WO2017101274A1 - 一种液相加氢异构系统及其工艺和应用 - Google Patents

一种液相加氢异构系统及其工艺和应用 Download PDF

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WO2017101274A1
WO2017101274A1 PCT/CN2016/085257 CN2016085257W WO2017101274A1 WO 2017101274 A1 WO2017101274 A1 WO 2017101274A1 CN 2016085257 W CN2016085257 W CN 2016085257W WO 2017101274 A1 WO2017101274 A1 WO 2017101274A1
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hydrogen
hydroisomerization
oil
reactor
liquid phase
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PCT/CN2016/085257
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English (en)
French (fr)
Inventor
马守涛
黄小侨
孙发民
马庆丰
谢方明
段永生
吴显军
李凤铉
葛冬梅
夏恩冬
李瑞峰
季荣磊
刘丽莹
秦丽红
孟祥彬
董春明
陆雪峰
王锐
徐铁钢
倪术荣
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Petrochina Co Ltd
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Petrochina Co Ltd
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Priority to US15/748,851 priority Critical patent/US10683459B2/en
Publication of WO2017101274A1 publication Critical patent/WO2017101274A1/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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
    • 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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/72—Controlling or regulating
    • 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
    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
    • C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
    • C10G65/043—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps at least one step being a change in the structural skeleton
    • 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
    • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
    • C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
    • 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
    • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
    • C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • C10L1/08—Liquid carbonaceous fuels essentially based on blends of hydrocarbons for compression ignition
    • C—CHEMISTRY; METALLURGY
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M101/00—Lubricating compositions characterised by the base-material being a mineral or fatty oil
    • C10M101/02—Petroleum fractions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/02—Well-defined hydrocarbons
    • C10M105/04—Well-defined hydrocarbons aliphatic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M177/00—Special methods of preparation of lubricating compositions; Chemical modification by after-treatment of components or of the whole of a lubricating composition, not covered by other classes
    • 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
    • C10G2300/1011—Biomass
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/1048—Middle distillates
    • C10G2300/1055—Diesel having a boiling range of about 230 - 330 °C
    • 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
    • C10G2300/1062—Lubricating oils
    • 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
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/42—Hydrogen of special source or of special composition
    • 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
    • C10G2400/04—Diesel oil
    • 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
    • C10G2400/10—Lubricating oil
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/02—Well-defined aliphatic compounds
    • C10M2203/0206—Well-defined aliphatic compounds used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/102—Aliphatic fractions
    • C10M2203/1025—Aliphatic fractions used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/02—Viscosity; Viscosity index
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/02—Pour-point; Viscosity index
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

  • the invention belongs to the field of hydrocarbon conversion processes for oil products, and in particular relates to a liquid phase hydroisomerization system and a process and application thereof.
  • Hydrocracking tail oil is the best raw material for producing APIIII base oil with low viscosity, low pour point and viscosity index greater than 120, but the tail oil has high freezing point, pour point and high cloud point, and contains partially hydrogenated aromatic hydrocarbons. Poor stability, should further saturate aromatics on the basis of isomerization dewaxing. Chevron is the world's first hydrocracking-isomerization dewaxing-hydrogenation process (Isodewaxing process) to produce lubricant base oils, which has been widely used.
  • hydroisomerization techniques typically employ a three-phase reaction (gas/liquid/solid catalyst), such as conventional trickle bed technology, to convert normal paraffins to isoparaffins.
  • the continuous phase in the reactor is the gas phase and typically requires a large amount of hydrogen to maintain the gas phase continuous in the reactor.
  • the hydroisomerization dewaxing reaction is a micro exothermic reaction, in order to maintain the reaction temperature, excess hydrogen is required to carry away the heat of reaction through the catalyst bed; on the other hand, in the gas-liquid-solid three In the reaction of the phase, maintaining a high hydrogen partial pressure is advantageous for the hydrogenation reaction, suppressing coke formation, and prolonging the life of the catalyst.
  • the excess hydrogen is typically pressurized by a recycle hydrogen compressor and mixed with fresh hydrogen to continue as a hydrogen feed to the reaction.
  • This process can also be defined as a gas phase circulating trickle bed hydrogenation process.
  • providing such a large amount of gaseous hydrogen for isomerization under operating conditions adds complexity and expense.
  • the final reactor effluent is typically separated into a hydrogen-containing gas phase component and a liquid component.
  • the gas phase components typically enter the compressor and are then recycled back to the reactor inlet to help provide a large amount of hydrogen to maintain a continuous gas phase.
  • the circulating hydrogen compressor has a higher proportion of the cost of the entire hydrogenation unit, and the hydrogen heat exchange system consumes more energy. If the hydrogen flow rate in the hydrogenation process can be reduced and the hydrogen cycle is omitted. System and circulating hydrogen compressors can save investment costs for companies.
  • the hydroisomerization reaction generally does not consume a large amount of hydrogen.
  • a large excess of hydrogen is often present throughout the heterogeneous reaction system to form a continuous gas phase which is generally not required for the isomerization reaction.
  • Excess hydrogen is separated from the final effluent and then treated with additional separators and piping for further processing. As discussed above, if this excess hydrogen is recycled to the hydroisomerization inlet to supply hydrogen to the system, the hydrogen must provide the reactor with the desired high pressure hydrogen through a high pressure compressor.
  • Two-phase hydrogenation processes eg, liquid materials and solid catalysts
  • conversion of certain hydrocarbon-containing materials to other more valuable hydrocarbons liquid phase reactors can be used in the process
  • liquid phase reactors can be used in the process
  • a two-phase system liquid phase reactor
  • liquid phase reactors Other uses for liquid phase reactors are hydrocracking and hydrotreating of hydrocarbonaceous materials.
  • hydrotreating and hydrocracking require a corresponding chemical conversion of a large amount of hydrogen. Therefore, even if these reactions are all in the liquid phase system, a large amount of hydrogen is still required. Therefore, in order to maintain the hydrogen required for such a liquid phase hydrotreating or hydrocracking reaction, it is necessary to introduce an additional diluent or solvent into the raw material of the existing liquid phase system for diluting the reaction group in the feed. And reduce the temperature rise of the reactor. Thus, the diluent and solvent need to have a greater concentration of dissolved hydrogen relative to the feedstock, ensuring that sufficient conversion can occur in the liquid phase.
  • these reaction systems often require larger, more complex, and more expensive liquid phase reactors to achieve the desired conversion.
  • the two-phase process mainly includes the IsoTherming technology of DuPont, and the company's patents US6881326B2 and ZL200680018017.3 disclose the use of a diluent or a solvent to provide a larger hydrogen concentration, using a product as a diluent or a solvent, but due to the occurrence Hydrocracking or hydrotreating reaction, the consumption of hydrogen is large, resulting in a large amount of product circulation.
  • No. 7,803,269 B2 discloses a liquid phase hydroisomerization process for the hydroisomerization of Fischer-Tropsch synthetic oil or vegetable oil consisting of C8-C30 linear paraffins to reduce cloud point, pour point, and pour point.
