced into the system) Amount,
  • the pre-passivation method of the above reforming device is to inject a chemical into the reaction system under a condition of a certain temperature and a flow of the gaseous medium before the continuous reforming device is introduced into the reaction raw material, by controlling a certain sulfur content in the gas. Passivation of the high temperature vessel and the pipe wall of the reaction system of the continuous reformer can effectively suppress the catalytic coking of the metal wall of the device. More sulfide should be injected into the system, and then the amount of sulfide introduced should be adjusted to make the device operate normally under the specified conditions.
  • the method of the invention can effectively passivate the wall of the reaction device before or at the beginning of the reforming reaction, prevent coking caused by active metal catalysis of the wall, and reduce the operational risk of the device.
  • Figures 1 and 2 are electron micrographs of the carbon blocks collected in Comparative Example 1.
  • Figure 3 is a photograph of the coke at the bottom of the reactor in Comparative Example 1.
  • Figure 4 is an electron micrograph of a coke sample in Comparative Example 2, which is a filamentous carbon with iron particles on top. detailed description
  • a telluride is added to the flowing gaseous medium in the reaction system before the catalyst is charged in the continuous reforming unit, and the high temperature portion of the reactor such as the continuous regenerative reforming unit and the heating furnace tube is added.
  • the wall is sufficiently passivated, and then the reaction device is purged with a gas that does not affect the reaction, so that the sulfur content in the device does not affect the catalytic method.
  • the method of introducing the device before the reforming reaction can inhibit the high temperature hydrogen site.
  • the catalytic activity of the wall metal prevents the catalytic coking caused by the metal wall during the reaction and reduces the operational risk of the device.
  • the process of the present invention pre-passivates the walls of the gas flowing into the gas flowing into the system prior to the oil reforming of the continuous reformer.
  • the recycle gas generally refers to the gas circulating within the system as a passivating medium.
  • the recycle gas is preferably hydrogen, an inert gas or a mixture of hydrogen and an inert gas.
  • the inert gas is preferably nitrogen.
  • the reforming reactor is first charged with a catalyst, pre-twisted
  • the temperature is from 100 to 650 ° C, preferably from 100 to 450 ° C, more preferably from 150 to 300 ° C.
  • Gas circulation is established in the system and the reactor is heated.
  • the inlet temperature of the reactor is raised to 120 to 2 60 ° C
  • the sulfide is injected and the temperature is raised.
  • the inlet temperature of the reactor is raised to 370 to 420 ° C, the temperature is maintained for 1 to 50 hours, preferably 2 to 10 hours.
  • the sulfur content of the gas in the reaction device during the pre-passivation process is controlled to be 0.5 to 100 x 1 (T 6 L/L, preferably 2 to 20 x 1 (T 6 L/L, more preferably 3 to 20 10- 6 L/L, most gas means preferably 3 ⁇ 6x lO_ 6 L / L.
  • the exhaust gas after the pre-passivation, into the reforming reaction does not affect the subsequent replacement of the replacement gas, the exhaust gas to a sulfur content of not greater than 5.0x lO- 6 L / L, preferably When it is not more than 2.0x lO _6 L/L, the reforming reaction is carried out according to the conventional reaction conditions.
  • the replacement gas used for the original circulating gas in the displacement device is hydrogen, an inert gas or a mixture of an inert gas and hydrogen.
  • hydrogen or nitrogen is used.
  • 0.1 to 5.0 MPa preferably 0.35 to 2.0 MPa, temperature 350 to 600 ° C, preferably 430 to 560 ° C, more preferably 490 to 545 ° C, hydrogen/hydrocarbon molar ratio 1 to 20, preferably 2 to: 10, liquid hourly space Speed (LHSV) l ⁇ 10hr _1 , preferably l ⁇ 5hr -1 .
  • LHSV liquid hourly space Speed
  • the sulfide to be injected into the circulating gas is preferably hydrogen sulfide, carbon disulfide, dimercapto disulfide, aliphatic sulfur-containing compound, alicyclic sulfur-containing compound, aromatic sulfur-containing compound, thiophene, morpholine compound or Any two or a mixture of two or more of the compounds, wherein the thiophene or morpholine compound means a derivative of thiophene or morpholine.
  • the injected sulfide is preferably hydrogen sulfide; when the passivation is shielded by hydrogen, the injected sulfide may be hydrogen sulfide or the above organic sulfide.
  • the continuous reforming reaction system in the initial stage of the reaction, is first introduced into the oil at a low temperature, and a certain amount of sulfide is introduced into the reaction system during the temperature rise of the reaction system and the constant temperature dehydration and conditioning operation.
  • the sulfur content entering the system reaches a relatively high level, that is, the ratio of the total sulfur in the controlled introduction system to the reforming feedstock oil is between more than 0.5 g/g and 5 ( ⁇ g/g, when hydrogen sulfide in the recycle gas
  • the sulfur content of the introduction system is further lowered, and after the water content in the system is qualified, the reaction temperature is raised to make the device perform a normal production operation.
  • the manner of introducing the sulfide into the reaction system may be Adding sulfide to the reforming feedstock oil, or adding hydrogen sulfide or hydrogen sulfide-containing gas to the recycle gas, or adding hydrogen sulfide or hydrogen sulfide-containing gas to the recycle gas, and
  • the whole feedstock oil is added with 3 ⁇ 4IL.
  • the hydrogen sulfide-containing gas is hydrogen from a reforming pre-hydrogenation system, or other hydrogen-containing gas having a higher concentration of hydrogen sulfide, the hydrogen-containing gas.
  • hydrogen content of 50 ⁇ 500 ⁇ L / L, preferably 100 ⁇ 200 ( ⁇ L / L, and more preferably 200 ⁇ 80( ⁇ L/L.
  • the continuous reforming reactor and the heating furnace tube wall can be sufficiently and quickly passivated, thereby suppressing the occurrence of coking. Affects the progress of the operation of the device and the reactivity of the catalyst when the continuous reformer is operated under high severity conditions.
  • the step (1) is the low-temperature injection of sulfur after the start of the operation of the device, and the introduction of the device at the same time or after the introduction of the oil at a low temperature, preferably controlling the total sulfur amount and the reforming feedstock in the introduction system.
  • the ratio is 0.6 to 2 C ⁇ g/g, and more preferably 1.0 to: I0 g/g.
  • the hydrogen sulfide content in the recycle gas of the reformer should be periodically checked. When the concentration of sulphuric hydrogen in the recycle gas reaches 2.0 ⁇ 30 ⁇ , preferably 2.0 ⁇ 6.0 ⁇ , it will be introduced into the system. The total amount of sulfide is lowered.
  • the ratio of total sulfur to reformate feedstock introduced into the system is adjusted to 0.2 to 0.5 g/g.
  • step (1) after the total sulfur content in the reaction system is lowered, the ratio of the total sulfur amount in the introduction system to the reforming feedstock oil is reduced to 0.2 to 2. ( ⁇ g/g, preferably (10 g/g) After the concentration of hydrogen sulfide in the gas to be recycled is less than 5. ( ⁇ L/L, preferably 0.2 to 2. C ⁇ L / L, depending on the carbon deposition of the catalyst, the regeneration system can be started to carry out the catalyst regeneration.
  • the sulfide introduced in the step (1) is hydrogen sulfide, carbon disulfide, dimercapto disulfide, aliphatic compound, alicyclic sulfur compound, aromatic sulfur compound, thiazine, morpholine A compound or a mixture of any two or more of the compounds, wherein the thiophene or morpholine compound means a derivative of thiophene or morpholine.
  • hydrogen, thioether, hydrogen sulfide or carbon disulfide is preferred, and the thioether is preferably dimethyl disulfide or dimethyl ketone.
  • chlorides should also be introduced while introducing sulfide into the reforming system.
  • the amount of chlorine injected can be carried out according to the conventional chlorine injection requirements. Generally, when the water content in the circulating hydrogen is greater than 500 L/L, the amount of chlorine injected is 30 to 50 g/g; when the water content in the circulating hydrogen is 300 to 50 ( ⁇ L/L, the amount of chlorine injected is 15 to 3) ( ⁇ g/g; When the water content in circulating hydrogen is 100 ⁇ 200 L/L, the amount of chlorine injected is 5 ⁇ l ( ⁇ g/g; when the water content in circulating hydrogen is 50 ⁇ 100 L/L, the amount of chlorine injected) It is 2 to 5 g/g.
  • the chloride used for chlorine injection is preferably a halogenated alkane or a halogenated alkene such as dichloroethane, trichloroethane, tetrachloroethylene, tetrachloropropene or carbon tetrachloride.
  • Step (2) of the embodiment is a constant temperature control process which maintains a lower amount of sulfide introduced into the reaction system, and the ratio of the total sulfur amount of the introduced system to the reforming feedstock is controlled to 0.2 to 0.5 g. /g, the reaction temperature is raised to the desired reforming reaction temperature after the water content in the circulating gas is reduced to a prescribed value, and the preferred method of operation is when the water in the circulating gas is contained After the amount is less than 200 ⁇ ! ⁇ , the reaction temperature is raised to 460 ⁇ 490 °C, and the drainage is continued at this temperature. When the water content in the circulating gas is lower than 5 ( ⁇ L/L, the reforming is carried out according to the design amount.
  • the raw material is raised according to the octane number of the liquid product, and the reaction temperature is generally raised to 490 to 545 ° C to carry out a normal reforming operation.
  • the pressure for controlling the reforming reaction during operation is 0.1 to 5.0 MPa.
  • the molar ratio of hydrogen to feedstock oil is from 1 to 20, preferably from 2 to 10;
  • the feed hourly space velocity (LHSV) is l lOhf 1 , preferably from 1 to 5 hr -
  • the feed amount of the reformate feedstock in the step (1) of the embodiment is generally lower than the design feed amount of the apparatus, preferably from 50 to 75 mass% of the reformer design feed amount.
  • the reforming raw oil is introduced into the reforming unit according to the design amount of the reforming device in the step (2) for the normal reforming reaction.
  • the recycle gas refers to a gas which is recycled to the reaction system after the reforming reaction product is gas-liquid separated, and is mainly hydrogen.
  • the gas before the oil feed refers to the gas circulating in the system, and the recycle gas is preferably hydrogen, an inert gas or a mixture of hydrogen and an inert gas, preferably nitrogen.
  • the reforming catalyst charged into the reaction system is preferably a series of double or multimetal catalysts containing platinum tin.
  • the reforming catalyst comprises a carrier and 0.01% by mass, preferably 0.1 to 1.0% by mass, based on the dry carrier, of a platinum group metal, 0.01 to 5.0% by mass, preferably 0.12.0% by mass of tin and 0.1 to 10% by mass, preferably 0.15.0% by mass of halogen;
  • the platinum group metal is platinum, rhodium, palladium, iridium, ruthenium or osmium, preferably platinum, preferably chloro
  • the carrier is preferably alumina, more preferably ⁇ -oxidation aluminum.
  • it may further contain a third and/or a ruthenium metal component selected from the group consisting of ruthenium, osmium, titanium and the like to further improve the catalytic performance of the catalyst, and the content of the third and/or ruthenium metal component in the catalyst is 0.01 to 5.0 mass.
  • % is preferably 0.05 to 3.0% by mass, and more preferably 0.1 to 2.0% by mass.
  • the continuous reforming apparatus described in the method of the present invention is a variety of moving bed continuous regenerative catalytic reforming units.
  • the continuously reformed feedstock oil may be straight run naphtha, hydrocracked heavy naphtha, hydrocoking gasoline, ethylene cracked gasoline raffinate oil, catalytically cracked gasoline, or a mixture of several of the raw materials.
  • the range of the distillation range controlled by the feedstock varies depending on the target product.
  • the initial boiling point of the feedstock oil is generally 60 to 95 ° C, and the final boiling point is generally 135 to 180 °C.
  • the impurities of the reforming feedstock are: ⁇ 0.5 g/g, nitrogen ⁇ 0.5 g/g, arsenic ⁇ lng/g, H0ng/g, copper ⁇ 101 ⁇ , water ⁇ 5.
  • the reforming device passivation method of the invention is suitable for the continuous regenerative reforming device of the platinum tin series catalyst, and is particularly suitable for the first use process of the new continuous reforming device.
