WO2014183429A1 - 一种非均相煤基油品悬浮床加氢方法 - Google Patents

一种非均相煤基油品悬浮床加氢方法 Download PDF

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WO2014183429A1
WO2014183429A1 PCT/CN2013/089213 CN2013089213W WO2014183429A1 WO 2014183429 A1 WO2014183429 A1 WO 2014183429A1 CN 2013089213 W CN2013089213 W CN 2013089213W WO 2014183429 A1 WO2014183429 A1 WO 2014183429A1
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oil
catalyst
coal
reaction
bed hydrogenation
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PCT/CN2013/089213
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English (en)
French (fr)
Inventor
张晓静
李培霖
毛学锋
王勇
王雨
胡发亭
石智杰
颜丙锋
黄澎
赵渊
杜淑凤
谷小会
朱肖曼
吴艳
赵鹏
张帆
马炳辰
周铭
钟金龙
孙竟晔
李伟林
陈来夫
常秋连
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煤炭科学研究总院
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Publication of WO2014183429A1 publication Critical patent/WO2014183429A1/zh

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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G3/00Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G47/00Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/24Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions with moving solid particles
    • C10G47/26Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions with moving solid particles suspended in the oil, e.g. slurries
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40Characteristics of the process deviating from typical ways of processing
    • C10G2300/44Solvents
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/80Additives
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00Technologies relating to oil refining and petrochemical industry
    • Y02P30/20Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

  • the invention belongs to the field of coal chemical industry, and particularly relates to a heterogeneous coal-based oil product suspension bed hydrogenation method for producing engine fuel and chemical raw materials with coal-based oil products as raw materials.
  • Coal-based oil products refer to oils produced during coal conversion, including coal pyrolysis and gasification by-products of low-temperature coal tar, coal coking by-product high-temperature coal tar, coal direct liquefaction oil, and Fischer-Tropsch synthetic oil.
  • the conventional processing process of coal-based oil products in China is to process various fractions concentrated by pre-treatment and distillation, and then treat various fractions by physical or chemical methods (such as acid-base washing, distillation, polymerization, crystallization).
  • a large number of chemicals are extracted, and a large part is directly burned off as a crude fuel instead of heavy oil.
  • the traditional processing method is backward, the separation and purification are difficult, the scale is not easy to form, and a large amount of sewage, waste residue, and environmental pollution are generated.
  • due to the high content of sulfur and nitrogen compounds in the coal-based oil direct combustion will generate a large amount of S0 X and N0 X cause serious environmental pollution. Therefore, the clean processing and effective utilization of coal-based oils have become more and more important.
  • the hydrogenation process can effectively remove impurities such as sulfur and nitrogen in the coal-based oil, reduce the density and achieve light weight.
  • coal-based oil raw materials have high hetero atom content, high ash content, high polycyclic aromatic hydrocarbon content, high gum content and high asphaltene content, which makes coal-based oil products use conventional petroleum hydrogenation.
  • problems such as coking deposition of the reaction system and short catalyst life in the catalyst and process.
  • U.S. Patent 4,855,037 discloses a catalyst and method for hydrotreating a coal-based oil product, the hydrotreated coal-based oil being used for delayed coking.
  • the method mainly improves the catalyst by improving the pore size, pore distribution and metal composition of the catalyst, and selecting suitable process conditions.
  • the stability allows the catalyst to maintain long-period operation in the treatment of coal-based oil full fractions or tar pitch, and to improve the quality of coke formation in delayed coking.
  • CN1351130A discloses a method for hydrogenating diesel oil in a hydrotreating unit by separating the distillate oil from the coal-based oil product;
  • Chinese patent CN1876767A discloses that the coal-based oil product is less than 600 ° C and is produced by a fixed bed hydrocracking process. Method for steam and diesel;
  • Chinese patent CN101240192A discloses a method for producing diesel oil by using a hydrorefining-hydrocracking upgrading combined process for heavy fraction of coal-based oil.
  • Chinese patent CN101307256A discloses a single-stage method for hydrogenation and upgrading of coal-based oil products, which adopts a hydrorefining method to upgrade a light fraction of coal-based oil products to produce naphtha and diesel products, and a heavy fraction of coal-based oil products. Reconcile and produce fuel oil.
  • Chinese patent CN101307257A discloses a two-stage method for hydrogenation and upgrading of coal-based oil products to produce naphtha and diesel oil. The method uses a hydrotreating two-stage hydrotreating for the distillate oil after the coal-based oil product is indignant. The process produces naphtha and diesel.
  • Chinese patent CN101074381A discloses a method for producing steam, middle distillate oil and modified coal pitch by using a fixed bed hydrocracking process for a full-distillate coal-based oil product.
  • Chinese patent CN1766058A discloses a method in which a whole fraction of a coal-based oil product is mixed with a homogeneous catalyst water-soluble nickel phosphomolybdate, and after hydrogenation in a suspension bed reactor, a fraction of less than 370 ° C is subjected to fixed bed hydrotreating to produce gasoline. , diesel, while more than 370 ° tail oil is partially recycled to the suspended bed reactor to further convert light oil, part of the external helium.
  • a disadvantage of these methods is that the coal-based oil feedstock is not fully utilized.
  • the applicant's previously granted patent CN101885982A provides a coal-based oil suspension bed hydrogenation of a heterogeneous catalyst that produces a maximum amount of coal-based oil raw materials for the production of light oil, greatly improving the utilization of raw materials and the efficiency of the catalyst.
  • Method in the actual use process of the patent, the applicant finds that the source process of the coal-based oil raw material is different, the coal-based oil raw material needs to be pretreated to meet the production needs, and the cutting of the patent CN101885982A
  • the method is obviously not flexible enough, especially when the viscosity of the pretreatment object is large, there is a phenomenon that it cannot be transported.
  • the method for hydrogenating a coal-based oil suspension bed of the heterogeneous catalyst comprises the following steps:
  • coal-based oil raw material is subjected to conventional dehydration and removal of mechanical impurities, and then subjected to distillation separation, or directly subjected to step 2 of coal-based oil product suspension bed hydrogenation;
  • the coal-based oil raw material is separated into a phenol oil fraction or a naphtha fraction, a diesel fraction and a heavy oil fraction, that is, when the content of the phenol in the coal-based oil raw material is low, when the content is less than 3%, the coal-based
  • the oil raw material is distilled and separated into a naphtha fraction, a diesel fraction and a heavy oil fraction.
  • the coal-based oil raw material can also be distilled and separated into a naphtha-diesel mixed fraction and a heavy oil fraction according to the requirements of subsequent processing and upgrading.
  • the coal-based oil raw material can be distilled and separated into naphtha fraction and phenol. Oil fraction, diesel fraction and heavy oil fraction.
  • the phenol content in the coal-based oil raw material is higher, the content is higher than 3%, and when the naphtha fraction is low, when the content is less than 5%, the coal-based oil may be used.
  • Distillation of raw materials into naphtha-phenol oil mixed with anger, diesel fraction and heavy oil fraction If the coal-based oil feedstock is heavy or too viscous, it may not be separated by distillation.