  • the hydroisomerization process has low hydrogen consumption, no circulation of products, and no additional hydrogen supplementation in the hydroisomerization reaction zone, but the process is not suitable for high dry point or/and high aromatic content.
  • Mineral oil fraction or synthetic oil is hydroisomerized. Moreover, this process cannot hydrotreat the hydroisomerized oil, and the aromatic hydrocarbon cannot be further saturated. Therefore, in order to improve the color and oxidation stability of the product, an additional additive is required.
  • Another object of the present invention is to provide a liquid phase hydroisomerization process utilizing the above system.
  • liquid phase hydroisomerization system comprising:
  • the hydrogen solvator includes an oil feed line, a hydrogen feed line, and a hydrogen oil mixture line, the hydrogen oil mixture line is in communication with a bottom of the hydroisomerization reactor, the hydroisomerization reactor The top is in communication with the fractionation column;
  • the hydroisomerization reactor comprises at least two catalyst beds, at least between a group of two adjacent catalyst beds is provided with a supplemental hydrogen-dissolving inner member;
  • the supplementary hydrogen-dissolving inner member comprises a bottom mesh isolation plate, a middle mixing space and a top insulation plate, the top insulation plate is provided with a plurality of drainage pipes, the middle mixing space is provided with a hydrogen inlet and a hydrogen outlet; hydrogen and oil The product is mixed in the middle mixed space, and the liquid phase in which the hydrogen is dissolved is discharged through the drain pipe, and the undissolved hydrogen is discharged through the hydrogen outlet.
  • At least one cutting fraction line other than the product of interest in the fractionation column is in communication with the oil feed line.
  • the number of catalyst beds is 2 to 5.
  • the system further comprises a hydrotreating reactor, which is disposed before or after the hydroisomerization reactor;
  • the hydrogen oil mixture line is in communication with the bottom of the hydrofinishing reactor, the top of the hydrofinishing reactor and the hydroisomerization reactor The bottom is connected, and the top of the hydroisomerization reactor is in communication with the fractionation column;
  • the hydrogen oil mixture line is in communication with the bottom of the hydroisomerization reactor, the top of the hydroisomerization reactor and the hydrofining reactor
  • the bottom of the hydrotreating reactor is in communication with the fractionation column;
  • the hydrofinishing reactor comprises at least two catalyst beds, and a supplemental hydrogen-dissolving inner member is arranged in two adjacent catalyst beds;
  • the number of catalyst beds is from 2 to 5.
  • the number of catalyst beds in each reactor may be based on the nature of the raw materials and the reaction. The processing amount of the material is adjusted accordingly.
  • the present invention further provides a liquid phase hydroisomerization process utilizing the above system, the process comprising the steps of:
  • step (3) The product obtained in the step (2) is sent to a fractionation column for fractional distillation, and fractionated to obtain a desired product.
  • the oil and hydrogen are formed into a pure liquid hydrogen oil mixture by a hydrogen hydride (conventional gas-liquid mixer), and this hydrogen required for a part of the reaction is preliminarily
  • a hydrogen hydride conventional gas-liquid mixer
  • the hydrogen oil mixture is formed from the bottom up through the catalyst bed of the hydroisomerization reactor.
  • the upflow reactor bottom feed, upper discharge
  • the upflow reactor has a higher catalyst loading rate, requires less internal components and mature technology, has less space for internal components, has high space utilization rate of the reactor, and has small maintenance work.
  • the reactor has a small pressure drop and saves energy.
  • the hydrogen oil mixture is replenished with hydrogen by replenishing the hydrogen-dissolving internal component (the supplemented hydrogen is substantially completely dissolved in the oil, and the hydrogen which is reacted here is supplemented), so that the hydrogenation is different.
  • the hydrogen-dissolving internal component There is always a constant amount of dissolved hydrogen in the constitutive zone (can be maintained at ⁇ 5% of the saturated hydrogen solubility); in addition, the supplemental hydrogen-dissolving internal component also has the effect of absorbing part of the reaction heat of the previous bed and reducing the temperature rise of the bed. .
  • the liquid phase hydroisomerization process provided by the present invention ensures the continuous isomerization reaction rate and the isoparaffin yield by the above characteristics.
  • the liquid phase hydroisomerization process provided by the present invention greatly reduces the amount of hydrogen in the reaction system by using a normal paraffin in a continuous liquid phase reaction zone for isomerization of a hydrocarbon feedstock in an oil, rather than A three-phase reaction system that requires a large amount of high pressure hydrogen to maintain a continuous gas phase.
  • the hydrogenated heterogeneous region can be The conditions of the continuous liquid phase and the rate of reaction of the continuous equilibrium are maintained.
  • suitable hydrogen storage and/or selection may be selected according to the quality of the oil and the specific process requirements.
  • the amount of hydrogen replenishment for example, when the amount of hydrogen required for the isomerization reaction is small, hydrogen can be supplied mainly by the hydrogen hydrider, and the amount of hydrogen replenished by the internal component of the replenished hydrogen is correspondingly reduced.
  • the liquid phase hydroisomerization process provided by the invention can reduce at least one value of the cloud point, the pour point and the cold filter point in the hydrocarbon raw material by the continuous liquid phase hydroisomerization process.
  • the oil is distillate
  • the distillate has a distillation range of 65 ° C to 550 ° C; further preferably, the distillate is a hydrocracking tail a combination of one or more of oil, catalytic diesel, coker diesel, straight run diesel, straight run wax oil, vacuum distillate oil, coker wax oil, deasphalted oil, and synthetic oil; more preferably, the distillate oil It is a hydrocracking tail oil.
  • the hydrogen dissolved in the hydrogen oil mixture is in a saturated state or a supersaturated state.
  • the amount of hydrogen dissolved in the hydrogen oil mixture can be appropriately adjusted according to the different properties of the oil. When the oil needs to consume more hydrogen, the dissolved amount of hydrogen can be adjusted to a supersaturated state.
  • the amount of hydrogen dissolved in the liquid phase continuous phase in the hydroisomerization reaction and/or the hydrofinishing reaction is sufficient to maintain the stability of the reaction.
  • the catalyst used in the hydroisomerization reaction is generally related to the nature of the raw material to be processed, and is generally a conventional noble metal catalyst or a non-precious metal catalyst.
  • the precious metal catalyst can be a hydrogenation isomerization catalyst such as PIC-802 and PIC-812 produced by Beijing Sanju Environmental Protection New Material Co., Ltd.; the non-precious metal catalyst can be a diesel equivalent such as HIDW produced by the catalyst of PetroChina Fushun Petrochemical Company. Decreasing catalyst.
  • the hydroisomerization reaction conditions are: a reaction pressure of 6.0 MPa to 16.0 MPa, a reaction temperature of 320 ° C to 395 ° C, and a volumetric space velocity of 0.2 h - 1 -2.0h -1 .