  • the invention is further illustrated by the following examples, but the invention is not limited thereto. Example 1
  • the reforming catalyst was packed in a continuous reforming unit containing 0.29% by mass of platinum, 0.31% by mass of tin, and the balance being ⁇ -alumina.
  • the continuous reforming unit was first replaced with nitrogen having a purity of 99.8 mol% until the oxygen content of the exhaust gas was less than 0.5 mol%, and then the system was replaced with hydrogen having a purity of 96 mol% to a hydrogen content of the exhaust gas of more than 90 mol%.
  • the pressure of the reforming high-pressure separator was pressurized with hydrogen to 350 KPa, and the reforming compressor cycle was started so that the circulating gas volume was 5 x 10 4 Nm 3 /h. After each reactor was heated at a rate of 20 to 40 ° C per hour until the inlet temperature of the reactor was 200 ° C, the injection of dimethyl diether into the recycle gas was started and the temperature was further increased, and the dimercapto sulphate was charged.
  • the content of ruthenium in the recycle gas is 3 ⁇ 5xl (T 6 L/L.
  • T 6 L/L the content of ruthenium in the recycle gas
  • the inlet temperature of the reactor is raised to 370 °C, the temperature is kept constant for 3 hours, then the sulphur injection is stopped, and the system is replaced with hydrogen with a purity of 96 mol%.
  • the content of 3 ⁇ 4 in the recycle gas is reduced to 2x l (below T 6 L/L, and then the reforming feedstock is introduced to carry out the reforming reaction.
  • the composition of the reforming feedstock is shown in Table 1.
  • the reaction conditions and results are shown in Table 2. No carbon block was observed during sampling, and no coking was observed in the high temperature parts such as the shutdown check reactor. Comparative Example 1
  • the reforming catalyst was charged in a continuous reforming unit having the same composition as in Example 1.
  • the continuous reforming unit was first replaced with nitrogen having a purity of 99.8 mol% until the oxygen content of the exhaust gas was less than 0.5 mol%, and then the system was replaced with hydrogen having a purity of 93 mol% to a hydrogen content of the exhaust gas of more than 60 mol%.
  • the pressure of the reforming high-pressure separator was pressurized to 350 KPa with hydrogen, and the reforming compressor cycle was started to make the circulating gas flow rate 4 ⁇ 10 4 Nm 3 /h, and the respective reactors were heated at a rate of 20 to 40 ° C per hour. To 370 ° C.
  • the reforming feedstock oil was introduced into the reforming reactor, and its composition is shown in Table 1.
  • the dimethyl disulfide is injected into the raw material to make the sulfur content in the raw material 0.2 to 0.3 g/g, and then the reaction is carried out under the normal operation of the reforming operation conditions, the main operating conditions and the reaction results. See Table 2.
  • the catalyst sample is collected from the separation hopper after the reformer is operated for 3 months, the carbon block of 1 ⁇ 5mm size is often found.
  • the electron micrographs of the carbon block sample are shown in Figure 1 and Figure 2 respectively. The photo shows that the carbon block is on the top. Filamentous carbon of iron particles.
  • Table 1 Table 1
  • the average pressure of the reaction system for controlling the continuous reformer is 0.45 MPa, and the high partial pressure is 0.34 MPa.
  • the catalyst amount of the reaction system was 50060 kg, which contained 0.28% by mass of platinum, 0.31% by mass of tin, and 1.10% by mass of chlorine.
  • the naphtha shown in Table 3 was used as a raw material.
  • the reactor temperature is raised to 490 Torr and dehydrated at this temperature, while dehydrating, the amount of chlorine injected is gradually lowered according to the water content in the circulating gas.
  • the water in the recycle gas is less than 50 L/L
  • the feed amount is gradually increased to 95 ton / hr, and the inlet temperature of each reactor is reformed to 530 °C.
  • the continuous reforming unit described in Comparative Example 2 was normally shut down, overhauled, unloaded, the inside of the reactor was cleaned, and a small amount of small carbon particles in the catalyst was separated by sieving and gravity sedimentation, and the catalyst was recharged. After the production.
  • the reforming feedstock and catalyst described in Comparative Example 2 were used. After checking the system for hydrogen gas tightness, start the hydrogen cycle and start to warm the reaction system at a rate of 40 ⁇ 50 / hour.
  • the reforming feedstock is started, and the feed amount is 57 ton / hr, while raising the reactor to 480 ° C at a rate of 20 ⁇ 30 ° C / hour, while heating, inject dimethyl disulfide and tetrachloroethylene into the reforming feed, and control
  • the reforming feed had a sulfur content of 6.0 g/g. After the sulfide was injected into the raw material, the concentration of hydrogen sulfide in the reforming cycle gas was analyzed every two hours.
  • the concentration of hydrogen sulfide in the recycle gas reaches 2 L/L
  • the amount of sulfide injected is lowered to a sulfur content of 0.2 to 0.5 g/g in the reforming feed.
  • the water content in the reforming cycle gas is lower than 20 ( ⁇ L/L, the reactor temperature is raised to 490 °C and dehydrated at this temperature, while dehydrating, the amount of chlorine injected is gradually reduced according to the water content in the circulating gas.
  • the reforming feed amount is gradually increased to 95 ton / hr, and the reforming reactor inlet temperature is raised to 530 ° C.
  • Example 4 According to the method of Example 2, the continuous reforming device was normally shut down for maintenance and unloading, and the reaction was started after the catalyst was charged. The difference was that the sulfur injection amount in the reforming reaction raw material after the reforming reactor was fed was 10 g/g. The main operating conditions and reaction results of each reactor after normal operation are shown in Table 4. Example 4
  • the continuous reforming device was normally shut down for maintenance and unloading, and the reaction was started after the catalyst was charged.
  • the difference was that the reforming reactor did not inject organic sulfur compounds into the raw material oil after the feeding, but the reforming was carried out.
  • the pre-hydrogenation tail gas is introduced into the reforming system, the sulfur content in the tail gas is 550 ⁇ 7 ⁇ , the hydrogen purity is 94%, the introduction flow rate is controlled at 500-550 Nm 3 /h, and the ratio of sulfur introduced into the system to the reforming feedstock entering the system is 4 g/g, when the concentration of hydrogen sulfide in the recycle gas of the reformer reaches 2 ⁇ 7 ⁇ , the introduction flow rate of the pre-hydrogenated tail gas is controlled to 30 ⁇ 40Nm 3 /h, that is, the total sulfur content of the introduced system is lowered to the reforming feedstock oil.
  • the ratio is 0.3 to 0.5 g/g.
  • the reactivity of the catalyst in the process of the present invention was not affected by the high sulfur content in the feedstock oil at the initial stage of the reaction as compared with the result of the reaction of Comparative Example 2. After the unit was put into operation for one year, the reaction and recycling system was operating normally. When the catalyst sample was collected from the separation hopper, no carbon block of the filamentous carbon was found, and the catalyst and the heating tube did not undergo metal catalytic coking. Alkane 49.78 group composition, mass% cycloalkane 41.94 aromatics 8.24

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Description

一种连续重整装置预钝化和初始反应的钝化方法 技术领域.
本发明为一种连续重整装置预钝化和初始反应钝化方法， 具体地 说， 是一种连续重整装置进料反应前或反应初期反应装置的钝化方法。 背景技术