  • the pretreated coal-based oil product is subjected to a distillation method to obtain a naphtha fraction, a phenol oil fraction, a diesel fraction and a heavy oil fraction by controlling the cut point temperature of the fraction, wherein the cutting temperature of the naphtha fraction is IBP ⁇ 170 °C.
  • the final cut-off temperature of the phenol oil fraction is between 210 and 260 °C
  • the final cut-off temperature of the diesel fraction is between 300 and 380 °C
  • the remainder is the heavy oil fraction.
  • the phenol oil fraction, the diesel fraction and the heavy oil fraction may be directly obtained without separately cutting the naphtha fraction, and the initial cutting point temperature of the phenol oil fraction is the initial boiling point.
  • IBP the initial cutting point temperature of the phenol oil fraction
  • the traditional coal-based oil product dephenolation method or other dephenolization method is used, and the dephenolation unit is subjected to dephenolation treatment to obtain dephenolized oil and crude phenol, and the crude phenol is further refined and rectified in the crude phenol refining unit.
  • Phenolic compounds (such as phenol, cresol, xylenol, etc.) are isolated.
  • the heavy distillate here has a cutting point of 160 to 360 ° C, and can be selected by a person skilled in the art according to actual needs.
  • coal-based oil feedstock If the coal-based oil feedstock is heavy or too viscous, it can be separated without distillation. Hydrocracking is carried out.
  • the catalyst, the vulcanizing agent and the solvent oil are mixed and added together to a catalyst slurry preparation device with a stirring device, and fully mixed to form a catalyst slurry under normal pressure at a temperature of 80 ° C to 200 ° C.
  • the solvent oil comprises at least one or more of a coal-based oil full fraction or a heavy distillate, and a catalyst-removed circulating oil, which is used for preparing a catalyst slurry, which can be selected by a person skilled in the art as needed.
  • the type of oil and the amount of oil added are selected by a person skilled in the art as needed.
  • the catalyst is a powdery granular coal-based oil suspension bed hydrogenation catalyst having a single metal active component containing phase, nickel, cobalt, tungsten or iron or a composite multi-metal active component having a particle diameter of 1 to 100 ⁇ .
  • the thinning agent is a substance capable of generating hydrogenation under the reaction conditions, such as smectic or dimethyl disulfide, and the vulcanizing agent is added in an amount to ensure that the hydrogen sulfide content of the system circulating hydrogen is not less than 1000 ppm, the catalyst oil.
  • the solid concentration of the slurry can be controlled at 20 to 45% by weight, preferably between 25 and 40% by weight.
  • the catalyst slurry obtained in step 2 is mixed with the coal-based oil product or the heavy distillate oil and the circulating oil containing the catalyst, and is heated by the raw material pump, heated by the mixed hydrogen, and then introduced into one or more series of suspended bed hydrogenation.
  • the reactor is subjected to a hydrocracking reaction.
  • the hydrocracking process conditions are a reaction temperature of 320 to 480 ° C, preferably 350 to 450; a reaction pressure of 8 to 25 Mpa, preferably 10 to 19 Mpa; a volumetric space velocity of 0.3 to 3. Oh" 1 , preferably 0.5 ⁇ 2.
  • the catalyst is added in an amount to control the total amount of metal of the active component and the weight of the coal-based oil raw material is 0.1: 100 to 4: 100, preferably from 0.5:100 to 2:100.
  • the suspended bed hydrogenation reactor reaction effluent is separated by a separation unit (the separation unit may be composed of two or more separators) to obtain a liquid solid phase mixture stream (separated by two separators or a plurality of separators to obtain solid oil) and
  • the hydrogen-rich gas, the hydrogen-rich gas is used as the circulating hydrogen; the liquid-solid mixture stream is continuously subjected to hydrocracking reaction as a circulating oil or treated to obtain a circulating oil, and the hydrocracking reaction is continued.
  • the liquid-solid mixture stream can be separated by several methods:
  • the fractional distillation column is fractionated, the top of the column is lightly distillate (the temperature at the final cutting point can be between 300 and 380 ° C), and the bottom of the column is a bottom-bottom heavy oil (or tail oil) containing a catalyst, wherein Most (about two-thirds to four-fifths) of the bottom heavy oil is directly circulated as circulating oil
  • the hydrogenation and lightening reaction is further carried out in the suspension bed hydrogenation reactor, and the remaining small portion (about one-third to one-fifth) of the bottom-bearing heavy oil enters the solid-liquid separation system for solid-liquid separation, and the solid-liquid separation can be performed.
  • the catalyst residue and the suspended bed hydrogenation heavy distillate are obtained, and the heavy distillate or the circulating oil is directly mixed with the reaction raw material of the suspended bed, or is prepared as a catalyst slurry.
  • Part of the solvent recycled into the suspension bed hydrogenation reactor for further hydrogenation and lightening reaction, the catalyst for the removal of the catalyst or regeneration, or
  • the suspended bed hydrogenation reactor reaction effluent is separated by a separation unit (the separation unit can be composed of two or more separators) to obtain a light oil and a solid oil (separated by two separators or a plurality of separators)
  • a separation unit can be composed of two or more separators
  • the solid-containing oil is directly subjected to solid-liquid separation by means of sedimentation or centrifugation or filtration or decompression, and the de-stabilized reaction product is circulated into a suspended bed hydrogenation reactor for further hydrogenation and lightening.
  • the reaction, the desorbed catalyst is externally en
  • the whole light distillate obtained in the above steps 1 to 2 is subjected to a conventional upgrading process, and the atmospheric pressure overhead of the step 2 is obtained by the suspension bed hydrogenation reaction product light distillate and the coal-based oil diesel fraction obtained by the step 1 distillation.
  • the phenol oil or light oil fraction is used together as a raw material oil for the upgrading of distillate oil, and is processed to produce fuel oil and chemical raw materials, wherein the naphtha fraction can be produced by catalytic reforming or catalytic reforming-aromatic extraction combined process Or aromatic products, coal-fired fractions can be produced by hydrorefining or selective hydrocracking technology for aviation kerosene and diesel products.
  • the coal-based oil raw material can be separated into a phenol oil fraction or a naphtha fraction, a diesel fraction and a heavy oil fraction or a light fraction and a heavy fraction, or directly without distillation. Used as a hydrocracking solution, the solution is more flexible and optimized, and the processing steps can be eliminated while meeting the actual production and operation needs;
  • a typical coal tar is selected as the raw material of the coal-based oil in this case.
  • the properties of the coal-based oil raw materials after conventional dehydration and mechanical impurities are as shown in Table 1:
  • the pretreated coal-based oil is separated into IBP ⁇ 260°C, 260-350°C and heavy fractions greater than 350°C, and heavy distillate greater than 350°C as the feedstock oil of the suspended bed hydrogenation reactor.
  • the hydrocracking lightening reaction is carried out.
  • the catalyst used in this embodiment is a ferromolybdenum composite suspended bed hydrogenation catalyst, and the catalyst used comprises a high active metal component molybdenum and a low active metal component iron, wherein the high active component metal molybdenum and the low active component metallic iron
  • the weight ratio is 1:500, and the catalyst water content is less than 0.5 wt%.