  • the hydrotreating reaction conditions are: a reaction pressure of 6.0 MPa to 16.0 MPa, a reaction temperature of 220 ° C to 385 ° C, and a volumetric space velocity of 0.2 h -1 . -3.0h -1 .
  • hydroisomerization and hydrofinishing can be carried out in the prior art form, such as a series hydrogenation process for isomerization dewaxing - hydrofining (two Hydrogenation reactors, or a series of series hydrogenation processes for hydrorefining - heterogeneous pour point depressing (two hydrogenation reactors).
  • the process further comprises the step of transferring one or more fractions other than the product of interest obtained after fractionation into the oil.
  • the hydrocarbon feedstock in the oil (or at least in part) is mixed with the fraction from the fractionation column, then hydrogenated by a hydrogen hydrider, and then passed to a continuous liquid phase hydroisomerization zone reaction.
  • the above scheme is to use a part of the fraction as a liquid phase circulation to assist the hydrogen storage, which is equivalent to improving the liquid phase heterogeneous zone dissolution.
  • the ratio of hydrogen to reactants; and, as the reaction proceeds, hydrogen is consumed, and a certain amount of hydrogen is supplied to the reaction zone by replenishing the hydrogen-dissolving internals, and the liquid phase recycle can still dissolve a certain amount of hydrogen in the reaction zone.
  • the liquid phase hydroisomerization process can determine whether product circulation and circulating oil properties are required according to the actual situation of hydrogenation isomerization to ensure the yield and selectivity of the target product.
  • the hydrogen gas is mainly in a dissolved state (substantially free of hydrogen bubbles or only a small amount of bubbles).
  • liquid product circulating oil is described, but the patent is a product cycle of a gas-liquid countercurrent reactor; and the second reactor in the patent is not a liquid phase reaction.
  • the reactor is a gas-liquid reverse flow reactor, and therefore, the final reaction product properties and reaction conditions are different from those of a pure liquid phase reactor.
  • the hydrogen gas discharged from the hydrogen-soluble internal member is supplied to the hydrogen circulation system.
  • the invention also provides the application of the above liquid phase hydroisomerization process in the production of lubricating base oil of lubricating oil raw materials or the production of low-condensation diesel oil by hydroisomerization and dehydration of diesel oil.
  • liquid phase hydroisomerization system and process provided by the invention eliminates the circulating hydrogen compressor, and the oil product hydrogenation process is simple, reducing the investment cost and the operation risk.
  • Embodiment 1 is a schematic structural view of a hydrogen-dissolving inner member in Embodiment 1;
  • Example 2 is a schematic view showing a liquid phase hydroisomerization process in Example 1;
  • This example provides a liquid phase hydroisomerization system (the first reactor is a hydroisomerization reactor and the second is a hydrotreating reactor) comprising the following apparatus:
  • the hydroisomerization reactor 4 is provided with three catalyst beds, and respectively, a supplemental hydrogen-dissolving inner member is disposed between adjacent catalyst beds, and each catalyst bed is filled with a hydroisomerization dewaxing catalyst;
  • the above-mentioned supplementary hydrogen-dissolving inner member (the structural schematic diagram thereof is as shown in FIG. 1) comprises a bottom screen partitioning plate, a middle mixing space and a top separating plate, the top separating plate is provided with a plurality of liquid discharging pipes, and the middle mixed space is provided with a hydrogen inlet and a hydrogen gas. Export; hydrogen and oil are mixed in the middle mixed space, the liquid phase in which the hydrogen is dissolved is discharged through the drain pipe, and the undissolved hydrogen is discharged through the hydrogen outlet;
  • the hydrotreating reactor 5 is provided with three catalyst beds, and respectively, a supplemental hydrogen-dissolving inner member is disposed between adjacent catalyst beds, and each catalyst bed is filled with a hydrotreating catalyst;
  • the hydrogen pipeline 1 is divided into three branches, which are the first branch of hydrogen, the second branch of hydrogen and the third branch of hydrogen.
  • the first branch of hydrogen is connected with the oil feed line 2, and the second branch of hydrogen Two parts, respectively, and hydroisomerization
  • the two supplemental hydrogen-dissolving inner members of the reactor 4 are connected, and the third branch of the hydrogen gas is divided into two parts and is respectively connected with two supplementary hydrogen-dissolving inner members in the hydrofining reactor 5;
  • the oil feed line 2 is in communication with the gas-liquid mixer 3, and the gas-liquid mixer 3 is connected to the bottom feed port of the hydroisomerization reactor 4 through a hydrogen oil mixture line, and the top of the hydroisomerization reactor 4 is discharged.
  • the mouth is connected to the bottom feed port of the hydrofining reactor 5, and the top discharge port of the hydrofining reactor 5 is connected to the rectification column 6, which is provided with a product line 7 and a non-product fraction line, and a product line. 7 Leading out of the boundary zone, the non-product distillate line is in communication with the inlet of the circulation pump 8, and the outlet of the circulation pump 8 is in communication with the oil feed line 2.
  • a liquid phase hydroisomerization process using the above system (the schematic diagram of the process is shown in FIG. 2), specifically comprising the following steps:
  • the hydrogen oil mixture is subjected to hydroisomerization reaction to obtain a hydroisomerization reaction product, and the hydroisomerization process conditions are: hydrogen partial pressure 12.2 MPa, reaction temperature 320 ° C , the volumetric space velocity is 1.2h -1 ; the isomerization dewaxing catalyst used in the reaction is the precious metal catalyst PIC-812;
  • the hydroisomerization reaction product is sent from the bottom to the hydrotreating reactor 5 for hydrorefining, and then the hydrofinished product is sent to the fractionation column 6.
  • the hydrorefining process conditions are: hydrogen partial pressure of 12.2 MPa, The reaction temperature is 220 ° C, and the volumetric space velocity is 2.0 h -1 ;
  • This example provides a liquid phase hydroisomerization process that utilizes a system similar to that of Example 1, except that the hydroisomerization reactor and the hydrofinishing reactor are each provided with four catalyst beds.
  • a supplemental hydrogen-dissolving inner member is respectively disposed between two adjacent catalyst beds, and the process specifically includes the following steps:
  • the hydrogen oil mixture is subjected to hydroisomerization reaction to obtain a hydroisomerization reaction product, and the hydroisomerization process conditions are: hydrogen partial pressure 12.2 MPa, reaction temperature 365 ° C , the volume space velocity is 0.85h -1 ; the isomerization dewaxing catalyst used in the reaction is the precious metal catalyst PIC-812;
  • the hydroisomerization reactor 4 is provided with five catalyst beds, and respectively, a supplemental hydrogen-dissolving inner member is disposed between adjacent catalyst beds, and each catalyst bed is filled with a hydroisomerization dewaxing catalyst;
  • the above-mentioned supplementary hydrogen-dissolving inner member comprises a bottom screen partitioning plate, a middle mixing space and a top separating plate, the top separating plate is provided with a plurality of liquid discharging pipes, the middle mixing space is provided with a hydrogen inlet and a hydrogen outlet; and the hydrogen and oil are mixed in the middle space. Mixing, the liquid phase in which the hydrogen is dissolved is discharged through the drain pipe, and the undissolved hydrogen is discharged through the hydrogen outlet;
  • the hydrogen pipeline 1 is divided into two branches, which are the first branch of hydrogen and the second branch of hydrogen.