石脑油连续再生式催化重整以其液收高、 氢气产率高和芳烃产率 高等特点， 在高辛烷值汽油和芳烃的生产中受到人们的极大重视。 目 前， 连续重整装置使用的重整催化剂为含铂锡的系列双或多金属催化 剂， 与仅含铂的催化剂相比， 铂锡催化剂对 化物更敏感。 因此， 要 保证催化重整装置的正常运行， 对重整原料油中的硫含量要有严格的 限制。
CN1234455C, US6495487B1和 US6780814B2均公开了一种铂锡 多金属重整催化剂的使用环境要求， 指出在连续重整反应正常运行期 间， 用于重整的石脑油原料采用催化脱克和吸附脱^ ^的方式将油中的 硫脱除到最低水平， 无硫最理想。
《石油炼制与化工》 2002年第 33卷第 8期笫 26~29页和《工业催 化》 2003年第 11卷第 9期第 5〜8页，分别介绍了连续重整正常运转时， 使用铂锡系列重整催化剂对重整原料杂质含量的控制指标要求， 其中 硫含量一般控制在不大于 0.5 g/g。
连续重整操作压力相对较低、 反应温度较高、 氢 /油比较低， 反应 过程中装置更易结焦。 随着技术的进步， 连续重整不断向超低压、 低 氢 /油比、 低空速等苛刻度不断提高的方向发展， 反应器和加热炉管结 焦的倾向也在不断增加。 至今已有多套连续重整装置发生反应器壁结 焦。 结焦会导致催化剂流动不畅、 反应器内构件损坏， 甚至导致装置 停工， 因而给炼厂带来巨大的经济损失。
《催化重整工艺与工程》 （2006年 11月第一版，中国石化出版社） 第 522〜534 页， 对连续重整装置结焦的机理进行了分析： 在还原气氛 中烃类分子被吸附在反应器壁金属晶粒的表面， 在器壁金属催化作用 下过度脱氢生成碳原子， 并溶入或渗入金属的晶粒间或颗粒间。 由于 炭的沉积和生长使金属晶粒与基体分离， 结果产生前端带有金属铁粒 子的丝状炭。 这种炭与催化剂上的积炭明显不同， 具有较高的催化脱 氢和氢解活性， 一经生成， 就在高温下不断地反应， 生成速度继续加 快， 丝状炭不断变长、 变粗、 变硬。 丝状炭的发展一般经历软炭、 软 底炭、 硬炭几个发展阶段， 其形成时间越长， 带来的后果越严重。 装 置生焦早期， 可能会造成循环系统堵塞， 不能正常循环； 严重时会损 坏扇形筒、 中心管等反应器的内构件。 生成的焦炭若进入再生系统， 还会造成再生器烧焦区的局部超温和氧氯化区的超温， 烧坏再生器的 内构件。 反应器和再生器内构件的损坏程度随运转时间的延长会变得 更加严重。
为了防止连续重整装置金属器壁催化结焦， 《催化重整》 （ 2004 年 4月第一版， 中国石化出版社） 第 200〜202页， 介绍目前公知的 文 法是在正常的重整操作中， 向重整进料中注入有机硫化物， 控制重整 进料的硫含量为 0.2~0.3 g/g, 以抑制反应器内壁和加热炉管内壁金属 表面的催化活性。 但并没有介绍在连续重整装置^ ί氏温进油时即向原料 中注入硫化物， 一种比较普遍的做法是在各反应器入口温度达到
480-490 °C以上时开始往反应系统中注入^ <化物。
目前， 连续重整操作基于炼厂物料平衡、 氢气平衡和产品的需要， 往往在进油后， 待气中水合格时即较快地提高反应的苛刻度。 重整进 料的硫含量控制在 0.2〜0.5 g/g之间，特别是对于首次使用的新建装置， 不足以迅速、 充分地钝化反应器和加热炉管器壁， 相当一部分连续重 整装置采用上述钝化方法后， 在运转过程中仍出现反应系统结焦的情 况。 因此， 如何有效地抑制连续重整反应器和加热炉管器壁的金属催 化结焦成为连续重整技术人员关注的重要课题。
石油化工其它领域防止烃类在反应器高温部位结焦的方法有多 种， 其中 CN1160435C公开了一种热解炉中抑制焦炭沉积的方法， 该 法在向热裂解炉中通入烃原料之前， 用含硫和含磷的化合物处理热解 炉， 所迷硫 /磷的原子比至少为 5 , 在含磷化合物中加入足够量的含硫 化合物可使在热解炉的表面形成一层均匀、 有效的钝化层以抑制焦炭 的沉积。
CN85106828A公开了一种金属零件表面形成^ ^化物层的方法及设 备， 将金属零件放置在真空炉内反应室的阴极盘上， 同时在真空炉中 放置固体硫， '固体石克通过加热而气化， 气化硫在电场的作用下轰击位 于阴极盘上金属零件， 从而在其表面形成硫化层。
CN 1126607C 公开了一种抑制和減緩烃类高温裂解中焦炭形成与 沉积的方法， 该法用预处理剂在裂解原料通入前随水蒸汽一起注入裂 解设备中对金属表面进行预处理， 预处理剂是^ L化氢、 有机硫化合物、 有机磷以及有机硫磷化合物的一种或两种以上的混合物。 该法可使裂 解炉金属表面钝化以抑制和减少裂解过程以及后续处理过程中的焦炭 形成和沉积。
由于铂锡系连续重整催化剂对杂质极为敏感， 对环境要求高， 上 述方法所涉及的各种物质均会造成重整催化剂严重中毒或不可逆中 毒， 故不适用于催化重整过程。 发明内容
本发明的目的是提供一种连续重整装置预钝化和初始反应的钝化 方法， 该法可有效抑制反应器壁和加热炉管器壁的金属催化结焦， 降 低装置的运行风险。
本发明提供的重整装置钝化方法有两种， 一种为重整反应原料进 入装置之前的预钝化， 另一种为反应原料进入装置进行初始反应的钝 化方法。
本发明提供的连续重整装置的预钝化方法， 包括在连续重整装置 中装入重整催化剂， 启动气体循环并升高反应器的温度， 在反应器温 度为 100〜650°C的范围内向所述气体中注入硫化物，控制气体中硫含量 为 0.5〜： l00x l(T6L/L, 以对所述装置进行钝化。
本发明提供的连续重整装置初始反应的钝化方法， 包括如下步骤： ( 1 )在连续重整装置中装入重整催化剂， 启动气体循环并升高反 应器的温度，当反应器的温度升高到 300〜460 °C时向反应系统中通入重 整原料油， 并在通入重整原料油同时或之后向所述反应系统中引入硫 化物， 控制引入系统中的总硫量与重整原料油的比在大于 0.5 g/g 至 50 g/g之间， 当循环气中 化氢浓度达到 2.(^L/L〜3(^L/L时， 下调引 入系统中 υ化物的量，
( 2 )将重整反应器保持在 460〜49(TC , 待循环气中的水含量低于 5C^L/L时， 控制引入系统的总硫量与重整原料油的比为 0.2~0.5 g/g, 将重整进料量调至装置设计值， 按液体产品辛烷值的要求提高重整反 应温度至 490~545 °C , 转入正常操作的条件进行反应。
上述重整装置的预钝化方法是在连续重整装置通入反应原料前， 在一定的温度和气体介质流动的条件下， 向反应系统中注入^化物， 通过控制气体中一定的硫含量对连续重整装置反应系统高温容器和管 路的器壁进行钝化， 可有效抑制装置金属器壁的催化结焦。 应系统内注入较多的硫化物， 然后再调整硫化物的引入量， 使装置在 规定的条件下正常运转。
本发明方法可在重整反应之前或反应初期有效钝化反应装置的器 壁， 防止器壁活性金属催化引起的结焦产生， 降低装置的运行风险。 附图说明
图 1和图 2为对比例 1 中采集的炭块的电镜照片。
图 3为对比例 1中反应器底部结焦的照片。
图 4为对比例 2 中结焦样品的电镜照片， 是顶部带有铁粒子的丝 状炭。 具体实施方式
在本发明的一个实施方式中， 在连续重整装置装填催化剂开始进 油反应前， 向反应系统内流动气体介质中加入 υ化物， 对连续再生式 重整装置反应器和加热炉管等高温部位的器壁进行充分地钝化， 然后 再用不影响反应的气体吹扫反应装置， 使装置内的硫含量不影响催化 发明方法在重整反应前通入装置的^ 化物可抑制高温临氢部位器壁金 属的催化活性， 防止反应过程中金属器壁引起的催化结焦， 降低装置 的运行风险。
本发明方法在连续重整装置进油反应前向系统内流动气体中加入 化物进行器壁的预钝化， 所述的循环气体一般指作为钝化介质在系 统内循环的气体。 循环气体优选氢气、 惰性气体或氢气与惰性气体的 混合物。 所述的惰性气体优选氮气。
在所述实施方式中， 先向所述的重整反应器中装填催化剂， 预飩 化温度为 100〜650°C , 优选为 100~450°C , 更优选 150〜300°C , 在系统 内建立气体循环并使反应器升温，当反应器入口温度升至 120〜260°C时 开始注入硫化物并继续升温，当反应器入口温度升至 370〜420°C时保持 恒温 1〜50小时， 优选 2〜10小时。 预钝化过程中反应装置内气体的硫 含量控制在 0.5〜100x l(T6L/L,优选 2~20x l(T6L/L,更优选 3~20 10-6L/L， 最优选 3〜6x lO_6L/L。 预钝化后， 通入不影响后续重整反应的置换气体 置换装置中的气体， 至排出气体中硫含量不大于 5.0x lO—6L/L, 优选不 大于 2.0x lO_6L/L时， 通入反应原料按常规反应条件进行重整反应。 优 选地， 用于置换装置中原有循环气体的置换气体为氢气、 惰性气体或 惰性气体与氢气的混合物， 优选氢气或氮气。
上述实施方式中所述的连续重整装置的常规反应条件为： 压力
0.1〜5.0MPa、 优选 0.35〜2.0MPa, 温度 350〜600°C、 优选 430〜560°C、 更优选 490〜545°C , 氢 /烃摩尔比 1〜20、 优选 2〜： 10, 液时空速（LHSV ) l~10hr_1 , 优选 l〜5hr-1。
所述向循环气体中注入的硫化物优选硫化氢、 二硫化碳、 二曱基 二硫醚、 脂肪族含硫化合物， 脂环族含硫化合物， 芳香族含硫化合物、 噻吩、 吗啉类化合物或所述化合物中任意两种或两种以上的混合物， 其中所述的噻吩、 吗啉类化合物是指噻吩或吗啉的衍生物。 当钝化以 惰性气体、 优选氮气为介质时， 注入的硫化物优选硫化氢； 当钝化以 氢气为介盾时， 注入的硫化物可为硫化氢， 也可以是上述有机硫化物。
在本发明的另一个实施方式中， 在反应初期， 先使连续重整反应 系统低温进油， 并且在反应系统升温和恒温脱水、 调整操作期间， 向 反应系统中引入一定量的硫化物， 使进入系统的硫含量达到一个比较 高的水平， 即控制引入系统中的总硫量与重整原料油的比在大于 0.5 g/g至 5(^g/g之间， 当循环气中硫化氢浓度达到一定值后， 再下调 引入系统的硫含量， 待系统中水含量合格后， 再提高反应温度使装置 进行正常的生产操作。 其中所述向反应系统弓 ]入硫化物的方式可为向 所述重整原料油中加入硫化物， 或者是向循环气中加入硫化氢或含硫 化氢的气体， 也可以是既向循环气中加入硫化氢或含硫化氢的气体， 又向所述重整原料油中加入 ¾IL化物。 所述的含硫化氢气体为来自重整 预加氢系统的氢气， 或其它装置硫化氢浓度较高的含氢气体， 所述含 氢气体中^ ^^；氢含量为 50〜500(^L/L , 优选 100〜200(^L/L , 更优选 200〜80(^L/L。 采用上述方法， 能够对连续重整反应器和加热炉管器壁 进行充分、 快速地钝化， 从而抑制结焦的发生。 反应初期较高的注 ^ 量不会影响装置操作调整进度和连续重整装置在高苛刻度条件下运行 时催化剂的反应活性。
在所述实施方式中， 步骤（ 1 ) 为装置开始操作后的低温注硫， 装 置进油的同时或之后在低温下引入^ >化物， 优选控制引入系统中的总 硫量与重整原料油的比为 0.6~2C^g/g, 更优选为 1.0〜： I0 g/g。 （ 1 ) 步 引入硫后， 应定期检测重整装置循环气中的硫化氢含量， 当循环气中 石克化氢浓度达到 2.0〜30μΙ ί 以上， 优选达到 2.0〜6.0μΙ ί时， 将引入 系统中的硫化物的总量下调。 优选将引入系统中的总硫量与重整原料 油的比下调至 0.2~0.5 g/g。
步骤 （ 1 ) 中将引入反应系统中的总硫量下调后， 当引入系统中的 总硫量与重整原料油的比降到 0.2~2.(^g/g, 优选（ l.O g/g后， 待循 环气中硫化氢浓度小于. 5.(^L/L, 优选为 0.2~2.C^L/L时， 视催化剂的 积炭情况， 可启动再生系统， 进行催化剂的循环再生。
所述步骤 （ 1 ) 中所引入的硫化物为硫化氢、 二硫化碳、 二曱基二 硫醚、 脂肪族含^ L化合物， 脂环族含硫化合物， 芳香族含硫化合物、 噻哈、 吗啉类化合物或所述化合物中任意两种或两种以上的混合物 , 其中所述的噻吩、 吗啉类化合物是指噻吩或吗啉的衍生物。 优选^ ^化 氢、 硫醚、 硫化氢或二硫化碳， 所述的硫醚优选二甲基二硫醚或二甲 基疏醚。
为维持重整催化剂的酸性功能， 在向重整系统中引入硫化物的同 时， 还应引入氯化物， 注氯量可根据常规的注氯要求进行。 一般地， 当循环氢中水含量大于 500 L/L时， 注氯量为 30 ~ 50 g/g; 循环氢中 水含量为 300~50(^L/L 时， 注氯量为 15〜3(^g/g; 循环氢中水含量为 100〜200 L/L时， 注氯量为 5~l(^g/g; 循环氢中水含量为 50~100 L/L 时， 注氯量为 2〜5 g/g。 注氯所用的氯化物优选卤代烷烃或卤代烯烃， 如二氯乙烷、 三氯乙烷、 四氯乙烯、 四氯丙稀或四氯化碳。
所述实施方式的步骤 （2 ) 为一个恒温控制过程， 此过程保持较低 的引入反应系统的硫化物的量， 将引入系统的总硫量与重整原料油的 比控制为 0.2~0.5 g/g, 待循环气中水含量降为规定值后将反应温度提 高至所需的重整反应温度， 优选的操作方法是当所述的循环气中水含 量低于 200μ! ί后， 将反应温度提至 460~490°C , 并在此温度下继续排 水， 当循环气中水含量低于 5(^L/L后， 按设计量通入重整原料， 按液 体产品辛烷值的要求提高重整反应温度，一般将反应温度升至 490〜545 °C , 进行正常的重整反应操作。 操作时控制重整反应的压力为 0.1〜5.0MPa， 优选 0.35〜2.0MPa; 氢气与原料油的摩尔比为 1〜20, 优选 2-10; 进料液时空速（LHSV ) 为 l lOhf1 , 优选 l〜5hr—
在所述实施方式步骤（1 ) 中所述重整原料油的进料量通常低于所 述装置的设计进料量，优选为重整装置设计进料量的 50〜75质量％。 当 步骤 （ 1 ) 完成后， 再在步骤（2 ) 中按重整装置的设计量通入重整原 料油进行正常的重整反应。
在上述实施方式中， 在开始进油后， 所述循环气是指重整反应产 物经气液分离后循环回反应系统的气体， 主要为氢气。 进油前的循环 气指在系统内循环的气体， 所述的循环气优选氢气、 惰性气体或氢气 与惰性气体的混合物， 所述的惰性气体优选氮气。
在本发明的上述方法中， 向反应系统内装填的重整催化剂优选为 含铂锡的系列双或多金属催化剂。 优选地， 所述的重整催化剂包括载 体和以干基载体为计算基准的 0.01 2.0质量％、 优选 0.1〜1.0质量％的 铂族金属， 0.01〜5.0质量％、 优选 0.1 2.0质量％的锡和 0.1〜10质量％、 优选 0.1 5.0质量％的卤素； 所述的铂族金属为铂、 铑、 钯、 铱、 钌或 锇， 优选铂， 素优选氯， 载体优选氧化铝， 更优选 γ-氧化铝。 此外， 还可含有选自铕、 铈、 钛等进一步改善催化剂反应性能的第三和 /或笫 四金属组元， 第三和 /或笫四金属组元在催化剂中的含量为 0.01〜5.0质 量％, 优选 0.05〜3.0质量％, 更优选为 0.1〜2.0质量％。
本发明方法所述的连续重整装置为各类移动床连续再生式催化重 整装置。 所述连续重整的原料油可以是直馏石脑油、 加氢裂化重石脑 油、 加氢焦化汽油、 乙烯裂解汽油抽余油、 催化裂化汽油， 也可以是 其中几种原料的混合物。 根据目标产物的不同， 原料油控制的餾程范 围有所不同。 所述原料油的初馏点一般为 60〜95 °C , 终馏点一般为 135~180 °C。 重整原料油的杂质要求为： <0.5 g/g, 氮 <0.5 g/g, 砷 <lng/g, H0ng/g, 铜<101^, 水<5 。
本发明所述的重整装置钝化方法适用于铂锡系列催化剂的连续再 生式重整装置， 特别适用于新建连续重整装置的首次使用过程。 下面通过实例进一步说明本发明， 但本发明并不限于此。 实例 1
在连续重整装置内装填好重整催化剂， 所述催化剂含 0.29质量％ 的铂、 0.31质量％的锡， 其余为 γ-氧化铝。
先用纯度为 99.8摩尔％的氮气置换连续重整装置至排出气体的氧 含量小于 0.5摩尔％ ,然后用纯度为 96摩尔％的氢气置换系统至排出气 体的氢含量大于 90 摩尔％。 用氢气充压至重整高压分离器的压力为 350KPa, 启动重整压缩机循环， 使循环气量为 5x l04Nm3/h。 将各反应 器以每小时 20〜40°C的速率升温至反应器入口温度为 200°C后， 开始向 循环气中注入二甲基二^ 醚并继续升温， 注入二曱基二石充醚， 使循环 气中的 υ含量为 3~5xl(T6L/L。 当反应器入口温度升至 370 °C时恒温 3 小时， 然后停止注硫， 用纯度为 96摩尔％的氢气置换系统， 将循环气 中¾含量降至 2x l(T6L/L以下， 之后通入重整反应原料进行重整反应， 重整原料油组成见表 1 , 反应条件及结果见表 2。 运转中催化剂采样时 未见炭块， 停工检查反应器等高温部位未见结焦。 对比例 1
在连续重整装置中装填好重整催化剂， 所述催化剂的组成同实例 1。
先用纯度为 99.8摩尔％的氮气置换连续重整装置至排出气体的氧 含量小于 0.5摩尔％，然后用纯度为 93摩尔％的氢气置换系统至排出气 体的氢含量大于 60 摩尔％。 用氢气充压至重整高压分离器的压力为 350KPa, 启动重整压缩机循环， 使循环气流量为 4x l04Nm3/h, 将各反 应器以每小时 20〜40 °C的速率升温至 370°C。 向重整反应器中通入重整 原料油，其组成见表 1。重整进料后即开始向原料中注入二甲基二硫醚， 使原料中的硫含量为 0.2〜0.3 g/g, 然后按正常运转的重整操作条件进 行反应， 主要操作条件和反应结果见表 2。 重整装置运行 3个月后从分 离料斗处采集催化剂样品时， 经常会发现 l~5mm大小的炭块， 炭块样 品的电镜照片分别见图 1和图 2 ,照片显示炭块是顶部带有铁粒子的丝 状炭。 在装置停工后检查时发现， 反应器底部结焦明显， 见图 3。 表 1
Figure imgf000011_0001
表 2
Figure imgf000011_0002
于比例 2
控制连续重整装置反应系统平均压力为 0.45MPa, 高分压力为 0.34MPa。反应系统催化剂装量 50060kg,其中含 0.28质量％的铂、 0.31 质量％的锡、 1.10质量％的氯。 以表 3所示的石脑油为原料。