  • the particle diameter is 1-100 ⁇ ⁇ powdery particles.
  • the catalyst is pulverized into a particle size of 58 wt% hematite (mainly Fe 2 O 3 ) to be less than ⁇ ⁇ ⁇ ⁇ , and then 10% aqueous ammonium molybdate solution is sprayed onto the particles.
  • the powdery particulate catalyst having a water content of less than 0.5 wt%, is obtained by drying at 100 ° C for 1 hour.
  • the suspension bed hydrogenation process of the present embodiment is: firstly, a small portion of the heavy oil of the catalyst oil and/or the coal-based oil of more than 350 ° C and the powdery granular molybdenum having a catalyst particle size of less than 100 ⁇ m.
  • the solid concentration of the slurry is about 25 wt%.
  • the catalyst slurry and most of the remaining coal-based oil products are greater than 35 (TC heavy distillate oil feedstock and suspended bed hydrogenation reaction product often pressure tower after the anger of the catalyst-containing circulating oil (that is, about four-fifths of the bottom Heavy oil) mixing, after the raw material pump is boosted, the hydrogen is heated, and then enters two series of suspended bed hydrogenation reactors for hydrocracking reaction.
  • the process conditions are shown in Table 2, and the catalyst is added to control the active components.
  • the ratio of the weight of the metal to the coal-based oil raw material is 0.8: 100, and the suspended bed reactor reaction effluent passes through the high-temperature separator and the low-temperature separator to obtain a liquid-solid phase high-low-oil mixture flow and a hydrogen-rich gas. Hydrogen gas is used as circulating hydrogen.
  • the bottom heavy oil is directly recycled to the suspension bed hydrogenation reactor as a circulating oil to further carry out the hydrogenation lightening reaction; the remaining small part (about one-fifth) of the bottom-heavy heavy oil is used.
  • the method comprises solid-liquid separation, and after separation, a catalyst residue and a suspended bed hydrogenation heavy distillate are obtained, and the part of the heavy distillate oil is directly mixed with the reaction raw material of the suspended bed or is used as a partial solvent prepared by the catalyst oil slurry, and is circulated into the suspended bed.
  • the hydrogenation reactor is further subjected to a hydrogenation lightening reaction, and the desorbed catalyst is externally recycled or regenerated.
  • Table 3 The yield of some of the obtained products is shown in Table 3.
  • the light oil obtained by the test can be upgraded and processed to produce fuel oil and chemical raw materials by using existing processing techniques.
  • the naphtha fraction can be used in catalytic reforming or catalytic reforming-aromatic extraction combined process technology for gasoline or aromatic products, wherein the coal fraction can be produced by hydrorefining or selective hydrocracking technology to produce aviation kerosene and diesel products. .
  • a heavy distillate is separated by distillation at a cutting temperature of 230 ° C, which also has a certain viscosity, and a similar effect can be obtained by the above method, and since a lower selection is selected At the cutting point, the quality of the diesel fraction is also improved.
  • a coal-based oil with a high content of heavy fraction is selected as the raw material of the coal-based oil in this example.
  • the properties of the coal-based oil raw materials after conventional dehydration and mechanical impurities pretreatment are shown in Table 4:
  • the weight of the raw oil The content of the fraction is high and the viscosity is high.
  • the viscosity at 40 °C is more than 17 times that of the feedstock of Example 1. Considering the problem of transportation of industrial equipment, the viscosity of the material is too high to be transported.
  • the pretreatment of the raw material is distillation separation.
  • the cut temperature of the heavy distillate should be 31 ° ° C.
  • the pretreated coal-based oil is separated into IBP ⁇ 310 ° C and a heavy fraction greater than 310 ° C, and the heavy distillate greater than 310 ° C is used as a feed oil for the suspension bed hydrogenation reactor for hydrocracking.
  • Light weight reaction the heavy distillate greater than 310 ° C is used as a feed oil for the suspension bed hydrogenation reactor for hydrocracking.
  • the catalyst used in this embodiment is a ferromolybdenum composite suspended bed hydrogenation catalyst, and the catalyst used comprises a high active metal component molybdenum and a low active metal component iron, wherein the high active component metal molybdenum and the low active component metallic iron
  • the weight ratio is 1:500, the catalyst water content is less than 0.5 wt%, and the particle diameter is 1-100 ⁇ powdery particles.
  • the catalyst is prepared by pulverizing hematite having a iron content of 58% by weight of hematite (mainly Fe 2 O 3 ) into less than ⁇ , and then spraying 10% of an aqueous solution of ammonium molybdate onto the granules, spraying
  • the amount is about molybdenum: the weight ratio of iron is equal to 1:500, and it is dried at 100 ° C for 1 hour to obtain a powdery particle catalyst having a water content of less than 0.5 wt %.
  • the suspension bed hydrogenation process of the present embodiment is: firstly, a small part of the heavy oil of the catalyst oil and/or the coal-based oil which is more than 310 ° C, and the powdery granular molybdenum having a catalyst particle size of less than 100 ⁇ m.
  • the solid concentration of the slurry is about 25 wt%.
  • the catalyst slurry and most of the other coal-based oil products are greater than 31 (TC heavy distillate feedstock and suspended bed hydrogenation reaction product often pressure tower after the anger of the catalyst-containing circulating oil (that is, about four-fifths of the bottom Heavy oil) mixing, after the raw material pump is boosted, the hydrogen is heated, and then enters two suspended beds in series.
  • the ratio of the amount of the metal of the active component to the weight of the coal-based oil raw material is 1. 5: 100 , the reaction of the suspended bed reactor is effluxed.
  • the hydrogenation reactor is subjected to a hydrocracking reaction, and the process conditions are as shown in Table 5.
  • the liquid solid phase high and low oil separation mixture flow and the hydrogen rich gas are obtained.
  • a hydrogen rich gas is used as the circulating hydrogen.
  • the liquid-solid phase high-low oil-separating mixture flow often inverts the tower, the tower top gets less than 37 CTC light distillate, the bottom of the tower gets the bottom-bearing heavy oil containing the catalyst, most of which (about four-fifths) of the bottom heavy oil as a cycle
  • the oil is directly recycled to the suspension bed hydrogenation reactor for further hydrogenation and lightening reaction; the remaining small portion (about one-fifth) of the bottom-base heavy oil is subjected to solid-liquid separation by filtration, and the catalyst residue and suspension are obtained after separation.
  • the light oil obtained from the trial can be upgraded and processed to produce fuel oil and chemical raw materials by using existing processing technology.
  • the naphtha fraction can be catalytically reformed Or catalytic reforming-aromatic extraction combined process technology gasoline or aromatic products, wherein the coal fraction can be produced by hydrorefining or selective hydrocracking technology to produce aviation kerosene and diesel products.
  • a coal-based oil with a high content of heavy fraction is selected as the raw material of the coal-based oil in this example.
  • the properties of the coal-based oil raw materials after conventional dehydration and mechanical impurities pretreatment are as follows: Table 7: The weight of the raw oil The content of the fraction is high and the viscosity is high. The viscosity at 40 °C is more than 17 times that of the feedstock of Example 1. Considering the problem of transportation of industrial equipment, the viscosity of the material is too high to be transported.