  • the first branch of hydrogen is connected with the oil feed line 2, and the second branch of hydrogen is divided into four parts, and respectively Communicating with four supplementary hydrogen-dissolving inner members in the hydroisomerization reactor 4;
  • the oil feed line 2 is in communication with the gas-liquid mixer 3, and the gas-liquid mixer 3 is connected to the bottom feed port of the hydroisomerization reactor 4 through a hydrogen oil mixture line, and the top of the hydroisomerization reactor 4 is discharged.
  • the port is connected to the rectification column 6, the rectification column 6 is provided with a product line 7 and a non-product distillate line, the product line 7 is taken out of the boundary zone, and the products in the non-product distillate line are not recycled.
  • the hydrogen oil mixture is subjected to hydroisomerization reaction to obtain a hydroisomerization reaction product;
  • the hydroisomerization process conditions are: hydrogen partial pressure of 15.6 MPa, reaction temperature of 340 ° C , the volume space velocity is 1.5h -1 ;
  • the isomerization dewaxing catalyst used in the reaction is the precious metal catalyst PIC-812;
  • the hydrocracking tail oil base oil yield is over 80%, and 2cSt, 4cSt II/II+, 5cSt III, 6cSt III can be produced according to different processing schemes. , 8cSt III base oil.
  • This embodiment provides a liquid phase hydroisomerization system and process (the first reactor is a hydrotreating reactor and the second is a hydroisomerization reactor) comprising the following apparatus:
  • the above-mentioned supplementary hydrogen-dissolving inner member comprises a bottom screen partitioning plate, a middle mixing space and a top separating plate, the top separating plate is provided with a plurality of liquid discharging pipes, the middle mixing space is provided with a hydrogen inlet and a hydrogen outlet; and the hydrogen and oil are mixed in the middle space. Mixing, the liquid phase in which the hydrogen is dissolved is discharged through the drain pipe, and the undissolved hydrogen is discharged through the hydrogen outlet;
  • the hydrotreating reactor 5 is provided with three catalyst beds, and respectively, a supplemental hydrogen-dissolving inner member is disposed between adjacent catalyst beds, and each catalyst bed is filled with a hydrotreating catalyst;
  • the hydrogen pipeline 1 is divided into three branches, which are the first branch of hydrogen, the second branch of hydrogen and the third branch of hydrogen.
  • the first branch of hydrogen is connected with the oil feed line 2, and the second branch of hydrogen It is two parts and is respectively connected with two supplementary hydrogen-dissolving internal components in the hydroisomerization reactor 4, and the third branch of hydrogen is divided into two parts, and respectively supplemented with two of the hydrorefining reactors 5 Hydrogen internal components are connected;
  • the process specifically includes the following steps:
  • the hydrogen oil mixture is subjected to a hydrotreating reaction, and the hydrorefining process conditions are: a reaction system pressure of 6.5 MPa, a reaction temperature of 355 ° C, and a space velocity of 1.5 h -1 ;
  • the hydrofining reaction product is sent to the hydroisomerization reactor 4 for hydrogenation isomerization reaction to obtain a hydroisomerization reaction product, and the hydrogenation isomerization process conditions are: reaction system pressure 6.5 MPa, reaction temperature 350 °C, space velocity 1.5h -1 ;
  • the heterogeneous pour point depressing catalyst used in the reaction is non-precious metal catalyst HIDW, and the product does not circulate.
  • the raw material oil D and product properties are listed in Table 5.

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Abstract

一种液相加氢异构系统及其工艺和应用，该系统包括气液混合器（3）、加氢异构反应器（4）和分馏塔（6）；将油品和氢气混合成液态氢油混合物并引入加氢异构反应器进行加氢异构反应，产物分馏后引出目的产品；至少在一组相邻的两个催化剂床层之间设有补充溶氢内构件用于向反应物中补充氢气。该工艺取消了循环氢压缩机，工艺流程简单，可应用于润滑油原料加氢异构生产润滑油基础油或柴油原料加氢异构降凝生产低凝柴油。

Description

一种液相加氢异构系统及其工艺和应用 技术领域
本发明属于油品的烃类转化工艺领域，具体涉及一种液相加氢异构系统及其工艺和应用。
背景技术
随着原油重质化程度不断加剧以及对清洁燃料需求不断增加，各国炼厂已建成投产多套大型加氢裂化装置，加氢裂化处理能力越来越大。由于裂化反应前要对原料加氢精制，以除去硫、氮等非烃杂质，同时发生芳烃饱和、开环、脱烷基和异构化等反应，因而原油经加氢裂化处理后，尾油饱和烃(主要为C20-C30正构烷烃)含量高达96.8％以上，芳烃含量小于1％，具有硫、氮、金属等杂质含量低等显著特点，可直接进行加氢异构，节省了原料预处理环节的投资和加工成本，是生产中、低粘度Ⅱ、Ⅲ类基础油的优异原料。随着加氢裂化装置的普及，以尾油为原料生产润滑油基础油成为主流方向。
加氢裂化尾油是生产低粘度、低倾点、粘度指数大于120的APIⅢ类基础油的最佳原料，但尾油凝点、倾点、浊点很高，含有部分加氢的芳烃，光安定性差，应在异构脱蜡基础上进一步饱和芳烃。Chevron公司在世界上第一个采用加氢裂化－异构脱蜡－加氢后处理工艺(Isodewaxing工艺)生产润滑油基础油，该工艺已得到了广泛的应用。
当前，加氢异构技术通常采用三相反应(气/液/固体催化剂)，如传统的滴流床技术，将正构烷烃转化成异构烷烃。在这些体系中，反应器中的连续相是气相，通常需要大量的氢气以维持反应器中始终是气相连续的。这是因为，一方面，加氢异构脱蜡反应是一个微放热反应，为了维持反应温度，需要过量的氢气通过催化剂床层带走反应热；另一方面，在气-液-固三相的反应中，维持较高的氢分压有利于加氢反应，抑制焦炭生成，延长催化剂寿命。富余的氢气通常经循环氢压缩机增压后与新氢混合继续作为反应的氢气进料。这个工艺过程也可以定义为气相循环滴流床加氢工艺。然而，在操作条件下，为异构化提供如此大量的气态氢，增加了复杂性和费用。
例如，为提供和维持气相连续所需数量的氢气，异构反应器最终流出物通常分离成一个含氢气的气相组分和一个液态组分。气相组分通常进入压缩机，然后循环回到反应器入口，以帮助提供大量的氢气，以此维持连续气相。循环氢压缩机作为加氢过程的关键设备，投资占整个加氢装置成本的比例较高，氢气换热系统能耗较大，如果能够将加氢过程中的氢气流量减小并省去氢气循环系统和循环氢压缩机，可以为企业节省投资成本。
另一方面，虽然这样的三相系统通常需要大量的氢，以保持连续气相，但加氢异构化反应通常不消耗大量的氢。但是某些情况下也有可能消耗一定量的氢气，例如在异构反应区，可能发生少部分裂化。于是，在整个异构反应系统往往存在大量过剩氢，形成一个连续的气相，而这通常是异构化反应所不需要的。过剩的氢从最终流出物中分离出来，然后再用额外的分离器和管道进行下一步处理。如以上所讨论的，如果这个过剩氢循环到加氢异构反应入口给系统供氢，则氢气必须通过高压压缩机给反应器提供所需的高压氢气。
两相加氢工艺(例如，液态物料和固体催化剂)也是提出了在某些情况下，将某些含烃物料转化成其他更有价值的烃类(液相反应器可被用于该工艺)。比如，通过氢预饱和，可以采用两相系统(液相反应器)降低某些烃流中的硫，而不是使用传统的三相系统。
对液相反应器的其他使用是加氢裂化和含烃物料的加氢处理。然而，加氢处理和加氢裂化需要大量氢气发生相应的化学转化。因此，即使这些反应全部在液相系统中，仍然需要大量的氢气。因此，为了维持这样一种液相加氢处理或加氢裂化反应所需的氢气，需要在现有的液相系统的原料中引入额外的稀释剂或溶剂，用于稀释进料中的反应组分以及降低反应器温升。于是，相对于原料来说，稀释剂和溶剂需要具有更大的溶氢浓度，确保可以在液相中发生足够的转化率。但这些反应系统往往需要更大、更加复杂、更贵的液相反应器，以实现所需的转化。
目前两相工艺主要有DuPont公司的IsoTherming技术，该公司的专利US6881326B2和ZL200680018017.3中公开了使用稀释剂或溶剂提供更大的溶氢浓度，采用产品作为稀释剂或溶剂的方案，但由于发生加氢裂化或加氢处理反应，氢气消耗量较大，导致产品循环量较大。
US7803269B2公开了一种液相加氢异构工艺，用于由C8-C30的直链烷烃组成的费托合成油或植物油加氢异构，降低浊点、倾点、凝点。该加氢异构工艺具有氢耗低，产品不需循环，并且加氢异构反应区也不需要额外补氢等特点，但该工艺不适用于干点较高或/和芳烃含量较高的矿物油馏分或者合成油加氢异构。而且，该工艺不能对加氢异构生成油进行加氢精制，无法进一步将芳烃饱和，因此，为了改进产品的颜色和氧化安定性，还需要额外添加添加剂。
发明内容
为克服上述问题，本发明的目的在于提供一种液相加氢异构系统。
本发明的另一目的是提供一种利用上述系统的液相加氢异构工艺。
本发明的又一目的是提供上述液相加氢异构工艺在润滑油原料加氢异构生产润滑油基础油或柴油加氢异构降凝生产低凝柴油方面的应用。
为达到上述目的，本发明提供了一种液相加氢异构系统，该系统包括：
溶氢器、加氢异构反应器和分馏塔；