检查系统氢气气密合格后， 启动氢气循环， 并开始以 40~50°C/小 时的速率将反应系统升温， 待各反应器温度达到 370°C时， 开始通入重 整原料， 进料量为 57吨 /小时， 同时以 20〜30 C/小时的速率将反应器向 48CTC升温， 升温的同时， 向反应原料中注入二甲基二硫醚， 控制重整 进料中的硫含量为 0.3~0.5 g/g。 进油的同时根据循环气中水含量向原 料油中注入四氯乙烯。
当重整循环气中水含量低于 20C^L/L后， 将反应器温度升至 490 Ό并在此温度下脱水， 脱水的同时， 根据循环气中的水含量逐渐下调 注氯量。 当循环气中水小于 50 L/L时， 将进料量逐渐提至 95吨 /小时， 重整各反应器入口温度提至 530 °C。 通入原料油 96小时后， 启动催化 剂循环再生系统。 催化剂再生系统正常运转后， 停止原料油注氯。 各 反应器主要操作条件和反应结果见表 4。 该装置投产后运行 6个月， 反 应系统和循环再生系统运行正常， 没有出现循环系统堵塞的现象， 但 从分离料斗处采集催化剂样品时 ,经常会发现少量 1 ~5mm大小的炭块， 电镜照片显示仍为丝状炭， 如图 4 所示。 正常停工后检查， 反应器壁 仍有少量焦炭， 但未发现反应器和加热炉管发生金属催化严重结焦现 象。 实例 2
对比例 2 中所述的连续重整装置正常停工、 检修、 卸剂， 将反应 器内部清扫干净， 并利用过筛和重力沉降的方法将催化剂中少量的小 炭粒分离出来， 重新装入催化剂后投产。 使用对比例 2 所述的重整原 料和催化剂。检查系统氢气气密合格后，启动氢气循环，并开始以 40〜50 /小时的速率将反应系统升温， 在各反应器温度达到 370 °C时， 开始 通入重整反应原料，进料量为 57吨 /小时， 同时以 20~30 °C/小时的速率 将反应器向 480 °C升温， 在升温的同时， 向重整进料中注入二甲基二硫 醚和四氯乙烯， 并控制重整进料的硫含量为 6.0 g/g。 向原料中注入硫 化物后， 每隔两小时分析重整循环气中的硫化氢浓度。 当循环气中硫 化氢浓度达到 2 L/L 时， 将注入硫化物的量下调至重整进料中硫含量 为 0.2〜0.5 g/g。 当重整循环气中水含量低于 20(^L/L后， 将反应器温 度升至 490 °C并在此温度下脱水， 脱水的同时， 根据循环气中的水含量 逐渐下调注氯量。 当循环气中水含量小于 50μ17ί, 且循环气中硫化氢 浓度小于 2 L/L时， 将重整进料量逐渐提至 95吨 /小时， 重整各反应器 入口温度提至 530 °C。 通入原料油 96小时后， 启动催化剂循环再生系 统。 催化剂再生系统正常运转后， 停止原料油注氯， 进行正常的重整 反应操作。 各反应器主要操作条件和反应结果见表 4。 实例 3
按实例 2 的方法将连续重整装置正常停工检修、 卸剂， 装入催化 剂后开始进行反应， 不同的是重整反应装置进料后向重整反应原料中 的注硫量为 l.O g/g, 正常运转后各反应器的主要操作条件和反应结果 见表 4。 实例 4
按实例 2 的方法将连续重整装置正常停工检修、 卸剂， 装入催化 剂后开始进行反应， 不同的是重整反应装置进料后未向原料油中注入 有机硫化物， 而是将重整预加氢尾气引入重整系统， 该尾气中硫含量 为 550μΙ7Ι 氢纯度为 94%, 引入流量控制在 500~550Nm3/h, 引入系 统中的硫与进入系统的重整原料油的比为 4 g/g, 当重整装置循环气中 硫化氢浓度达到 2μΙ7ί 时， 将预加氢尾气的引入流量控制在 30~40Nm3/h , 即引入系统的总硫量下调至与重整原料油的比为 0.3〜0.5 g/g。 当重整循环气中水含量低于 20(^L/L后， 将反应器温度 升至 490 °C并在此温度下脱水， 脱水的同时， 根据循环气中的水含量逐 渐下调注氯量。 当循环气中水含量小于 50μΙ , 且循环气中硫化氢浓 度小于 2 L/L时， 将重整进料量逐渐提至 95吨 /小时， 重整各反应器入 口温度提至 530°C。 通入原料油 96小时后， 启动催化剂循环再生系统。 催化剂再生系统正常运转后， 停止原料油注氯， 进行正常的重整反应 操作。 正常运转后各反应器的主要操作条件和反应结果见表 4。
与对比例 2 的反应结果相比， 本发明方法中催化剂的反应活性未 受到反应初期原料油中高硫含量的影响。 装置投产后运行一年， 反应 和循环再生系统运行正常， .从分离料斗处采集催化剂样品时， 没有再 发现丝状炭的炭块， 反应器和加热炉管没有发生金属催化结焦现象。 烷烃 49.78 族组成， 质量％ 环烷烃 41.94 芳烃 8.24
ASTMD86馏程， °C 85 - 163 总疏含量， g/g <0.2 表 4
Figure imgf000014_0001

Claims

权 利 要 求
1. 一种连续重整装置的预钝化方法， 其包括：
在连续重整装置中装入重整催化剂， 启动气体循环并升高反应器 的温度， 在反应器温度为 100〜650 °C的范围内向所述气体中注入 ¾化 物， 控制循环气体中硫含量为 0.5〜100x lCT6L/L, 以对所述装置进行钝 化。
2. 按照权利要求 1所述的方法， 其特征在于控制循环气中硫含量 为 3〜20χ 10-6 。
3. 按照权利要求 1所述的方法， 其特征在于所述的循环气体为惰
,[·生气体时， 注入的 化物为 υ化氢。
4. 按照权利要求 1所述的方法， 其特征在于所述钝化完成后， 先 通入置换气体置换装置中的气体， 当从所述反应器出口离开的循环气 流中硫化氢含量不大于 5 x l(T6L/L时， 通入反应原料进行正常的重整反 应操作， 所述置换气体是氢气、 惰性气体或惰性气体与氢气的混合物。
5. 一种连续重整装置初始反应的钝化方法， 其包括：
( 1 )在连续重整装置中装入重整催化剂， 启动气体循环并升高反 应器的温度，当反应器的温度升高到 300〜460 °C时向反应系统中通入重 整原料油， 并在通入重整原料油的同时或之后向所述反应系统中引入 硫化物， 控制引入系统中的总硫量与重整原料油的比在大于 0.5 g/g至 5C^g/g之间， 当循环气中硫化氢浓度达到 2.C^L/L〜3(^L/L时， 下调引 入系统中^ <化物的量，
( 2 )将重整反应器保持在 460〜490 °C , 待循环气中的水含量低于 5C^L/L时， 控制引入系统的总硫量与重整原料油的比为 0.2〜0.5 g/g, 将重整进料量调至装置设计值， 按液体产品辛烷值的要求提高重整反 应温度至 490〜545 °C , 转入正常操作的条件进行反应。
6. 按照权利要求 5所述的方法， 其特征在于向反应系统中引入硫 化物的方式为向所述重整原料油中加入^ L化物。
7. 按照权利要求 5所述的方法，其特征在于向反应系统中引入硫化 物的方式为向循环气中加入^ L化氢或含硫化氢的气体。
8. 按照权利要求 5所述的方法， 其特征在于向反应系统中引入石克 化物的方式为既向循环气中加入 化氢或含^ L化氢的气体， 又向所述 重整原料油中加入 υ化物。
9. 按照权利要求 7或 8所述的方法， 其特征在于所述的含硫化氢 气体为硫化氢含量为 50~500(^L/L的含氢气体。
10. 按照权利要求 5所述的方法， 其特征在于步骤 （1 ) 中通入的 重整原料油为重整装置设计进料量的 50~75质量％。
11. 按照权利要求 5所述的方法， 其特征在于步骤 （ 1 )初始引入 的硫化物应使系统中引入的总硫量与重整原料油的比为 0.6〜2(^g/g。
12. 按照权利要求 5所述的方法， 其特征在于步骤 （1 ) 中当循环 气中硫化氢浓度达到 2.0~4.0 L/L时，控制引入系统的总硫量与重整原 料油的比为 0.2〜0.5 g/g。
13. 按照权利要求 5所述的方法， 其特征在于步驟（1 ) 中使引入 系统的总硫量与重整原料油的比下降至 0.2〜2.0 g/g后， 待循环气中硫 化氢浓度小于 5.(^L/L时， 启动再生系统， 进行催化剂的循环再生。
14. 按照权利要求 1或 5所述的方法，其特征在于所述的循环气体 为氢气、 惰性气体或惰性气体与氢气的混合物。
15. 按照权利要求 3或 14所述的方法， 其特征在于所述的惰性气 体为氮气。
16. 按照权利要求 1或 5所述的方法，其特征在于所述的硫化物为 」 化氢、 二硫化碳、 二甲基二硫醚、 脂肪族含硫化合物， 脂环族含硫 化合物， 芳香族含硫化合物、 噻吩、 吗啉类化合物或所述化合物中任 意两种或两种以上的混合物。
17. 按照权利要求 1或 5所述的方法，其特征在于所述的催化剂包 括载体和以干基载体为计算基准的 0.05〜1.0 质量％的铂族金属、
0.05〜： 1.0质量％的锡和 0.1〜5.0质量％的卤素。
18. 按照权利要求 17所述的方法， 其特征在于所述的重整催化剂 中的铂族金属为铂， 卤素为氯， 载体为氧化铝。
PCT/CN2008/001819 2007-10-31 2008-10-30 A predeactivation method and a deactivation method during initial reaction for a continuous reforming apparatus WO2009067858A1 (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120277511A1 (en) * 2011-04-29 2012-11-01 Uop Llc High Temperature Platformer
US9199893B2 (en) 2014-02-24 2015-12-01 Uop Llc Process for xylenes production

Families Citing this family (315)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10378106B2 (en) 2008-11-14 2019-08-13 Asm Ip Holding B.V. Method of forming insulation film by modified PEALD
US9394608B2 (en) 2009-04-06 2016-07-19 Asm America, Inc. Semiconductor processing reactor and components thereof
US8802201B2 (en) 2009-08-14 2014-08-12 Asm America, Inc. Systems and methods for thin-film deposition of metal oxides using excited nitrogen-oxygen species
US9312155B2 (en) 2011-06-06 2016-04-12 Asm Japan K.K. High-throughput semiconductor-processing apparatus equipped with multiple dual-chamber modules
US10364496B2 (en) 2011-06-27 2019-07-30 Asm Ip Holding B.V. Dual section module having shared and unshared mass flow controllers
US10854498B2 (en) 2011-07-15 2020-12-01 Asm Ip Holding B.V. Wafer-supporting device and method for producing same
US20130023129A1 (en) 2011-07-20 2013-01-24 Asm America, Inc. Pressure transmitter for a semiconductor processing environment
US9017481B1 (en) 2011-10-28 2015-04-28 Asm America, Inc. Process feed management for semiconductor substrate processing
US9558931B2 (en) * 2012-07-27 2017-01-31 Asm Ip Holding B.V. System and method for gas-phase sulfur passivation of a semiconductor surface
US9659799B2 (en) 2012-08-28 2017-05-23 Asm Ip Holding B.V. Systems and methods for dynamic semiconductor process scheduling
US9021985B2 (en) 2012-09-12 2015-05-05 Asm Ip Holdings B.V. Process gas management for an inductively-coupled plasma deposition reactor
US10714315B2 (en) 2012-10-12 2020-07-14 Asm Ip Holdings B.V. Semiconductor reaction chamber showerhead
US20160376700A1 (en) 2013-02-01 2016-12-29 Asm Ip Holding B.V. System for treatment of deposition reactor
US9589770B2 (en) 2013-03-08 2017-03-07 Asm Ip Holding B.V. Method and systems for in-situ formation of intermediate reactive species
US9484191B2 (en) 2013-03-08 2016-11-01 Asm Ip Holding B.V. Pulsed remote plasma method and system
US8993054B2 (en) 2013-07-12 2015-03-31 Asm Ip Holding B.V. Method and system to reduce outgassing in a reaction chamber
US9240412B2 (en) 2013-09-27 2016-01-19 Asm Ip Holding B.V. Semiconductor structure and device and methods of forming same using selective epitaxial process
US9605343B2 (en) 2013-11-13 2017-03-28 Asm Ip Holding B.V. Method for forming conformal carbon films, structures conformal carbon film, and system of forming same
US10683571B2 (en) 2014-02-25 2020-06-16 Asm Ip Holding B.V. Gas supply manifold and method of supplying gases to chamber using same
US10167557B2 (en) 2014-03-18 2019-01-01 Asm Ip Holding B.V. Gas distribution system, reactor including the system, and methods of using the same
US11015245B2 (en) 2014-03-19 2021-05-25 Asm Ip Holding B.V. Gas-phase reactor and system having exhaust plenum and components thereof
US10858737B2 (en) 2014-07-28 2020-12-08 Asm Ip Holding B.V. Showerhead assembly and components thereof
US9890456B2 (en) 2014-08-21 2018-02-13 Asm Ip Holding B.V. Method and system for in situ formation of gas-phase compounds
US9657845B2 (en) 2014-10-07 2017-05-23 Asm Ip Holding B.V. Variable conductance gas distribution apparatus and method
US10941490B2 (en) 2014-10-07 2021-03-09 Asm Ip Holding B.V. Multiple temperature range susceptor, assembly, reactor and system including the susceptor, and methods of using the same
KR102300403B1 (ko) 2014-11-19 2021-09-09 에이에스엠 아이피 홀딩 비.브이. 박막 증착 방법
KR102263121B1 (ko) 2014-12-22 2021-06-09 에이에스엠 아이피 홀딩 비.브이. 반도체 소자 및 그 제조 방법
US10529542B2 (en) 2015-03-11 2020-01-07 Asm Ip Holdings B.V. Cross-flow reactor and method
US10276355B2 (en) 2015-03-12 2019-04-30 Asm Ip Holding B.V. Multi-zone reactor, system including the reactor, and method of using the same