  • the pretreatment of the raw material is distillation separation. The cut temperature of the heavy distillate should be at 28 °C.
  • the pretreated coal-based oil is separated by distillation into I BP ⁇ 280 °C and heavy fraction of more than 280 °C, and the heavy distillate of more than 280 °C is used as the feedstock for the suspension bed hydrogenation reactor for hydrogenation. Cracking lightening reaction.
  • the catalyst used in this embodiment is a ferromolybdenum composite suspension bed hydrogenation catalyst. 5 ⁇ % , The water content of the catalyst is less than 0.5% by weight, and the water content of the catalyst is less than 0.5% by weight.
  • the particle diameter is 1-100 ⁇ ⁇ powdery particles.
  • the catalyst is pulverized into a particle size of 58 wt% hematite (mainly Fe 2 O 3 ) to be less than ⁇ ⁇ ⁇ ⁇ , and then 10% aqueous ammonium molybdate solution is sprayed onto the particles.
  • the powdery particulate catalyst having a water content of less than 0.5 wt%, is obtained by drying at 100 ° C for 1 hour.
  • the suspension bed hydrogenation process of the present embodiment is: firstly, a small part of the heavy oil of the catalyst oil and/or the coal-based oil of more than 280 ° C and the powdery particle molybdenum having a catalyst particle size of less than 100 ⁇ m are removed.
  • the solid concentration of the slurry is about 25 wt%.
  • the catalyst oil slurry and most of the remaining coal-based oil products are greater than 28 (TC heavy distillate oil feedstock and suspended bed hydrogenation reaction product often pressure tower after the anger of the catalyst-containing circulating oil (that is, about four-fifths of the bottom Heavy oil) mixing, after the raw material pump is boosted, the hydrogen is heated, and then enters two series of suspended bed hydrogenation reactors for hydrocracking reaction.
  • the process conditions are as shown in Table 8, and the catalyst is added to control the active components.
  • the ratio of the weight of the metal to the coal-based oil raw material is 2.0: 100, and the suspended bed reactor reaction effluent passes through the high-temperature separator and the low-temperature separator to obtain a liquid-solid phase high-low-oil mixture flow and a hydrogen-rich gas. Hydrogen gas is used as circulating hydrogen. Liquid solid phase high and low oil separation mixture flow often after the tower is indignant, the top of the tower gets less than 37 CTC light distillate, the bottom of the tower gets the catalyst bottom oil, most of which (about five cents 4) The bottom heavy oil is directly recycled to the suspension bed hydrogenation reactor as a circulating oil to further carry out the hydrogenation lightening reaction;
  • the light oil obtained by the test can be upgraded and processed to produce fuel oil and chemical raw materials by using existing processing techniques.
  • the naphtha fraction can be used in catalytic reforming or catalytic reforming-aromatic extraction combined process technology for gasoline or aromatic products, wherein the coal fraction can be produced by hydrorefining or selective hydrocracking technology to produce aviation kerosene and diesel products. .
  • a coal-based oil with a higher content of heavy fraction and a higher viscosity is selected as the raw material of the coal-based oil in this example.
  • the properties of the coal-based oil raw materials after conventional dehydration and mechanical impurities pretreatment are shown in Table 10:
  • the oil has a high content of heavy fraction and a high viscosity.
  • the viscosity at 40 °C is more than 26 times that of the feed oil of Example 1, up to 1528. 5 ⁇ 7s.
  • the viscosity of the material is too high to be realized. Transportation, this test considers the whole anger into the suspended bed hydrocracking reaction system, without involuntary cutting and separation.
  • the pretreated coal-based oil full distillate is used as the feedstock oil in the suspension bed hydrogenation reactor for the hydrocracking and lightening reaction.
  • the catalyst used in this embodiment is a ferromolybdenum composite suspended bed hydrogenation catalyst, and the catalyst used comprises a high active metal component molybdenum and a low active metal component iron, wherein the high active component metal molybdenum and the low active component metallic iron
  • the weight ratio is 1:500, the catalyst water content is less than 0.5 wt%, and the particle diameter is 1-100 ⁇ powdery particles.
  • the catalyst is prepared by pulverizing hematite having a iron content of 58% by weight of hematite (mainly Fe 2 O 3 ) into less than ⁇ , and then spraying 10% of an aqueous solution of ammonium molybdate onto the granules, spraying
  • the amount is about molybdenum: the weight ratio of iron is equal to 1:500, and it is dried at 100 ° C for 1 hour to obtain a powdery particle catalyst having a water content of less than 0.5 wt %.
  • the suspension bed hydrogenation process of the present embodiment is: firstly removing a small portion of the catalyst-removed circulating oil and/or the coal-based oil full distillate and the powdery particle ferromolybdenum composite suspension bed having a catalyst particle size of less than 100 ⁇ . Hydrogenation catalyst (and metal molybdenum: iron weight ratio of 1:500) and vulcanizing agent dimethyl disulfide together under 80 °C stirring conditions to obtain catalyst slurry, control the solid concentration of catalyst slurry At around 25wt%.
  • the catalyst slurry is mixed with the remaining most of the coal-based oil products, the whole distillate raw material and the suspended bed hydrogenation reaction product, and the catalyst-containing circulating oil (that is, about four-fifths of the bottom-heavy heavy oil) is often irritated by the pressure tower.
  • the catalyst-containing circulating oil that is, about four-fifths of the bottom-heavy heavy oil
  • the two series of suspended bed hydrogenation reactors are sequentially introduced into the hydrocracking reaction.
  • the process conditions are shown in Table 11, and the catalyst is added to control the metal and coal base of the active component.
  • the ratio of the weight of the oil raw material is 3.0: 100, and the reaction effluent of the suspended bed reactor passes through the high temperature separator and the low temperature separator to obtain a liquid solid phase high and low oil separation mixture flow and a hydrogen rich gas.
  • a hydrogen rich gas is used as the circulating hydrogen.
  • the filtration method performs solid-liquid separation, and after separation, a catalyst residue and a suspended bed hydrogenation heavy distillate are obtained, and the part of the heavy distillate oil is directly mixed with the reaction raw material of the suspended bed or is used as a partial solvent prepared by the catalyst oil slurry, and is circulated into the suspended bed. Further, the hydrogenation and lightening reaction is carried out in the hydrogenation reactor, and the catalyst which is taken out is externally recycled or regenerated. The yields of the obtained partial products are shown in Table 12.
  • the yield of the light oil is 90. lwt%.
  • the light oil obtained by the experiment can be upgraded and processed to produce fuel oil and chemical raw materials by using existing processing techniques.
  • the naphtha fraction can be used in catalytic reforming or catalytic reforming-aromatic extraction combined process technology for gasoline or aromatic products, wherein the coal fraction can be produced by hydrorefining or selective hydrocracking technology to produce aviation kerosene and diesel products. .
  • the present invention can solve the problem of heavy distillate transportation of coal-based oil products, and can also improve the hexadecane of the diesel oil fraction in the heavy oil suspended bed hydrocracking product.