所述溶氢器包括油品进料管线、氢气进料管线和氢油混合物管线，所述氢油混合物管线与所述加氢异构反应器的底部连通，所述加氢异构反应器的顶部与所述分馏塔连通；
所述加氢异构反应器中包括至少两个催化剂床层，至少在一组相邻的两个催化剂床层之间设有补充溶氢内构件；
所述补充溶氢内构件包括底部筛孔隔离板、中部混合空间和顶部隔离板，所述顶部隔离板设置有若干排液管道，所述中部混合空间设有氢气入口和氢气出口；氢气与油品在中部混合空间进行混合，溶解了氢气的液相通过排液管道排出，未被溶解的氢气通过氢气出口排出。
在上述液相加氢异构系统中，优选地，所述分馏塔中至少有一个除目的产品之外的切割馏分管线与所述油品进料管线连通。
在上述液相加氢异构系统中，优选地，在所述加氢异构反应器中，催化剂床层的个数为2-5个。
在上述液相加氢异构系统中，优选地，该系统还包括加氢精制反应器，所述加氢精制反应器设于加氢异构反应器之前或之后；
当加氢精制反应器设于加氢异构反应器之前时，所述氢油混合物管线与加氢精制反应器的底部连通，所述加氢精制反应器的顶部与加氢异构反应器的底部连通，所述加氢异构反应器的顶部与所述分馏塔连通；
当加氢精制反应器设于加氢异构反应器之后时，所述氢油混合物管线与加氢异构反应器的底部连通，所述加氢异构反应器的顶部与加氢精制反应器的底部连通，所述加氢精制反应器的顶部与所述分馏塔连通；
进一步优选地，所述加氢精制反应器中包括至少两个催化剂床层，在相邻的两个催化剂床层中设有补充溶氢内构件；
更优选地，在加氢精制反应器中，催化剂床层的个数为2-5个。
在上述液相加氢异构系统中，各反应器中催化剂床层的数目可根据原料性质、反应 物料的加工量等进行相应调整。
本发明另外提供了一种利用上述系统的液相加氢异构工艺，该工艺包括以下步骤：
(1)将油品和氢气在溶氢器中混合为液态的氢油混合物；
(2)将氢油混合物送入后续的加氢异构反应器和/或加氢精制反应器，进行加氢异构反应和/或加氢精制反应；
(3)将经步骤(2)制得的产物送入分馏塔进行分馏，经分馏获得目的产品。
在上述液相加氢异构工艺中，一方面，通过溶氢器(常规的气液混合器)使油品和氢气形成纯液体状态的氢油混合物，这种预先使一部分反应所需的氢气溶解于油品中的操作，可使加氢异构反应具有较快的速率和较好的反应效果；另外，使氢油混合物从下而上通过加氢异构反应器的催化剂床层，形成了一种上行式液相加氢流程。
加氢异构反应中，为了保证反应器中液相的溶解氢始终处于饱和状态，会有少量的过剩氢在反应器出口以气相形态存在，此时反应器中的液相为连续相，少量的气相为分散相，为防止分散相的气体聚集在反应器的局部部位，影响反应物流流动的均匀性，所以选择上流式反应器(底部进料、上部出料)。因为在上流式反应中，反应物流的气、液两相自下而上流过催化剂床层，介质流动方向与气体扩散方向一致，最大程度的减小了气体在反应器内局部累积的可能性，有利于将少量的氢气分布均匀。而下行式反应器气体浮力和气体流量偏小是较难解决的技术难题，床层间也需设置排气措施以维持液位稳定。另外，与下行式反应器相比，上流式反应器具有较高的催化剂装填率，需要的内构件少且技术成熟，内构件占用空间小，反应器的空间利用率高，检修工作量小，反应器压降小，节约能耗。
加氢异构反应中，通过补充溶氢内构件向氢油混合物补充氢气(补充后的氢气在油品中基本为全溶解态，此处补充的是被反应掉的氢气)，使加氢异构区始终存在含量基本恒定的溶解氢(可维持在饱和溶氢量的±5％)；另外，补充溶氢内构件还具有吸收上一床层的部分反应热，降低床层温升的作用。本发明提供的液相加氢异构工艺通过上述特点确保了连续异构化反应速率和异构烷烃收率。
本发明提供的液相加氢异构工艺大大减少了反应系统中的氢气用量，该工艺是在一个连续液相反应区利用正构烷烃进行油品中烃类原料的异构化反应，而非一个需要大量高压氢气来维持气相连续的三相反应系统。在上述连续液相反应的异构化系统中，通过事先将一定量的氢气(至少部分氢气)混合到烃类原料中，以及在异构过程中补充溶氢，使加氢异构区域中可保持连续液相的条件和连续平衡的反应速率。
在本发明提供的液相加氢异构工艺中，利用溶氢器溶氢和/或补充溶氢内构件补氢时，可根据油品的品质和具体工艺要求选择合适的溶氢和/或补氢量，例如，当异构反应需要的氢量较少时，可主要靠溶氢器供氢，同时相应地减少补充溶氢内构件的补氢量。
本发明提供的液相加氢异构工艺，通过连续液相加氢异构过程可至少减少烃类原料中浊点、倾点、冷滤点中的一个数值。
在上述液相加氢异构工艺中，优选地，所述油品为馏分油，所述馏分油的馏程范围为65℃-550℃；进一步优选地，所述馏分油为加氢裂化尾油、催化柴油、焦化柴油、直馏柴油、直馏蜡油、减压馏分油、焦化蜡油、脱沥青油和合成油中的一种或几种的组合；更优选地，所述馏分油为加氢裂化尾油。
在上述液相加氢异构工艺中，优选地，所述氢油混合物中溶解的氢气是处于饱和状态或过饱和状态。可根据油品的不同性质对氢油混合物中氢气的溶解量进行适当调节，当油品需要消耗较多的氢时，可将氢气的溶解量调整至过饱和状态。
在上述液相加氢异构工艺中，优选地，加氢异构反应和/或加氢精制反应中的液相连续相中溶解的氢气量足以维持反应稳定的需求。
在上述液相加氢异构工艺中，优选地，所述加氢异构反应中使用的催化剂通常与加工的原料性质有关，一般为常规的贵金属催化剂或非贵金属催化剂。贵金属催化剂可以为北京三聚环保新材料股份有限公司生产的PIC-802、PIC-812等润滑油加氢异构催化剂；非贵金属催化剂可以为中国石油抚顺石油化工公司催化剂厂生产的HIDW等柴油异构降凝催化剂。
在上述液相加氢异构工艺中，优选地，所述加氢异构的反应条件为：反应压力为6.0MPa-16.0MPa，反应温度为320℃-395℃，体积空速为0.2h-1-2.0h-1。
在上述液相加氢异构工艺中，优选地，所述加氢精制的反应条件为：反应压力为6.0MPa-16.0MPa，反应温度为220℃-385℃，体积空速为0.2h-1-3.0h-1。
在上述液相加氢异构工艺中，加氢异构和加氢精制的具体操作可以采用本领域现有技术形式，如一段串联加氢工艺进行异构脱蜡——加氢精制(两个加氢反应器)、也可以采用一段串联加氢工艺进行加氢精制——异构降凝(两个加氢反应器)。
在上述液相加氢异构工艺中，优选地，该工艺还包括，将分馏后得到的除目的产品之外的一种或几种馏分汇入所述油品的步骤。在该方案中，油品中的烃类原料(或至少部分)与来自分馏塔的馏分混合后，经过溶氢器进行溶氢，然后进入连续液相加氢异构区反应。上述方案是将部分馏分作为液相循环物辅助溶氢，相当于提高了液相异构区溶 氢与反应物的比例；而且，随着反应的进行消耗氢气，通过补充溶氢内构件向反应区补充一定量的氢气，液相循环物仍然可以在反应区溶解一定量的氢气。上述液相加氢异构工艺在具体应用中，可根据加氢异构的实际情况，确定是否需要产品循环以及循环油的性质，以确保目的产品收率和选择性。