US10458018B2 (en) 2015-06-26 2019-10-29 Asm Ip Holding B.V. Structures including metal carbide material, devices including the structures, and methods of forming same
US10600673B2 (en) 2015-07-07 2020-03-24 Asm Ip Holding B.V. Magnetic susceptor to baseplate seal
US10043661B2 (en) 2015-07-13 2018-08-07 Asm Ip Holding B.V. Method for protecting layer by forming hydrocarbon-based extremely thin film
FR3039082B1 (fr) * 2015-07-24 2017-07-21 Ifp Energies Now Catalyseur multi-metallique dope par du phosphore et un lanthanide
US10083836B2 (en) 2015-07-24 2018-09-25 Asm Ip Holding B.V. Formation of boron-doped titanium metal films with high work function
US10087525B2 (en) 2015-08-04 2018-10-02 Asm Ip Holding B.V. Variable gap hard stop design
US9647114B2 (en) 2015-08-14 2017-05-09 Asm Ip Holding B.V. Methods of forming highly p-type doped germanium tin films and structures and devices including the films
US9960072B2 (en) 2015-09-29 2018-05-01 Asm Ip Holding B.V. Variable adjustment for precise matching of multiple chamber cavity housings
US10211308B2 (en) 2015-10-21 2019-02-19 Asm Ip Holding B.V. NbMC layers
US10322384B2 (en) 2015-11-09 2019-06-18 Asm Ip Holding B.V. Counter flow mixer for process chamber
US9627221B1 (en) 2015-12-28 2017-04-18 Asm Ip Holding B.V. Continuous process incorporating atomic layer etching
US11139308B2 (en) 2015-12-29 2021-10-05 Asm Ip Holding B.V. Atomic layer deposition of III-V compounds to form V-NAND devices
US10468251B2 (en) 2016-02-19 2019-11-05 Asm Ip Holding B.V. Method for forming spacers using silicon nitride film for spacer-defined multiple patterning
US10529554B2 (en) 2016-02-19 2020-01-07 Asm Ip Holding B.V. Method for forming silicon nitride film selectively on sidewalls or flat surfaces of trenches
US10501866B2 (en) 2016-03-09 2019-12-10 Asm Ip Holding B.V. Gas distribution apparatus for improved film uniformity in an epitaxial system
US10343920B2 (en) 2016-03-18 2019-07-09 Asm Ip Holding B.V. Aligned carbon nanotubes
US9892913B2 (en) 2016-03-24 2018-02-13 Asm Ip Holding B.V. Radial and thickness control via biased multi-port injection settings
US10190213B2 (en) 2016-04-21 2019-01-29 Asm Ip Holding B.V. Deposition of metal borides
US10087522B2 (en) 2016-04-21 2018-10-02 Asm Ip Holding B.V. Deposition of metal borides
US10865475B2 (en) 2016-04-21 2020-12-15 Asm Ip Holding B.V. Deposition of metal borides and silicides
US10032628B2 (en) 2016-05-02 2018-07-24 Asm Ip Holding B.V. Source/drain performance through conformal solid state doping
US10367080B2 (en) 2016-05-02 2019-07-30 Asm Ip Holding B.V. Method of forming a germanium oxynitride film
KR102592471B1 (ko) 2016-05-17 2023-10-20 에이에스엠 아이피 홀딩 비.브이. 금속 배선 형성 방법 및 이를 이용한 반도체 장치의 제조 방법
US11453943B2 (en) 2016-05-25 2022-09-27 Asm Ip Holding B.V. Method for forming carbon-containing silicon/metal oxide or nitride film by ALD using silicon precursor and hydrocarbon precursor
US10388509B2 (en) 2016-06-28 2019-08-20 Asm Ip Holding B.V. Formation of epitaxial layers via dislocation filtering
US10612137B2 (en) 2016-07-08 2020-04-07 Asm Ip Holdings B.V. Organic reactants for atomic layer deposition
US9859151B1 (en) 2016-07-08 2018-01-02 Asm Ip Holding B.V. Selective film deposition method to form air gaps
US9793135B1 (en) 2016-07-14 2017-10-17 ASM IP Holding B.V Method of cyclic dry etching using etchant film
US10714385B2 (en) 2016-07-19 2020-07-14 Asm Ip Holding B.V. Selective deposition of tungsten
KR102354490B1 (ko) 2016-07-27 2022-01-21 에이에스엠 아이피 홀딩 비.브이. 기판 처리 방법
US10177025B2 (en) 2016-07-28 2019-01-08 Asm Ip Holding B.V. Method and apparatus for filling a gap
US9812320B1 (en) 2016-07-28 2017-11-07 Asm Ip Holding B.V. Method and apparatus for filling a gap
US9887082B1 (en) 2016-07-28 2018-02-06 Asm Ip Holding B.V. Method and apparatus for filling a gap
US10395919B2 (en) 2016-07-28 2019-08-27 Asm Ip Holding B.V. Method and apparatus for filling a gap
KR102532607B1 (ko) 2016-07-28 2023-05-15 에이에스엠 아이피 홀딩 비.브이. 기판 가공 장치 및 그 동작 방법
US10090316B2 (en) 2016-09-01 2018-10-02 Asm Ip Holding B.V. 3D stacked multilayer semiconductor memory using doped select transistor channel
US10410943B2 (en) 2016-10-13 2019-09-10 Asm Ip Holding B.V. Method for passivating a surface of a semiconductor and related systems
US10643826B2 (en) 2016-10-26 2020-05-05 Asm Ip Holdings B.V. Methods for thermally calibrating reaction chambers
US11532757B2 (en) 2016-10-27 2022-12-20 Asm Ip Holding B.V. Deposition of charge trapping layers
US10643904B2 (en) 2016-11-01 2020-05-05 Asm Ip Holdings B.V. Methods for forming a semiconductor device and related semiconductor device structures
US10229833B2 (en) 2016-11-01 2019-03-12 Asm Ip Holding B.V. Methods for forming a transition metal nitride film on a substrate by atomic layer deposition and related semiconductor device structures
US10435790B2 (en) 2016-11-01 2019-10-08 Asm Ip Holding B.V. Method of subatmospheric plasma-enhanced ALD using capacitively coupled electrodes with narrow gap
US10714350B2 (en) 2016-11-01 2020-07-14 ASM IP Holdings, B.V. Methods for forming a transition metal niobium nitride film on a substrate by atomic layer deposition and related semiconductor device structures
US10134757B2 (en) 2016-11-07 2018-11-20 Asm Ip Holding B.V. Method of processing a substrate and a device manufactured by using the method
KR102546317B1 (ko) 2016-11-15 2023-06-21 에이에스엠 아이피 홀딩 비.브이. 기체 공급 유닛 및 이를 포함하는 기판 처리 장치
US10340135B2 (en) 2016-11-28 2019-07-02 Asm Ip Holding B.V. Method of topologically restricted plasma-enhanced cyclic deposition of silicon or metal nitride
KR20180068582A (ko) 2016-12-14 2018-06-22 에이에스엠 아이피 홀딩 비.브이. 기판 처리 장치
US11447861B2 (en) 2016-12-15 2022-09-20 Asm Ip Holding B.V. Sequential infiltration synthesis apparatus and a method of forming a patterned structure
US9916980B1 (en) 2016-12-15 2018-03-13 Asm Ip Holding B.V. Method of forming a structure on a substrate
US11581186B2 (en) 2016-12-15 2023-02-14 Asm Ip Holding B.V. Sequential infiltration synthesis apparatus
KR20180070971A (ko) 2016-12-19 2018-06-27 에이에스엠 아이피 홀딩 비.브이. 기판 처리 장치
US10269558B2 (en) 2016-12-22 2019-04-23 Asm Ip Holding B.V. Method of forming a structure on a substrate
US10867788B2 (en) 2016-12-28 2020-12-15 Asm Ip Holding B.V. Method of forming a structure on a substrate
US11390950B2 (en) 2017-01-10 2022-07-19 Asm Ip Holding B.V. Reactor system and method to reduce residue buildup during a film deposition process
US10655221B2 (en) 2017-02-09 2020-05-19 Asm Ip Holding B.V. Method for depositing oxide film by thermal ALD and PEALD
US10468261B2 (en) 2017-02-15 2019-11-05 Asm Ip Holding B.V. Methods for forming a metallic film on a substrate by cyclical deposition and related semiconductor device structures
US10529563B2 (en) 2017-03-29 2020-01-07 Asm Ip Holdings B.V. Method for forming doped metal oxide films on a substrate by cyclical deposition and related semiconductor device structures
US10283353B2 (en) 2017-03-29 2019-05-07 Asm Ip Holding B.V. Method of reforming insulating film deposited on substrate with recess pattern
US10103040B1 (en) 2017-03-31 2018-10-16 Asm Ip Holding B.V. Apparatus and method for manufacturing a semiconductor device
USD830981S1 (en) 2017-04-07 2018-10-16 Asm Ip Holding B.V. Susceptor for semiconductor substrate processing apparatus
KR102457289B1 (ko) 2017-04-25 2022-10-21 에이에스엠 아이피 홀딩 비.브이. 박막 증착 방법 및 반도체 장치의 제조 방법
US10770286B2 (en) 2017-05-08 2020-09-08 Asm Ip Holdings B.V. Methods for selectively forming a silicon nitride film on a substrate and related semiconductor device structures
US10892156B2 (en) 2017-05-08 2021-01-12 Asm Ip Holding B.V. Methods for forming a silicon nitride film on a substrate and related semiconductor device structures
US10446393B2 (en) 2017-05-08 2019-10-15 Asm Ip Holding B.V. Methods for forming silicon-containing epitaxial layers and related semiconductor device structures
US10504742B2 (en) 2017-05-31 2019-12-10 Asm Ip Holding B.V. Method of atomic layer etching using hydrogen plasma