  • the value of the product improves the quality of the product, and also reduces the impurities such as sulfur, nitrogen, aromatics, colloid and asphaltene in the light oil of the coal-based oil, and reduces the operation of the light oil fixed bed hydrotreating reaction system. .

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Abstract

一种非均相煤基油品悬浮床加氢方法,包括下列步骤:1)将催化剂、硫化剂和溶剂油混合,于常压、80°C〜200°C温度条件下充分混合均匀制成催化剂油浆;2)催化剂油浆与煤基油品全馏分或重质馏分油、循环油混合后,进入悬浮床加氢反应器进行加氢裂化反应,其中催化剂的加入量以控制活性组分的金属总量与煤基油品原料重量之比为0.1:100至4:100,反应器内的反应温度320〜480°C,反应压力8〜25MPa,体积空速0.3〜3.0h—1,氢油体积比500〜2000,悬浮床加氢反应器反应流出物经过分离后得到液固相混合物流和富氢气体;液固相混合物流作为循环油继续进行加氢裂化反应或经处理得到循环油,继续进行加氢裂化反应;所述催化剂为煤基油品悬浮床加氢催化剂;所述的重质馏分油的切割点为160〜360°C。该方法实现了不同特性的煤基油品最大量、方便灵活的生产轻质油和催化剂循环利用,大大提高了原料和催化剂的利用效率及操作的灵活性。

Description

一种非均相煤基油品悬浮床加氢方法 技术领域
本发明属于煤化工领域,具体涉及一种以煤基油品为原料最大量生 产发动机燃料和化工原料的非均相煤基油品悬浮床加氢方法。
背景技术
煤基油品是指煤转化过程中产生的油品,包括煤炭热解及气化副产 中低温煤焦油、 煤炭炼焦副产高温煤焦油、 煤直接液化油、 费托合成油 等。
目前,我国煤基油品常规的加工过程是经过预处理蒸馏切取组分集 中的各种馏分,再对各种馏分采用物理或化学方法(如酸碱洗涤、蒸馏、 聚合、 结晶方法)进行处理提取各种化学品, 也有很大一部分作为粗燃 料替代重油直接烧掉。传统的加工方法工艺较落后, 分离和提纯难度较 大, 不易形成规模, 同时会产生大量污水、 废渣, 污染环境, 另外, 由 于煤基油品硫、 氮化合物含量高, 直接燃烧会产生大量的 S0X和 N0X , 造 成严重的环境污染。 因此, 煤基油品的洁净加工和有效利用也变得越加 重要。
利用加氢工艺可有效脱除掉煤基油品中的硫、 氮等杂质, 降低其密 度, 实现轻质化。 与石油重馏分油相比, 煤基油品原料具有杂原子含量 高、 灰分高, 多环芳烃含量高、 胶质、 沥青质含量高等特点, 这使得煤 基油品在采用常规的石油加氢催化剂及工艺过程时存在反应系统结焦 沉积、 催化剂使用寿命短等问题。
国内外研究机构对煤基油品加氢工艺技术做过一些研究,但目前还 没有完全成熟。 1985年日本专利 (申请号 85107441 )对煤基油品加氢 工艺及催化剂有详细描述,该日本专利采用加氢方法加工煤基油品的主 要目的是生产高品质的针状焦, 其使用钼、 镍、 钴等爾和 VIB的金属硫 化物作为活性金属组分。
美国专利 US4855037 介绍了一种加氢处理煤基油品的催化剂和方 法, 加氢处理后的煤基油品用于延迟焦化。 该方法主要是通过改进催化 剂的孔径、 孔分布和金属组分, 并选择合适的工艺条件以提高催化剂的 稳定性,使催化剂在处理煤基油品全馏分或焦油沥青时可保持长周期运 转, 并提高延迟焦化中生成焦的质量。
国内大多关于煤基油品加氢工艺的专利都是涉及煤基油品分馏后 的馏分油,采用石油加工领域广泛使用的常规的馏分油加氢精制或加氢 精制一加氢裂化工艺生产石脑油和柴油产品的工艺过程, 如中国专利
CN1351130A公开了一种将煤基油品分离后的馏分油在加氢精制装置中 进行加氢生产柴油的方法; 中国专利 CN1876767A公开了小于 600 °C煤 基油品采用固定床加氢裂化工艺生产汽、 柴油的方法; 中国专利 CN101240192A公开了煤基油品重馏分采用加氢精制 -加氢裂化改质联 合工艺生产柴油的方法。 中国专利 CN101307256A公开了一种单段法煤 基油品加氢改质方法,该方法采用加氢精制的方法改质煤基油品轻馏分 生产石脑油和柴油产品, 煤基油品重馏分进行调和, 生产燃料油。 中国 专利 CN101307257A公开了一种两段法煤基油品加氢改质方法生产石脑 油和柴油,该方法对煤基油品分愤后的馏分油采用一段加氢精制二段加 氢改质的工艺方法生产石脑油和柴油等。 中国专利 CN101074381A公开 了一种全馏分煤基油品采用固定床加氢裂化工艺生产汽、中间馏分油和 改质的煤沥青的方法。 中国专利 CN1766058A公开了一种将煤基油品全 馏分与均相催化剂水溶性磷钼酸镍混合, 经悬浮床反应器进行加氢后, 小于 370 °C馏分经固定床加氢精制处理生产汽油、 柴油, 同时大于 370 ° 尾油部分循环至悬浮床反应器进一步转化轻质油、 部分外甩的方法。 这些方法的缺点是没有将煤基油品原料充分利用。
本申请人在先申请的已授权专利 CN101885982A提供了使煤基油品 原料最大量生产轻质油,大大提高原料的利用率和催化剂的效率的非均 相催化剂的煤基油品悬浮床加氢方法,但是, 本申请人在该专利的实际 的使用过程中, 发现煤基油品原料的来源工艺过程不同时, 煤基油品原 料需要预处理才可以满足生产需要, 而该专利 CN101885982A的切割方 式显然不够灵活,尤其是当预处理对象粘度较大时, 会出现无法输送等 现象。
发明内容 料大量灵活的生产轻质油,并提高原料的利用率和催化剂的效率的非均 相煤基油品悬浮床加氢方法。
本发明提供的非均相催化剂的煤基油品悬浮床加氢方法,包括下列 步骤:
①煤基油品原料的预处理和蒸馏分离
i煤基油品原料的预处理
将煤基油品原料进行常规脱水和脱除机械杂质后进行蒸馏分离,或 者直接进行步骤②的煤基油品悬浮床加氢;
i i煤基油品原料蒸馏分离