在上述液相加氢异构工艺中，在加氢异构反应器和/或加氢精制反应器的液相物料中，氢气主要呈溶解状态(基本无氢气气泡或仅有少量的气泡)。在现有技术中，如CN103119133A公开的内容中，记载到：“氢气以长条(slug)或气泡的形式存在于液体充满空间区的外部或者内部”，“氢气应该以足够低的浓度存在以保证加氢操作反应器中的连续液相，但浓度要高到足以为加氢操作烃类进料提供足够的氢气”。据上述记载可知，在该专利中氢气是以气体或气泡形态存在(与本发明有本质的区别)，而气泡形式存在的氢气，说明该专利采用的技术如本发明背景技术中描述的那样，需要采用循环氢压缩机，带来较大成本问题。另外，CN103805240A公开的内容中，记载到：“液体产物循环油”一类词汇，但是该专利中是气液逆流反应器的产物循环；并且，该专利中的第二个反应器不是液相反应器，是气液逆向流动的反应器，因此，最终的反应产物性质以及反应条件与纯粹的液相反应器是有差别的。
在上述液相加氢异构系统中，优选地，补充溶氢内构件排出的氢气进入氢气循环系统。
本发明还提供了上述液相加氢异构工艺在润滑油原料加氢异构生产润滑油基础油或柴油加氢异构降凝生产低凝柴油中的应用。
与现有技术相比，本发明提供的液相加氢异构系统和工艺，取消了循环氢压缩机，油品加氢工艺流程简单，降低了投资成本和操作风险。
附图说明
图1为实施例1中补充溶氢内构件的结构示意图；
图2为实施例1中液相加氢异构工艺的示意图；
附图标号说明：
1氢气管线；2油品进料管线；3气液混合器；4加氢异构反应器；5加氢精制反应器；6分馏塔；7产品管线；8循环泵。
具体实施方式
为了对本发明的技术特征、目的和有益效果有更加清楚的理解，现对本发明的技术方案进行以下详细说明，但不能理解为对本发明的可实施范围的限定。
实施例1-3中所用到的原料见表1：
表1原料油A、B和C的性质
Figure PCTCN2016085257-appb-000001
实施例1
本实施例提供了一种液相加氢异构系统，该系统(第一个反应器为加氢异构反应器，第二个为加氢精制反应器)包括以下装置：
气液混合器3、加氢异构反应器4、加氢精制反应器5和分馏塔6；其中，
加氢异构反应器4设有三个催化剂床层，并分别在相邻的催化剂床层之间设有补充溶氢内构件，各催化剂床层中装填有加氢异构脱蜡催化剂；
上述补充溶氢内构件(其结构示意图如图1所示)包括底部筛孔隔离板、中部混合空间和顶部隔离板，顶部隔离板设置有若干排液管道，中部混合空间设有氢气入口和氢气出口；氢气与油品在中部混合空间进行混合，溶解了氢气的液相通过排液管道排出，未被溶解的氢气通过氢气出口排出；
加氢精制反应器5设有三个催化剂床层，并分别在相邻的催化剂床层之间设有补充溶氢内构件，各催化剂床层中装填有加氢精制催化剂；
氢气管线1分为三个支路，分别为氢气第一支路、氢气第二支路和氢气第三支路，氢气第一支路与油品进料管线2连通，氢气第二支路分为两部分，并分别与加氢异构反 应器4中的两个补充溶氢内构件连通，氢气第三支路分为两部分，并分别与加氢精制反应器5中的两个补充溶氢内构件连通；
油品进料管线2与气液混合器3连通，气液混合器3通过氢油混合物管线与加氢异构反应器4的底部进料口连通，加氢异构反应器4的顶部出料口与加氢精制反应器5的底部进料口连通，加氢精制反应器5的顶部出料口与精馏塔6连通，精馏塔6设有产品管线7和非产品馏分管线，产品管线7引出界区，非产品馏分管线与循环泵8的入口连通，循环泵8的出口与油品进料管线2连通。
液相加氢异构工艺：
一种利用工艺上述系统的液相加氢异构工艺(工艺的示意图如图2所示)，具体包括以下步骤：
1)将原料A和氢气在气液混合器3中进行混合，形成纯液体状态的氢油混合物，将该氢油混合物从底部送入加氢异构反应器4；
2)在加氢异构反应器4中，氢油混合物进行加氢异构反应，得到加氢异构反应产物，加氢异构的工艺条件为：氢分压12.2MPa，反应温度为320℃，体积空速为1.2h-1；反应中使用的异构脱蜡催化剂为贵金属催化剂PIC-812；
3)将加氢异构反应产物从底部送入加氢精制反应器5进行加氢精制，再将加氢精制产物送入分馏塔6，加氢精制的工艺条件为：氢分压12.2MPa，反应温度为220℃，体积空速为2.0h-1；
4)将分馏塔6中的混合产品切割后的2cSt(厘斯)或6cSt产品进行循环，保留另一目的产品(如果2cSt为目的产品，那么用6cSt作为循环油)，产品性质见表2。
表2本实施例制得的产品的性质
Figure PCTCN2016085257-appb-000002
由表2可见，利用本实施例提供的系统，基础油收率达到88.9％，可以最大量生产6cSt基础油。
实施例2
本实施例提供了一种液相加氢异构工艺，该工艺利用了类似实施例1中的系统，区别在于，加氢异构反应器和加氢精制反应器分别设有四个催化剂床层，在相邻的两个催化剂床层间分别设有补充溶氢内构件，该工艺具体包括以下步骤：
1)将原料油B和氢气在气液混合器3中进行混合，形成纯液体状态的氢油混合物，将该氢油混合物从底部送入加氢异构反应器4；
2)在加氢异构反应器4中，氢油混合物进行加氢异构反应，得到加氢异构反应产物，加氢异构的工艺条件为：氢分压12.2MPa，反应温度为365℃，体积空速为0.85h-1；反应中使用的异构脱蜡催化剂为贵金属催化剂PIC-812；
3)将所述加氢异构反应产物从底部送入加氢精制反应器5进行加氢精制，再将加氢精制产物送入分馏塔6，加氢精制的工艺条件为：氢分压12.2MPa，反应温度为230℃，体积空速为1.42h-1；
4)将分馏塔6中的混合产品切割后的2cSt(厘斯)产品进行循环，保留10cSt(厘斯)产品，产品性质见表3。
表3实施例2中制得的产品的性质
Figure PCTCN2016085257-appb-000003
由表3可见，采用该工艺技术，基础油收率达到81％，可以生产10cSt基础油。
实施例3
本实施例提供了一种液相加氢异构系统及工艺，该系统(仅有加氢异构反应器)包括以下装置：
气液混合器3、加氢异构反应器4和分馏塔6；其中，
加氢异构反应器4设有五个催化剂床层，并分别在相邻的催化剂床层之间设有补充溶氢内构件，各催化剂床层中装填有加氢异构脱蜡催化剂；
上述补充溶氢内构件包括底部筛孔隔离板、中部混合空间和顶部隔离板，顶部隔离板设置有若干排液管道，中部混合空间设有氢气入口和氢气出口；氢气与油品在中部混合空间进行混合，溶解了氢气的液相通过排液管道排出，未被溶解的氢气通过氢气出口排出；
氢气管线1分为两个支路，分别为氢气第一支路和氢气第二支路，氢气第一支路与油品进料管线2连通，氢气第二支路分为四部分，并分别与加氢异构反应器4中的四个补充溶氢内构件连通；
油品进料管线2与气液混合器3连通，气液混合器3通过氢油混合物管线与加氢异构反应器4的底部进料口连通，加氢异构反应器4的顶部出料口与精馏塔6连通，精馏塔6设有产品管线7和非产品馏分管线，产品管线7引出界区，非产品馏分管线中的产物不进行循环。
液相加氢异构工艺：
利用上述系统的液相加氢异构工艺，该工艺包括以下步骤：
1)将原料油C和氢气在气液混合器3中进行混合，形成纯液体状态的氢油混合物，将该氢油混合物从底部送入加氢异构反应器4；
2)在加氢异构反应器4中，氢油混合物进行加氢异构反应，得到加氢异构反应产物；加氢异构的工艺条件为：氢分压15.6MPa，反应温度为340℃，体积空速为1.5h-1；反应中使用的异构脱蜡催化剂为贵金属催化剂PIC-812；
3)将分馏塔6中的混合产品进行不同方案的实沸点切割(表4中提供了其中三种加工方案)，以生产不同的润滑油产品，如2cSt(厘斯)、4cSt(厘斯)、5cSt(厘斯)、6cSt(厘斯)、8cSt(厘斯)产品性质见表4；所有的分馏产品不进行循环。