US10886123B2 (en) 2017-06-02 2021-01-05 Asm Ip Holding B.V. Methods for forming low temperature semiconductor layers and related semiconductor device structures
US11306395B2 (en) 2017-06-28 2022-04-19 Asm Ip Holding B.V. Methods for depositing a transition metal nitride film on a substrate by atomic layer deposition and related deposition apparatus
US10685834B2 (en) 2017-07-05 2020-06-16 Asm Ip Holdings B.V. Methods for forming a silicon germanium tin layer and related semiconductor device structures
KR20190009245A (ko) 2017-07-18 2019-01-28 에이에스엠 아이피 홀딩 비.브이. 반도체 소자 구조물 형성 방법 및 관련된 반도체 소자 구조물
US10541333B2 (en) 2017-07-19 2020-01-21 Asm Ip Holding B.V. Method for depositing a group IV semiconductor and related semiconductor device structures
US11018002B2 (en) 2017-07-19 2021-05-25 Asm Ip Holding B.V. Method for selectively depositing a Group IV semiconductor and related semiconductor device structures
US11374112B2 (en) 2017-07-19 2022-06-28 Asm Ip Holding B.V. Method for depositing a group IV semiconductor and related semiconductor device structures
US10312055B2 (en) 2017-07-26 2019-06-04 Asm Ip Holding B.V. Method of depositing film by PEALD using negative bias
US10605530B2 (en) 2017-07-26 2020-03-31 Asm Ip Holding B.V. Assembly of a liner and a flange for a vertical furnace as well as the liner and the vertical furnace
US10590535B2 (en) 2017-07-26 2020-03-17 Asm Ip Holdings B.V. Chemical treatment, deposition and/or infiltration apparatus and method for using the same
US10692741B2 (en) 2017-08-08 2020-06-23 Asm Ip Holdings B.V. Radiation shield
US10770336B2 (en) 2017-08-08 2020-09-08 Asm Ip Holding B.V. Substrate lift mechanism and reactor including same
US11139191B2 (en) 2017-08-09 2021-10-05 Asm Ip Holding B.V. Storage apparatus for storing cassettes for substrates and processing apparatus equipped therewith
US11769682B2 (en) 2017-08-09 2023-09-26 Asm Ip Holding B.V. Storage apparatus for storing cassettes for substrates and processing apparatus equipped therewith
US10249524B2 (en) 2017-08-09 2019-04-02 Asm Ip Holding B.V. Cassette holder assembly for a substrate cassette and holding member for use in such assembly
US10236177B1 (en) 2017-08-22 2019-03-19 ASM IP Holding B.V.. Methods for depositing a doped germanium tin semiconductor and related semiconductor device structures
USD900036S1 (en) 2017-08-24 2020-10-27 Asm Ip Holding B.V. Heater electrical connector and adapter
US11830730B2 (en) 2017-08-29 2023-11-28 Asm Ip Holding B.V. Layer forming method and apparatus
US11056344B2 (en) 2017-08-30 2021-07-06 Asm Ip Holding B.V. Layer forming method
US11295980B2 (en) 2017-08-30 2022-04-05 Asm Ip Holding B.V. Methods for depositing a molybdenum metal film over a dielectric surface of a substrate by a cyclical deposition process and related semiconductor device structures
KR102491945B1 (ko) 2017-08-30 2023-01-26 에이에스엠 아이피 홀딩 비.브이. 기판 처리 장치
KR102401446B1 (ko) 2017-08-31 2022-05-24 에이에스엠 아이피 홀딩 비.브이. 기판 처리 장치
US10607895B2 (en) 2017-09-18 2020-03-31 Asm Ip Holdings B.V. Method for forming a semiconductor device structure comprising a gate fill metal
KR102630301B1 (ko) 2017-09-21 2024-01-29 에이에스엠 아이피 홀딩 비.브이. 침투성 재료의 순차 침투 합성 방법 처리 및 이를 이용하여 형성된 구조물 및 장치
US10844484B2 (en) 2017-09-22 2020-11-24 Asm Ip Holding B.V. Apparatus for dispensing a vapor phase reactant to a reaction chamber and related methods
US10658205B2 (en) 2017-09-28 2020-05-19 Asm Ip Holdings B.V. Chemical dispensing apparatus and methods for dispensing a chemical to a reaction chamber
US10403504B2 (en) 2017-10-05 2019-09-03 Asm Ip Holding B.V. Method for selectively depositing a metallic film on a substrate
US10319588B2 (en) 2017-10-10 2019-06-11 Asm Ip Holding B.V. Method for depositing a metal chalcogenide on a substrate by cyclical deposition
US10923344B2 (en) 2017-10-30 2021-02-16 Asm Ip Holding B.V. Methods for forming a semiconductor structure and related semiconductor structures
KR102443047B1 (ko) 2017-11-16 2022-09-14 에이에스엠 아이피 홀딩 비.브이. 기판 처리 장치 방법 및 그에 의해 제조된 장치
US10910262B2 (en) 2017-11-16 2021-02-02 Asm Ip Holding B.V. Method of selectively depositing a capping layer structure on a semiconductor device structure
US11022879B2 (en) 2017-11-24 2021-06-01 Asm Ip Holding B.V. Method of forming an enhanced unexposed photoresist layer
TWI791689B (zh) 2017-11-27 2023-02-11 荷蘭商Ａｓｍ智慧財產控股私人有限公司 包括潔淨迷你環境之裝置
WO2019103613A1 (en) 2017-11-27 2019-05-31 Asm Ip Holding B.V. A storage device for storing wafer cassettes for use with a batch furnace
US10290508B1 (en) 2017-12-05 2019-05-14 Asm Ip Holding B.V. Method for forming vertical spacers for spacer-defined patterning
US10872771B2 (en) 2018-01-16 2020-12-22 Asm Ip Holding B. V. Method for depositing a material film on a substrate within a reaction chamber by a cyclical deposition process and related device structures
US11482412B2 (en) 2018-01-19 2022-10-25 Asm Ip Holding B.V. Method for depositing a gap-fill layer by plasma-assisted deposition
TWI799494B (zh) 2018-01-19 2023-04-21 荷蘭商Ａｓｍ 智慧財產控股公司 沈積方法
USD903477S1 (en) 2018-01-24 2020-12-01 Asm Ip Holdings B.V. Metal clamp
US11018047B2 (en) 2018-01-25 2021-05-25 Asm Ip Holding B.V. Hybrid lift pin
US10535516B2 (en) 2018-02-01 2020-01-14 Asm Ip Holdings B.V. Method for depositing a semiconductor structure on a surface of a substrate and related semiconductor structures
USD880437S1 (en) 2018-02-01 2020-04-07 Asm Ip Holding B.V. Gas supply plate for semiconductor manufacturing apparatus
US11081345B2 (en) 2018-02-06 2021-08-03 Asm Ip Holding B.V. Method of post-deposition treatment for silicon oxide film
US10896820B2 (en) 2018-02-14 2021-01-19 Asm Ip Holding B.V. Method for depositing a ruthenium-containing film on a substrate by a cyclical deposition process
CN111699278B (zh) 2018-02-14 2023-05-16 Asm Ip私人控股有限公司 通过循环沉积工艺在衬底上沉积含钌膜的方法
US10731249B2 (en) 2018-02-15 2020-08-04 Asm Ip Holding B.V. Method of forming a transition metal containing film on a substrate by a cyclical deposition process, a method for supplying a transition metal halide compound to a reaction chamber, and related vapor deposition apparatus
KR102636427B1 (ko) 2018-02-20 2024-02-13 에이에스엠 아이피 홀딩 비.브이. 기판 처리 방법 및 장치
US10658181B2 (en) 2018-02-20 2020-05-19 Asm Ip Holding B.V. Method of spacer-defined direct patterning in semiconductor fabrication
US10975470B2 (en) 2018-02-23 2021-04-13 Asm Ip Holding B.V. Apparatus for detecting or monitoring for a chemical precursor in a high temperature environment
US11473195B2 (en) 2018-03-01 2022-10-18 Asm Ip Holding B.V. Semiconductor processing apparatus and a method for processing a substrate
US11629406B2 (en) 2018-03-09 2023-04-18 Asm Ip Holding B.V. Semiconductor processing apparatus comprising one or more pyrometers for measuring a temperature of a substrate during transfer of the substrate
US11114283B2 (en) 2018-03-16 2021-09-07 Asm Ip Holding B.V. Reactor, system including the reactor, and methods of manufacturing and using same
KR102646467B1 (ko) 2018-03-27 2024-03-11 에이에스엠 아이피 홀딩 비.브이. 기판 상에 전극을 형성하는 방법 및 전극을 포함하는 반도체 소자 구조
US11230766B2 (en) 2018-03-29 2022-01-25 Asm Ip Holding B.V. Substrate processing apparatus and method
US10510536B2 (en) 2018-03-29 2019-12-17 Asm Ip Holding B.V. Method of depositing a co-doped polysilicon film on a surface of a substrate within a reaction chamber
US11088002B2 (en) 2018-03-29 2021-08-10 Asm Ip Holding B.V. Substrate rack and a substrate processing system and method
KR102501472B1 (ko) 2018-03-30 2023-02-20 에이에스엠 아이피 홀딩 비.브이. 기판 처리 방법
KR20190128558A (ko) 2018-05-08 2019-11-18 에이에스엠 아이피 홀딩 비.브이. 기판 상에 산화물 막을 주기적 증착 공정에 의해 증착하기 위한 방법 및 관련 소자 구조
TW202349473A (zh) 2018-05-11 2023-12-16 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 用於基板上形成摻雜金屬碳化物薄膜之方法及相關半導體元件結構
KR102596988B1 (ko) 2018-05-28 2023-10-31 에이에스엠 아이피 홀딩 비.브이. 기판 처리 방법 및 그에 의해 제조된 장치
US11718913B2 (en) 2018-06-04 2023-08-08 Asm Ip Holding B.V. Gas distribution system and reactor system including same