在实际的使用过程中,发明人发现煤基油品原料的来源工艺过程不 同时,蒸馏分离的馏分切割温度需要更灵活和优化才能满足实际生产和 操作的需要, 可根据煤基油品的性质, 煤基油品原料分离为酚油馏分或 石脑油馏分、 柴油馏分和重油馏分, 也就是当煤基油品原料中的酚含量 较低时, 含量低于 3%时, 可将煤基油品原料蒸馏分离为石脑油馏分、 柴油馏分和重油馏分, 也可根据后续加工提质的要求, 将煤基油品原料 蒸馏分离为石脑油 -柴油的混合馏分和重油馏分, 当煤基油品原料中的 酚含量较高时, 含量高于 3%、 石脑油馏分含量较高时, 含量高于 5%时, 可将煤基油品原料蒸馏分离为石脑油馏分、 酚油馏分、 柴油馏分和重油 馏分, 当煤基油品原料中的酚含量较高时, 含量高于 3%、 石脑油馏分 含量较低时, 含量低于 5%时, 可将煤基油品原料蒸馏分离为石脑油 -酚 油混合愤分、 柴油馏分和重油馏分, 如果煤基油品原料油较重或粘度太 高, 可不进行蒸馏分离。 将预处理后的煤基油品采用蒸馏的方法, 通过 控制馏分切割点温度得到石脑油馏分、酚油馏分、柴油馏分和重油馏分, 其中石脑油馏分的切割温度为 IBP ~ 170 °C馏分, 酚油馏分的终切割点 温度为 210 ~ 260 °C之间的温度, 柴油馏分的终切割点温度为 300 ~ 380 °C之间的温度,剩余的为重油馏分。另外的,如果石脑油馏分含量很少, 也可以不单独切割石脑油馏分而直接得到酚油馏分、柴油馏分和重油馏 分, 此时酚油馏分的起始切割点温度则是初馏点( IBP )。 对于酚油馏分 采用传统煤基油品脱酚方法或其他脱酚方法,在脱酚单元中进行脱酚处 理, 获得脱酚油和粗酚, 粗酚在粗酚精制单元中进一步精制、 精馏分离 获得酚类化合物 (如苯酚、 甲酚、 二甲酚等)。
优选的, 此处重馏分油为切割点为 160 ~ 360 °C , 本领域技术人员 可以根据实际需要选择。
如果煤基油品原料油较重或粘度太高, 可不进行蒸馏分离, 而直接 进行加氢裂化。
②非均相催化剂的煤基油品悬浮床加氢
i悬浮床催化剂油浆制备
将催化剂、硫化剂和溶剂油混合, 一起加入到带有搅拌设施的催化 剂浆液制备装置中, 于常压、 80°C ~ 200°C温度条件下充分混合均匀制 成催化剂油浆。
所述溶剂油至少包括煤基油品全馏分或重馏分油、脱除了催化剂的 循环油中的一种或多种, 其用于制备催化剂油浆, 本领域技术人员人员 可以根据需要选择加入的油的种类和加入的油的量。
所述催化剂为含相、 镍、 钴、 钨或铁的单金属活性组分或复合多金 属活性组分的粒子直径为 1 ~100μηι 的粉状颗粒煤基油品悬浮床加氢 催化剂。
所述疏化剂为在反应条件下可生成疏化氢的物质,例如疏橫或二甲 基二硫醚等, 硫化剂的加入量应保证系统循环氢的硫化氢含量不小于 lOOOppm, 催化剂油浆的固体浓度可控制在 20 ~ 45% (重量), 优先控制 在 25 - 40% (重量)。
ii悬浮床加氢裂化
将步骤②中 i得催化剂油浆与煤基油品全愤分或重馏分油、含有催 化剂的循环油混和, 经原料泵升压、 混氢升温后进入一个或多个串联的 悬浮床加氢反应器进行加氢裂化反应, 加氢裂化工艺条件为反应温度 320 ~ 480°C, 优选 350 - 450; 反应压力 8 ~25Mpa, 优选 10~19Mpa; 体积空速 0.3 ~ 3. Oh"1, 优选 0.5 ~ 2. Oh"1; 氢油体积比 500 ~ 2000, 优 选 800 ~ 1500; 催化剂的加入量以控制活性组分的金属总量与煤基油品 原料重量之比为 0.1: 100至 4: 100, 优选为 0.5: 100至 2: 100。
悬浮床加氢反应器反应流出物经过分离单元(分离单元可由两个或 多个分离器组成)分离后得到液固相混合物流(经两分离器或多个分离 器分离得到含固油)和富氢气体, 富氢气体用作循环氢; 液固相混合物 流作为循环油继续进行加氢裂化反应或经处理得到循环油,继续进行加 氢裂化反应。
液固相混合物流可采用如下几种方法分离:
( 1 )经常压分馏塔分馏, 塔顶得到轻馏分油 (终切割点温度可为 300 ~ 380°C之间的温度), 塔底为含有催化剂的常底重油 (或称尾油), 其中大部分(大约三分之二到五分之四)常底重油作为循环油直接循环 到悬浮床加氢反应器内进一步进行加氢轻质化反应, 其余少部分(大约 三分之一到五分之一 )的常底重油进入固液分离系统进行固液分离, 固 液分离可采用过滤或离心分离或沉降或减压分馏的形式,分离后得到催 化剂残渣和悬浮床加氢重馏分油,重馏分油或者作为循环油直接和悬浮 床的反应原料混合, 或者作为催化剂油浆制备的部分溶剂, 循环进入悬 浮床加氢反应器内进一步进行加氢轻质化反应,脱出的催化剂外甩或再 生, 或
( 2 ) 悬浮床加氢反应器反应流出物经过分离单元(分离单元可由 两个或多个分离器组成)分离后得到轻质油、 含固油(经两分离器或多 个分离器分离得到轻质油或称低分油、含固油或称高分油)和富氢气体, 富氢气体用作循环氢, 轻质油作为下一步提质加工的原料油之一, 含固 油的大部分(大约三分之二到五分之四)作为循环油直接环进入悬浮床 加氢反应器内进一步进行加氢轻质化反应, 其余少部分(大约三分之一 到五分之一)的含固油直接采用沉降法或离心分离或过滤的方式或减压 分愤的方式进行固液的分离,脱固的反应产物循环进入悬浮床加氢反应 器内进一步进行加氢轻质化反应, 脱出的催化剂外甩或再生。
③提质加工
将上述步骤①至②得到的全部轻质馏分油进行常规提质加工 ,步骤 ②的常压塔顶得到悬浮床加氢反应产物轻馏分油和步骤①蒸馏得到的 煤基油品柴油馏分、脱酚油或轻质油馏分一起作为馏分油提质加工的原 料油, 并加工生产燃料油和化工原料, 其中的石脑油馏分可采用催化重 整或催化重整-芳烃抽提联合工艺生产汽油或芳烃产品, 煤柴馏分可采 用加氢精制或选择性加氢裂化技术生产航空煤油、 柴油产品。
本发明提供的方法的优点为:
1 )根据煤基油品的性质, 煤基油品原料可分离为酚油馏分或石脑 油馏分、 柴油馏分和重油馏分或轻质馏分和重质馏分, 也可以不经过蒸 馏而将其直接用作氢化裂化, 方案更灵活和优化, 在省去处理步骤的同 时可满足实际生产和操作的需要;
2 )对于较重的煤基油品原料, 可以解决煤基油品的重馏分油的输 送问题, 还可以提高重油悬浮床加氢裂化产物中柴油馏分的十六烷值, 提高产品的质量, 同时也降低了煤基油品轻质油中杂质如硫、氮、芳烃、 胶质和沥青质含量,降低了轻质油固定床加氢精制反应系统的操作可刻 实现发明的最佳方式