通过表4中的数据可知，采用本实施例提供的工艺技术，加氢裂化尾油基础油收率达到80％以上，根据不同的加工方案可以生产2cSt、4cSt II/II+、5cSt III、6cSt III、8cSt III基础油。
表4实施例3中不同加工方案制得的产品的性质
收率，％ 加工方案1 加工方案2 加工方案3
2cSt 9.46 9.70 7.08
4cSt II / 27.34 /
4cSt II+ 58.35 / /
5cSt III / / 83.07
6cSt III / 53.11 /
8cSt III 22.34 / /
总收率 100 100 100
总基础油收率 90.15 90.15 90.15
实施例4
本实施例提供了一种液相加氢异构系统及工艺，该系统(第一个反应器为加氢精制反应器，第二个为加氢异构反应器)包括以下装置：
气液混合器3、加氢异构反应器4、加氢精制反应器5和分馏塔6；其中，
加氢异构反应器4设有三个催化剂床层，并分别在相邻的催化剂床层之间设有补充溶氢内构件，各催化剂床层中装填有加氢异构脱蜡催化剂；
上述补充溶氢内构件包括底部筛孔隔离板、中部混合空间和顶部隔离板，顶部隔离板设置有若干排液管道，中部混合空间设有氢气入口和氢气出口；氢气与油品在中部混合空间进行混合，溶解了氢气的液相通过排液管道排出，未被溶解的氢气通过氢气出口排出；
加氢精制反应器5设有三个催化剂床层，并分别在相邻的催化剂床层之间设有补充溶氢内构件，各催化剂床层中装填有加氢精制催化剂；
氢气管线1分为三个支路，分别为氢气第一支路、氢气第二支路和氢气第三支路，氢气第一支路与油品进料管线2连通，氢气第二支路分为两部分，并分别与加氢异构反应器4中的两个补充溶氢内构件连通，氢气第三支路分为两部分，并分别与加氢精制反应器5中的两个补充溶氢内构件连通；
油品进料管线2与气液混合器3连通，气液混合器3通过氢油混合物管线与加氢精制反应器5的底部进料口连通，加氢精制反应器5的顶部出料口与加氢异构反应器4的 底部进料口连通，加氢异构反应器4的顶部出料口与精馏塔6连通，精馏塔6设有产品管线7和非产品馏分管线，产品管线7引出界区，非产品馏分管线与循环泵8的入口连通，循环泵8的出口与油品进料管线2连通。
液相加氢异构工艺
利用上述系统的液相加氢异构工艺，该工艺具体包括以下步骤：
1)将原料油D和氢气在气液混合器3中进行混合，形成纯液体状态的氢油混合物，将该氢油混合物从底部送入加氢精制反应器5；
2)在加氢精制反应器5中，氢油混合物进行加氢精制反应，加氢精制的工艺条件为：反应系统压力6.5MPa、反应温度355℃，空速1.5h-1；
3)将加氢精制反应产物送入加氢异构反应器4进行加氢异构反应，得到加氢异构反应产物，加氢异构的工艺条件为：反应系统压力6.5MPa、反应温度350℃，空速1.5h-1；反应中使用的异构降凝催化剂为非贵金属催化剂HIDW，产品不循环。原料油D及产品性质列于表5。
表5原料D及产品性质
油品性质 原料D 生成油
组成，％ 直馏柴油：催化柴油＝55:45  
密度，g/cm3 0.8395 0.8265
馏程，℃ 176-355 166-350
硫含量，μg/g 946 6.4
氮含量，μg/g 997 9.6
十六烷值 48.8 50.0
凝点，℃ -4.0 -35.7
柴油收率，％ / 89.7
由表5可见，采用该工艺技术，柴油收率达到89％，降凝幅度达到30℃以上，可以生产-35℃低凝柴油。

Claims (14)

  1. 一种液相加氢异构系统，其特征在于，该系统包括：
    溶氢器、加氢异构反应器和分馏塔；
    所述溶氢器包括油品进料管线、氢气进料管线和氢油混合物管线，所述氢油混合物管线与所述加氢异构反应器的底部连通，所述加氢异构反应器的顶部与所述分馏塔连通；
    所述加氢异构反应器中包括至少两个催化剂床层，至少在一组相邻的两个催化剂床层之间设有补充溶氢内构件；
    所述补充溶氢内构件包括底部筛孔隔离板、中部混合空间和顶部隔离板，所述顶部隔离板设置有若干排液管道，所述中部混合空间设有氢气入口和氢气出口；氢气与油品在中部混合空间进行混合，溶解了氢气的液相通过排液管道排出，未被溶解的氢气通过氢气出口排出。
  2. 根据权利要求1所述的液相加氢异构系统，其特征在于，所述分馏塔中至少有一个除目的产品之外的切割馏分管线与所述油品进料管线连通。
  3. 根据权利要求1所述的液相加氢异构系统，其特征在于，在所述加氢异构反应器中，催化剂床层的个数为2-5个。
  4. 根据权利要求1-3任一项所述的液相加氢异构系统，其特征在于，该系统还包括加氢精制反应器，所述加氢精制反应器设于加氢异构反应器之前或之后；
    当加氢精制反应器设于加氢异构反应器之前时，所述氢油混合物管线与加氢精制反应器的底部连通，所述加氢精制反应器的顶部与加氢异构反应器的底部连通，所述加氢异构反应器的顶部与所述分馏塔连通；
    当加氢精制反应器设于加氢异构反应器之后时，所述氢油混合物管线与加氢异构反应器的底部连通，所述加氢异构反应器的顶部与加氢精制反应器的底部连通，所述加氢精制反应器的顶部与所述分馏塔连通；
  5. 根据权利要求4所述的液相加氢异构系统，其特征在于，所述加氢精制反应器中包括至少两个催化剂床层，在相邻的两个催化剂床层中设有补充溶氢内构件。
  6. 根据权利要求5所述的液相加氢异构系统，其特征在于，在加氢精制反应器中，催化剂床层的个数为2-5个。
  7. 一种利用权利要求1-6任一项所述的系统的液相加氢异构工艺，其特征在于，该工艺包括以下步骤：
    (1)将油品和氢气在溶氢器中混合为液态的氢油混合物；
    (2)将氢油混合物送入后续的加氢异构反应器和/或加氢精制反应器，进行加氢异构反应和/或加氢精制反应；
    (3)将经步骤(2)制得的产物送入分馏塔进行分馏，经分馏获得目的产品。
  8. 根据权利要求7所述的工艺，其特征在于，所述油品为馏分油，所述馏分油的馏程范围为65℃-550℃。
  9. 根据权利要求8所述的工艺，其特征在于，所述馏分油包括加氢裂化尾油、催化柴油、焦化柴油、直馏柴油、直馏蜡油、减压馏分油、焦化蜡油、脱沥青油和合成油中的一种或几种的组合。
  10. 根据权利要求9所述的工艺，其特征在于，所述馏分油为加氢裂化尾油。
  11. 根据权利要求7所述的工艺，其特征在于，所述氢油混合物中溶解的氢气是处于饱和状态或过饱和状态。
  12. 根据权利要求7所述的工艺，其特征在于，所述加氢异构反应的工艺条件为：反应压力为6.0MPa-16.0MPa，反应温度为320℃-395℃，体积空速为0.2h-1-2.0h-1；
    所述加氢精制的反应条件为：反应压力为6.0MPa-16.0MPa，反应温度为220℃-385℃，体积空速为0.2h-1-3.0h-1。
  13. 根据权利要求7所述的工艺，其特征在于，该工艺还包括，将分馏后得到的除目的产品之外的一种或几种馏分汇入所述油品的步骤。
  14. 权利要求7-13任一项所述的工艺在润滑油原料加氢异构生产润滑油基础油或柴油加氢异构降凝生产低凝柴油中的应用。
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