US11270899B2 (en) 2018-06-04 2022-03-08 Asm Ip Holding B.V. Wafer handling chamber with moisture reduction
US11286562B2 (en) 2018-06-08 2022-03-29 Asm Ip Holding B.V. Gas-phase chemical reactor and method of using same
US10797133B2 (en) 2018-06-21 2020-10-06 Asm Ip Holding B.V. Method for depositing a phosphorus doped silicon arsenide film and related semiconductor device structures
KR102568797B1 (ko) 2018-06-21 2023-08-21 에이에스엠 아이피 홀딩 비.브이. 기판 처리 시스템
WO2020002995A1 (en) 2018-06-27 2020-01-02 Asm Ip Holding B.V. Cyclic deposition methods for forming metal-containing material and films and structures including the metal-containing material
KR20210027265A (ko) 2018-06-27 2021-03-10 에이에스엠 아이피 홀딩 비.브이. 금속 함유 재료를 형성하기 위한 주기적 증착 방법 및 금속 함유 재료를 포함하는 막 및 구조체
US10612136B2 (en) 2018-06-29 2020-04-07 ASM IP Holding, B.V. Temperature-controlled flange and reactor system including same
KR20200002519A (ko) 2018-06-29 2020-01-08 에이에스엠 아이피 홀딩 비.브이. 박막 증착 방법 및 반도체 장치의 제조 방법
US10388513B1 (en) 2018-07-03 2019-08-20 Asm Ip Holding B.V. Method for depositing silicon-free carbon-containing film as gap-fill layer by pulse plasma-assisted deposition
US10755922B2 (en) 2018-07-03 2020-08-25 Asm Ip Holding B.V. Method for depositing silicon-free carbon-containing film as gap-fill layer by pulse plasma-assisted deposition
US10767789B2 (en) 2018-07-16 2020-09-08 Asm Ip Holding B.V. Diaphragm valves, valve components, and methods for forming valve components
US10483099B1 (en) 2018-07-26 2019-11-19 Asm Ip Holding B.V. Method for forming thermally stable organosilicon polymer film
US11053591B2 (en) 2018-08-06 2021-07-06 Asm Ip Holding B.V. Multi-port gas injection system and reactor system including same
US10883175B2 (en) 2018-08-09 2021-01-05 Asm Ip Holding B.V. Vertical furnace for processing substrates and a liner for use therein
US10829852B2 (en) 2018-08-16 2020-11-10 Asm Ip Holding B.V. Gas distribution device for a wafer processing apparatus
US11430674B2 (en) 2018-08-22 2022-08-30 Asm Ip Holding B.V. Sensor array, apparatus for dispensing a vapor phase reactant to a reaction chamber and related methods
KR20200030162A (ko) 2018-09-11 2020-03-20 에이에스엠 아이피 홀딩 비.브이. 박막 증착 방법
US11024523B2 (en) 2018-09-11 2021-06-01 Asm Ip Holding B.V. Substrate processing apparatus and method
US11049751B2 (en) 2018-09-14 2021-06-29 Asm Ip Holding B.V. Cassette supply system to store and handle cassettes and processing apparatus equipped therewith
CN110970344A (zh) 2018-10-01 2020-04-07 Asm Ip控股有限公司 衬底保持设备、包含所述设备的系统及其使用方法
US11232963B2 (en) 2018-10-03 2022-01-25 Asm Ip Holding B.V. Substrate processing apparatus and method
KR102592699B1 (ko) 2018-10-08 2023-10-23 에이에스엠 아이피 홀딩 비.브이. 기판 지지 유닛 및 이를 포함하는 박막 증착 장치와 기판 처리 장치
US10847365B2 (en) 2018-10-11 2020-11-24 Asm Ip Holding B.V. Method of forming conformal silicon carbide film by cyclic CVD
US10811256B2 (en) 2018-10-16 2020-10-20 Asm Ip Holding B.V. Method for etching a carbon-containing feature
KR102546322B1 (ko) 2018-10-19 2023-06-21 에이에스엠 아이피 홀딩 비.브이. 기판 처리 장치 및 기판 처리 방법
KR102605121B1 (ko) 2018-10-19 2023-11-23 에이에스엠 아이피 홀딩 비.브이. 기판 처리 장치 및 기판 처리 방법
USD948463S1 (en) 2018-10-24 2022-04-12 Asm Ip Holding B.V. Susceptor for semiconductor substrate supporting apparatus
US10381219B1 (en) 2018-10-25 2019-08-13 Asm Ip Holding B.V. Methods for forming a silicon nitride film
US11087997B2 (en) 2018-10-31 2021-08-10 Asm Ip Holding B.V. Substrate processing apparatus for processing substrates
KR20200051105A (ko) 2018-11-02 2020-05-13 에이에스엠 아이피 홀딩 비.브이. 기판 지지 유닛 및 이를 포함하는 기판 처리 장치
US11572620B2 (en) 2018-11-06 2023-02-07 Asm Ip Holding B.V. Methods for selectively depositing an amorphous silicon film on a substrate
US11031242B2 (en) 2018-11-07 2021-06-08 Asm Ip Holding B.V. Methods for depositing a boron doped silicon germanium film
US10847366B2 (en) 2018-11-16 2020-11-24 Asm Ip Holding B.V. Methods for depositing a transition metal chalcogenide film on a substrate by a cyclical deposition process
US10818758B2 (en) 2018-11-16 2020-10-27 Asm Ip Holding B.V. Methods for forming a metal silicate film on a substrate in a reaction chamber and related semiconductor device structures
US10559458B1 (en) 2018-11-26 2020-02-11 Asm Ip Holding B.V. Method of forming oxynitride film
US11217444B2 (en) 2018-11-30 2022-01-04 Asm Ip Holding B.V. Method for forming an ultraviolet radiation responsive metal oxide-containing film
KR102636428B1 (ko) 2018-12-04 2024-02-13 에이에스엠 아이피 홀딩 비.브이. 기판 처리 장치를 세정하는 방법
US11158513B2 (en) 2018-12-13 2021-10-26 Asm Ip Holding B.V. Methods for forming a rhenium-containing film on a substrate by a cyclical deposition process and related semiconductor device structures
JP2020096183A (ja) 2018-12-14 2020-06-18 エーエスエム・アイピー・ホールディング・ベー・フェー 窒化ガリウムの選択的堆積を用いてデバイス構造体を形成する方法及びそのためのシステム
TW202405220A (zh) 2019-01-17 2024-02-01 荷蘭商Ａｓｍ Ｉｐ 私人控股有限公司 藉由循環沈積製程於基板上形成含過渡金屬膜之方法
KR20200091543A (ko) 2019-01-22 2020-07-31 에이에스엠 아이피 홀딩 비.브이. 기판 처리 장치
CN111524788B (zh) 2019-02-01 2023-11-24 Asm Ip私人控股有限公司 氧化硅的拓扑选择性膜形成的方法
KR102638425B1 (ko) 2019-02-20 2024-02-21 에이에스엠 아이피 홀딩 비.브이. 기판 표면 내에 형성된 오목부를 충진하기 위한 방법 및 장치
KR102626263B1 (ko) 2019-02-20 2024-01-16 에이에스엠 아이피 홀딩 비.브이. 처리 단계를 포함하는 주기적 증착 방법 및 이를 위한 장치
JP2020136677A (ja) 2019-02-20 2020-08-31 エーエスエム・アイピー・ホールディング・ベー・フェー 基材表面内に形成された凹部を充填するための周期的堆積方法および装置
KR20200102357A (ko) 2019-02-20 2020-08-31 에이에스엠 아이피 홀딩 비.브이. 3-d nand 응용의 플러그 충진체 증착용 장치 및 방법
JP2020133004A (ja) 2019-02-22 2020-08-31 エーエスエム・アイピー・ホールディング・ベー・フェー 基材を処理するための基材処理装置および方法
KR20200108243A (ko) 2019-03-08 2020-09-17 에이에스엠 아이피 홀딩 비.브이. SiOC 층을 포함한 구조체 및 이의 형성 방법
KR20200108248A (ko) 2019-03-08 2020-09-17 에이에스엠 아이피 홀딩 비.브이. SiOCN 층을 포함한 구조체 및 이의 형성 방법
KR20200108242A (ko) 2019-03-08 2020-09-17 에이에스엠 아이피 홀딩 비.브이. 실리콘 질화물 층을 선택적으로 증착하는 방법, 및 선택적으로 증착된 실리콘 질화물 층을 포함하는 구조체
JP2020167398A (ja) 2019-03-28 2020-10-08 エーエスエム・アイピー・ホールディング・ベー・フェー ドアオープナーおよびドアオープナーが提供される基材処理装置
KR20200116855A (ko) 2019-04-01 2020-10-13 에이에스엠 아이피 홀딩 비.브이. 반도체 소자를 제조하는 방법
US11447864B2 (en) 2019-04-19 2022-09-20 Asm Ip Holding B.V. Layer forming method and apparatus
KR20200125453A (ko) 2019-04-24 2020-11-04 에이에스엠 아이피 홀딩 비.브이. 기상 반응기 시스템 및 이를 사용하는 방법
KR20200130118A (ko) 2019-05-07 2020-11-18 에이에스엠 아이피 홀딩 비.브이. 비정질 탄소 중합체 막을 개질하는 방법
KR20200130121A (ko) 2019-05-07 2020-11-18 에이에스엠 아이피 홀딩 비.브이. 딥 튜브가 있는 화학물질 공급원 용기
KR20200130652A (ko) 2019-05-10 2020-11-19 에이에스엠 아이피 홀딩 비.브이. 표면 상에 재료를 증착하는 방법 및 본 방법에 따라 형성된 구조
JP2020188255A (ja) 2019-05-16 2020-11-19 エーエスエム アイピー ホールディング ビー．ブイ． ウェハボートハンドリング装置、縦型バッチ炉および方法
JP2020188254A (ja) 2019-05-16 2020-11-19 エーエスエム アイピー ホールディング ビー．ブイ． ウェハボートハンドリング装置、縦型バッチ炉および方法
USD975665S1 (en) 2019-05-17 2023-01-17 Asm Ip Holding B.V. Susceptor shaft
USD947913S1 (en) 2019-05-17 2022-04-05 Asm Ip Holding B.V. Susceptor shaft
USD935572S1 (en) 2019-05-24 2021-11-09 Asm Ip Holding B.V. Gas channel plate
USD922229S1 (en) 2019-06-05 2021-06-15 Asm Ip Holding B.V. Device for controlling a temperature of a gas supply unit
KR20200141002A (ko) 2019-06-06 2020-12-17 에이에스엠 아이피 홀딩 비.브이. 배기 가스 분석을 포함한 기상 반응기 시스템을 사용하는 방법
KR20200143254A (ko) 2019-06-11 2020-12-23 에이에스엠 아이피 홀딩 비.브이. 개질 가스를 사용하여 전자 구조를 형성하는 방법, 상기 방법을 수행하기 위한 시스템, 및 상기 방법을 사용하여 형성되는 구조
USD944946S1 (en) 2019-06-14 2022-03-01 Asm Ip Holding B.V. Shower plate
USD931978S1 (en) 2019-06-27 2021-09-28 Asm Ip Holding B.V. Showerhead vacuum transport
KR20210005515A (ko) 2019-07-03 2021-01-14 에이에스엠 아이피 홀딩 비.브이. 기판 처리 장치용 온도 제어 조립체 및 이를 사용하는 방법
JP2021015791A (ja) 2019-07-09 2021-02-12 エーエスエム アイピー ホールディング ビー．ブイ． 同軸導波管を用いたプラズマ装置、基板処理方法
CN112216646A (zh) 2019-07-10 2021-01-12 Asm Ip私人控股有限公司 基板支撑组件及包括其的基板处理装置
KR20210010307A (ko) 2019-07-16 2021-01-27 에이에스엠 아이피 홀딩 비.브이. 기판 처리 장치
KR20210010820A (ko) 2019-07-17 2021-01-28 에이에스엠 아이피 홀딩 비.브이. 실리콘 게르마늄 구조를 형성하는 방법
KR20210010816A (ko) 2019-07-17 2021-01-28 에이에스엠 아이피 홀딩 비.브이. 라디칼 보조 점화 플라즈마 시스템 및 방법
US11643724B2 (en) 2019-07-18 2023-05-09 Asm Ip Holding B.V. Method of forming structures using a neutral beam