本发明用下列实施例来进一步说明本发明,但本发明的保护范围并 非限于下列实施例。
实施例 1
选用一种典型煤焦油作为本例煤基油品原料, 经常规脱水、 除机械 杂质预处理后的煤基油品原料的性质如表 1:
表 1 煤基油品原料的性质
Figure imgf000008_0001
将预处理后的煤基油品经蒸馏分离为 IBP~ 260°C、 260 ~ 350°C和 大于 350°C重馏分, 大于 350°C重馏分油做为悬浮床加氢反应器的原料 油进行加氢裂化轻质化反应。
本实施例所用催化剂为一种钼铁复合型悬浮床加氢催化剂,所用催 化剂包括高活性金属组分钼与低活性金属组分铁,其中高活性组分金属 钼与低活性组分金属铁的重量比为 1: 500, 催化剂水含量低于 0.5 wt%, 粒子直径为 1-100 μ ηι粉状颗粒。 该催化剂是将铁含量为 58wt%赤铁矿 (主要成份为 Fe203 )粉碎成小于 Ι ΟΟ μ ηι的粉状颗粒, 然后将 10%的钼 酸铵水溶液均勾地喷淋在颗粒上, 喷淋量大约为钼:铁重量比等于 1 : 500 , 经 100 °C下烘干 1小时, 得到含水量小于 0. 5 wt %的粉状颗粒 催化剂,
本实施例的悬浮床加氢工艺过程为:首先将脱除了催化剂的循环油 和 /或煤基油品大于 350 °C重馏分油的一小部分与催化剂粒度小于 100 μ m 的粉状颗粒钼铁复合型悬浮床加氢催化剂 (且金属相:铁重量比为 1 : 500 )及硫化剂二甲基二硫醚一起在 80 °C的搅拌条件下充分混合均匀 制得催化剂油浆, 控制催化剂油浆的固体浓度在 25wt%左右。 然后催化 剂油浆与其余大部分煤基油品大于 35 (TC重馏分油原料及悬浮床加氢反 应生成物经常压塔分愤后的含有催化剂的循环油(即约五分之四的常底 重油)混和, 经原料泵升压、 混氢升温后依次进入两个串联的悬浮床加 氢反应器进行加氢裂化反应, 工艺条件如表 2所示, 催化剂的加入量以 控制活性组分的金属与煤基油品原料重量之比为 0. 8: 100 , 悬浮床反应 器反应流出物经过高温分离器、低温分离器后得到液固相高低分油混合 物流和富氢气体二部分。 富氢气体用作循环氢。 液固相高低分油混合物 流经常压塔分愤后, 塔顶得到小于 37 CTC轻馏分油, 塔底得到含有催化 剂的常底重油, 其中大部分(大约五分之四)常底重油作为循环油直接 循环到悬浮床加氢反应器内进一步进行加氢轻质化反应; 其余小部分 (大约五分之一)的常底重油采用过滤的方法进行固液分离, 分离后得 到催化剂残渣和悬浮床加氢重馏分油,这部分重馏分油或者直接和悬浮 床的反应原料混合或者作为催化剂油浆制备的部分溶剂,循环进入悬浮 床加氢反应器内进一步进行加氢轻质化反应, 脱出的催化剂外甩或再 生。 其所得部分产物产率分布于表 3所示。
本实施例在 1. 0千克原料油 /小时的连续悬浮床试验装置上进行, 表 2 工艺条件
反应温度, °c 4 30
反应氢分压, MPa 17
空速, h— 1 1. 0
氩油比, v/v 800
催化剂 (包括再生催化剂)加入量(铁 +钼) /原料 0. 8/ 100 油重量比
常底重油直接循环量 /去减压塔脱固量 4/ 1
硫化剂二甲基石克醚 /原料油 2/ 100
表 3 所得部分产物产率分布
Figure imgf000010_0001
可见, 采用本发明的悬浮床加氢工艺处理煤基油品的方法, 可使 轻质油产率达到 94. 7wt%。 试验得到的轻质油可采用现有的加工技术进 行提质加工生产燃料油和化工原料。其中的石脑油馏分可采用催化重整 或催化重整-芳烃抽提联合工艺技术汽油或芳烃产品, 其中的煤柴馏分 可采用加氢精制或选择性加氢裂化技术生产航空煤油、 柴油产品。
在本发明的另外一个实施例中,使用的为切割温度在 230 °C的蒸馏 分离重馏分油, 其也具有一定的粘度, 利用上述方法也可以获得类似的 效果, 并且由于选择了较低的切割点, 柴油馏分的质量也提高了。
实施例 2
选用一种重质馏分含量较高的煤基油品作为本例煤基油品原料,经 常规脱水、 除机械杂质预处理后的煤基油品原料的性质如表 4 : 该原料 油的重质馏分含量高, 粘度较高, 40 °C粘度是实施例 1原料油的 17倍 多, 考虑到工业装置输送的问题, 物料的粘度太高, 无法实现输送, 该 原料预处理是, 蒸馏分离重馏分油的切割温度宜在 31 0 °C 。
表 4 煤基油品原料的性质
项目 预处理后煤基油品全馏分 密度, kg/m3, 20 °C 1054. 8
运动粘度, 匪 7s, 40 °C
水分, wt % 1. 7
灰分, wt % 0. 1
残炭, wt % 14. 1
Figure imgf000011_0001
本试验将预处理后的煤基油品经蒸馏分离为 IBP ~ 310°C和大于 310°C重馏分, 大于 310°C重馏分油做为悬浮床加氢反应器的原料油进 行加氢裂化轻质化反应。
本实施例所用催化剂为一种钼铁复合型悬浮床加氢催化剂,所用催 化剂包括高活性金属组分钼与低活性金属组分铁,其中高活性组分金属 钼与低活性组分金属铁的重量比为 1: 500, 催化剂水含量低于 0.5 wt%, 粒子直径为 1-100 μηι粉状颗粒。 该催化剂是将铁含量为 58wt%赤铁矿 (主要成份为 Fe203 )粉碎成小于 ΙΟΟμηι的粉状颗粒, 然后将 10%的钼 酸铵水溶液均勾地喷淋在颗粒上, 喷淋量大约为钼:铁重量比等于 1: 500, 经 100°C下烘干 1小时, 得到含水量小于 0.5 wt %的粉状颗粒 催化剂,