JP2021019198A (ja) 2019-07-19 2021-02-15 エーエスエム・アイピー・ホールディング・ベー・フェー トポロジー制御されたアモルファスカーボンポリマー膜の形成方法
TW202113936A (zh) 2019-07-29 2021-04-01 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 用於利用n型摻雜物及/或替代摻雜物選擇性沉積以達成高摻雜物併入之方法
CN112309900A (zh) 2019-07-30 2021-02-02 Asm Ip私人控股有限公司 基板处理设备
CN112309899A (zh) 2019-07-30 2021-02-02 Asm Ip私人控股有限公司 基板处理设备
US11587815B2 (en) 2019-07-31 2023-02-21 Asm Ip Holding B.V. Vertical batch furnace assembly
US11587814B2 (en) 2019-07-31 2023-02-21 Asm Ip Holding B.V. Vertical batch furnace assembly
US11227782B2 (en) 2019-07-31 2022-01-18 Asm Ip Holding B.V. Vertical batch furnace assembly
KR20210018759A (ko) 2019-08-05 2021-02-18 에이에스엠 아이피 홀딩 비.브이. 화학물질 공급원 용기를 위한 액체 레벨 센서
USD965524S1 (en) 2019-08-19 2022-10-04 Asm Ip Holding B.V. Susceptor support
USD965044S1 (en) 2019-08-19 2022-09-27 Asm Ip Holding B.V. Susceptor shaft
JP2021031769A (ja) 2019-08-21 2021-03-01 エーエスエム アイピー ホールディング ビー．ブイ． 成膜原料混合ガス生成装置及び成膜装置
USD979506S1 (en) 2019-08-22 2023-02-28 Asm Ip Holding B.V. Insulator
KR20210024423A (ko) 2019-08-22 2021-03-05 에이에스엠 아이피 홀딩 비.브이. 홀을 구비한 구조체를 형성하기 위한 방법
USD930782S1 (en) 2019-08-22 2021-09-14 Asm Ip Holding B.V. Gas distributor
USD949319S1 (en) 2019-08-22 2022-04-19 Asm Ip Holding B.V. Exhaust duct
USD940837S1 (en) 2019-08-22 2022-01-11 Asm Ip Holding B.V. Electrode
KR20210024420A (ko) 2019-08-23 2021-03-05 에이에스엠 아이피 홀딩 비.브이. 비스(디에틸아미노)실란을 사용하여 peald에 의해 개선된 품질을 갖는 실리콘 산화물 막을 증착하기 위한 방법
US11286558B2 (en) 2019-08-23 2022-03-29 Asm Ip Holding B.V. Methods for depositing a molybdenum nitride film on a surface of a substrate by a cyclical deposition process and related semiconductor device structures including a molybdenum nitride film
KR20210029090A (ko) 2019-09-04 2021-03-15 에이에스엠 아이피 홀딩 비.브이. 희생 캡핑 층을 이용한 선택적 증착 방법
KR20210029663A (ko) 2019-09-05 2021-03-16 에이에스엠 아이피 홀딩 비.브이. 기판 처리 장치
US11562901B2 (en) 2019-09-25 2023-01-24 Asm Ip Holding B.V. Substrate processing method
CN112593212B (zh) 2019-10-02 2023-12-22 Asm Ip私人控股有限公司 通过循环等离子体增强沉积工艺形成拓扑选择性氧化硅膜的方法
TW202129060A (zh) 2019-10-08 2021-08-01 荷蘭商Ａｓｍ Ｉｐ控股公司 基板處理裝置、及基板處理方法
TW202115273A (zh) 2019-10-10 2021-04-16 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 形成光阻底層之方法及包括光阻底層之結構
KR20210045930A (ko) 2019-10-16 2021-04-27 에이에스엠 아이피 홀딩 비.브이. 실리콘 산화물의 토폴로지-선택적 막의 형성 방법
US11637014B2 (en) 2019-10-17 2023-04-25 Asm Ip Holding B.V. Methods for selective deposition of doped semiconductor material
KR20210047808A (ko) 2019-10-21 2021-04-30 에이에스엠 아이피 홀딩 비.브이. 막을 선택적으로 에칭하기 위한 장치 및 방법
KR20210050453A (ko) 2019-10-25 2021-05-07 에이에스엠 아이피 홀딩 비.브이. 기판 표면 상의 갭 피처를 충진하는 방법 및 이와 관련된 반도체 소자 구조
US11646205B2 (en) 2019-10-29 2023-05-09 Asm Ip Holding B.V. Methods of selectively forming n-type doped material on a surface, systems for selectively forming n-type doped material, and structures formed using same
KR20210054983A (ko) 2019-11-05 2021-05-14 에이에스엠 아이피 홀딩 비.브이. 도핑된 반도체 층을 갖는 구조체 및 이를 형성하기 위한 방법 및 시스템
US11501968B2 (en) 2019-11-15 2022-11-15 Asm Ip Holding B.V. Method for providing a semiconductor device with silicon filled gaps
KR20210062561A (ko) 2019-11-20 2021-05-31 에이에스엠 아이피 홀딩 비.브이. 기판의 표면 상에 탄소 함유 물질을 증착하는 방법, 상기 방법을 사용하여 형성된 구조물, 및 상기 구조물을 형성하기 위한 시스템
KR20210065848A (ko) 2019-11-26 2021-06-04 에이에스엠 아이피 홀딩 비.브이. 제1 유전체 표면과 제2 금속성 표면을 포함한 기판 상에 타겟 막을 선택적으로 형성하기 위한 방법
CN112951697A (zh) 2019-11-26 2021-06-11 Asm Ip私人控股有限公司 基板处理设备
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CN112885692A (zh) 2019-11-29 2021-06-01 Asm Ip私人控股有限公司 基板处理设备
JP2021090042A (ja) 2019-12-02 2021-06-10 エーエスエム アイピー ホールディング ビー．ブイ． 基板処理装置、基板処理方法
KR20210070898A (ko) 2019-12-04 2021-06-15 에이에스엠 아이피 홀딩 비.브이. 기판 처리 장치
TW202125596A (zh) 2019-12-17 2021-07-01 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 形成氮化釩層之方法以及包括該氮化釩層之結構
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CN113652258B (zh) * 2021-07-28 2023-04-07 宁波中金石化有限公司 一种防止金属催化结焦的芳烃生产系统及方法
USD990441S1 (en) 2021-09-07 2023-06-27 Asm Ip Holding B.V. Gas flow control plate
CN116020356A (zh) * 2021-10-25 2023-04-28 中国石油化工股份有限公司 一种逆流移动床低碳烷烃脱氢的方法和系统

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2863825A (en) * 1954-09-24 1958-12-09 Shell Dev Catalytic reforming of hydrocarbon oils
CA962210A (en) * 1971-03-11 1975-02-04 John C. Hayes Catalytic reforming of hydrocarbons
US3999961A (en) * 1974-11-20 1976-12-28 Ralph M. Parsons Company Sulfur control over carbon formation in high temperature reforming operations
US4159938A (en) * 1977-12-23 1979-07-03 Exxon Research & Engineering Co. Start-up procedure for reforming with platinum-iridium catalysts
US4220520A (en) * 1978-11-16 1980-09-02 Exxon Research & Engineering Co. Startup method for a reforming process
CN85106828A (zh) 1985-09-10 1987-03-11 张弋飞 金属零件表面形成硫化物层的方法及设备
CN1126607A (zh) * 1995-09-10 1996-07-17 段鑫 戒烟宝
CN1160435A (zh) 1994-10-18 1997-09-24 马尔科姆J·比尔 双活塞式内燃机
CN1234455A (zh) 1998-03-18 1999-11-10 株式会社日立制作所 镁合金构件及其应用
US6495487B1 (en) 1996-12-09 2002-12-17 Uop Llc Selective bifunctional multimetallic reforming catalyst
US6780814B2 (en) 2001-04-28 2004-08-24 China Petroleum & Chemical Corporation Multimetallic reforming catalyst comprising platinum and tin, the preparation and the application thereof

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US422520A (en) * 1890-03-04 Screw-driver
BR9205738A (pt) * 1991-03-08 1994-08-23 Chevron Res & Tech Processo para reformar hidrocarbonetos, sistemas de reator, tinta contendo estanho e processo para aumentar a resistência à carbonetação de pelo menos uma parte de um sistema de reator
US5200059A (en) * 1991-11-21 1993-04-06 Uop Reformulated-gasoline production
RU2108153C1 (ru) * 1994-05-30 1998-04-10 Юоп Каталитическая система для риформинга углеводородного сырья и способ риформинга
US5954943A (en) 1997-09-17 1999-09-21 Nalco/Exxon Energy Chemicals, L.P. Method of inhibiting coke deposition in pyrolysis furnaces
US5863825A (en) * 1997-09-29 1999-01-26 Lsi Logic Corporation Alignment mark contrast enhancement
CN1126607C (zh) 1998-05-27 2003-11-05 中国石化齐鲁石油化工公司 一种抑制和减缓烃类高温裂解中焦炭形成与沉积的方法
GB0130145D0 (en) * 2001-12-17 2002-02-06 Ici Plc Metal passivation
GB0521534D0 (en) * 2005-10-24 2005-11-30 Johnson Matthey Catalysts Metal passivation

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2863825A (en) * 1954-09-24 1958-12-09 Shell Dev Catalytic reforming of hydrocarbon oils
CA962210A (en) * 1971-03-11 1975-02-04 John C. Hayes Catalytic reforming of hydrocarbons
US3999961A (en) * 1974-11-20 1976-12-28 Ralph M. Parsons Company Sulfur control over carbon formation in high temperature reforming operations
US4159938A (en) * 1977-12-23 1979-07-03 Exxon Research & Engineering Co. Start-up procedure for reforming with platinum-iridium catalysts
US4220520A (en) * 1978-11-16 1980-09-02 Exxon Research & Engineering Co. Startup method for a reforming process
CN85106828A (zh) 1985-09-10 1987-03-11 张弋飞 金属零件表面形成硫化物层的方法及设备
CN1160435A (zh) 1994-10-18 1997-09-24 马尔科姆J·比尔 双活塞式内燃机
CN1126607A (zh) * 1995-09-10 1996-07-17 段鑫 戒烟宝
US6495487B1 (en) 1996-12-09 2002-12-17 Uop Llc Selective bifunctional multimetallic reforming catalyst
CN1234455A (zh) 1998-03-18 1999-11-10 株式会社日立制作所 镁合金构件及其应用
US6780814B2 (en) 2001-04-28 2004-08-24 China Petroleum & Chemical Corporation Multimetallic reforming catalyst comprising platinum and tin, the preparation and the application thereof

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
"Catalytic Reforming (1 st Edition", April 2004, CHINA PETROCHEMICAL PRESS, pages: 200 - 202
"Catalytic Reforming Process and Engineering (1" Edition", November 2006, CHINA PETROCHEMICAL PRESS, pages: 522 - 534
PETROLEUM PROCESSING AND PETROCHEMICALS AND INDUSTRIAL CATALYSIS, vol. 33, no. 8, 2002, pages 26 - 29
See also references of EP2210929A4 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120277511A1 (en) * 2011-04-29 2012-11-01 Uop Llc High Temperature Platformer
US9199893B2 (en) 2014-02-24 2015-12-01 Uop Llc Process for xylenes production

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