本实施例的悬浮床加氢工艺过程为:首先将脱除了催化剂的循环油 和 /或煤基油品大于 310°C重馏分油的一小部分与催化剂粒度小于 100 μ m 的粉状颗粒钼铁复合型悬浮床加氢催化剂 (且金属相:铁重量比为 1: 500 )及硫化剂二甲基二硫醚一起在 80°C的搅拌条件下充分混合均匀 制得催化剂油浆, 控制催化剂油浆的固体浓度在 25wt%左右。 然后催化 剂油浆与其余大部分煤基油品大于 31 (TC重馏分油原料及悬浮床加氢反 应生成物经常压塔分愤后的含有催化剂的循环油(即约五分之四的常底 重油)混和, 经原料泵升压、 混氢升温后依次进入两个串联的悬浮床加 氢反应器进行加氢裂化反应, 工艺条件如表 5所示, 催化剂的加入量以 控制活性组分的金属与煤基油品原料重量之比为 1. 5: 100 , 悬浮床反应 器反应流出物经过高温分离器、低温分离器后得到液固相高低分油混合 物流和富氢气体二部分。 富氢气体用作循环氢。 液固相高低分油混合物 流经常压塔分愤后, 塔顶得到小于 37 CTC轻馏分油, 塔底得到含有催化 剂的常底重油, 其中大部分(大约五分之四)常底重油作为循环油直接 循环到悬浮床加氢反应器内进一步进行加氢轻质化反应; 其余小部分 (大约五分之一)的常底重油采用过滤的方法进行固液分离, 分离后得 到催化剂残渣和悬浮床加氢重馏分油,这部分重馏分油或者直接和悬浮 床的反应原料混合或者作为催化剂油浆制备的部分溶剂,循环进入悬浮 床加氢反应器内进一步进行加氢轻质化反应, 脱出的催化剂外甩或再 生。 其所得部分产物产率分布于表 6所示。
本实施例在 1. 0千克原料油 /小时的连续悬浮床试验装置上进行, 表 5 工艺条件
Figure imgf000012_0001
表 6 所得部分产物产率分布
Figure imgf000012_0002
可见, 采用本发明的悬浮床加氢工艺处理煤基油品的方法, 可使 轻质油产率达到 93. 7wt%。 试险得到的轻质油可采用现有的加工技术进 行提质加工生产燃料油和化工原料。其中的石脑油馏分可采用催化重整 或催化重整-芳烃抽提联合工艺技术汽油或芳烃产品, 其中的煤柴馏分 可采用加氢精制或选择性加氢裂化技术生产航空煤油、 柴油产品。
实施例 3
选用一种重质馏分含量较高的煤基油品作为本例煤基油品原料,经 常规脱水、 除机械杂质预处理后的煤基油品原料的性质如表 7 : 该原料 油的重质馏分含量高, 粘度较高, 40 °C粘度是实施例 1原料油的 17倍 多, 考虑到工业装置输送的问题, 物料的粘度太高, 无法实现输送, 该 原料预处理是, 蒸馏分离重馏分油的切割温度宜在 28 0 °C。
表 7煤基油品原料的性质
Figure imgf000013_0001
本试验将预处理后的煤基油品经蒸馏分离为 I BP ~ 280 °C和大于 280 °C重馏分, 大于 280 °C重馏分油做为悬浮床加氢反应器的原料油进 行加氢裂化轻质化反应。
本实施例所用催化剂为一种钼铁复合型悬浮床加氢催化剂,所用催 化剂包括高活性金属组分钼与低活性金属组分铁,其中高活性组分金属 钼与低活性组分金属铁的重量比为 1 : 500 , 催化剂水含量低于 0. 5 wt% , 粒子直径为 1-100 μ ηι粉状颗粒。 该催化剂是将铁含量为 58wt%赤铁矿 (主要成份为 Fe203 )粉碎成小于 Ι ΟΟ μ ηι的粉状颗粒, 然后将 10%的钼 酸铵水溶液均勾地喷淋在颗粒上, 喷淋量大约为钼:铁重量比等于 1 : 500 , 经 100 °C下烘干 1小时, 得到含水量小于 0. 5 wt %的粉状颗粒 催化剂,
本实施例的悬浮床加氢工艺过程为:首先将脱除了催化剂的循环油 和 /或煤基油品大于 280 °C重馏分油的一小部分与催化剂粒度小于 100 μ m 的粉状颗粒钼铁复合型悬浮床加氢催化剂 (且金属相:铁重量比为 1 : 500 )及硫化剂二甲基二硫醚一起在 80 °C的搅拌条件下充分混合均匀 制得催化剂油浆, 控制催化剂油浆的固体浓度在 25wt%左右。 然后催化 剂油浆与其余大部分煤基油品大于 28 (TC重馏分油原料及悬浮床加氢反 应生成物经常压塔分愤后的含有催化剂的循环油(即约五分之四的常底 重油)混和, 经原料泵升压、 混氢升温后依次进入两个串联的悬浮床加 氢反应器进行加氢裂化反应, 工艺条件如表 8所示, 催化剂的加入量以 控制活性组分的金属与煤基油品原料重量之比为 2. 0: 100 , 悬浮床反应 器反应流出物经过高温分离器、低温分离器后得到液固相高低分油混合 物流和富氢气体二部分。 富氢气体用作循环氢。 液固相高低分油混合物 流经常压塔分愤后, 塔顶得到小于 37 CTC轻馏分油, 塔底得到含有催化 剂的常底重油, 其中大部分(大约五分之四)常底重油作为循环油直接 循环到悬浮床加氢反应器内进一步进行加氢轻质化反应; 其余小部分
(大约五分之一)的常底重油采用过滤的方法进行固液分离, 分离后得 到催化剂残渣和悬浮床加氢重馏分油,这部分重馏分油或者直接和悬浮 床的反应原料混合或者作为催化剂油浆制备的部分溶剂,循环进入悬浮 床加氢反应器内进一步进行加氢轻质化反应, 脱出的催化剂外甩或再 生。 其所得部分产物产率分布于表 9所示。
本实施例在 1. 0千克原料油 /小时的连续悬浮床试验装置上进行, 表 8 工艺条件
反应温度, °c 460
反应氢分压, MPa 19
空速, h— 1 1. 0 氩油比, v/v 1 000 催化剂 (包括再生催化剂 )加入量(铁 +钼 ) /原料 2. 0/ 100 油重量比
常底重油直接循环量 /去减压塔脱固量 4/ 1
硫化剂二甲基石克醚 /原料油 2/ 100
表 9所得部分产物产率分布
Figure imgf000015_0001
可见, 采用本发明的悬浮床加氢工艺处理煤基油品的方法, 可使 轻质油产率达到 92. 6wt%。 试验得到的轻质油可采用现有的加工技术进 行提质加工生产燃料油和化工原料。其中的石脑油馏分可采用催化重整 或催化重整-芳烃抽提联合工艺技术汽油或芳烃产品, 其中的煤柴馏分 可采用加氢精制或选择性加氢裂化技术生产航空煤油、 柴油产品。
实施例 4
选用一种重质馏分含量较高粘度较高的煤基油品作为本例煤基油 品原料, 经常规脱水、 除机械杂质预处理后的煤基油品原料的性质如表 10: 该原料油的重质馏分含量高, 粘度较高, 40 °C粘度是实施例 1原料 油的 26倍多, 高达 1528. 5 匪 7s,考虑到工业装置输送的问题, 物料的 粘度太高, 无法实现输送, 本试验考虑全愤分进悬浮床加氢裂化反应系 统, 不进行愤分切割分离。
表 10实施例 4的煤基油品原料的性质
项目 预处理后煤基油品全馏分 密度, kg/m3, 20 °C 1118. . 2
运动粘度, 匪 7s, 40 °C
水分, wt % 2. 9
灰分, wt % 0. 6
残炭, wt % 19. 78
甲苯不溶物, wt % 1. 2 C 86.10
1 H 6.56
元素组成 oo , wt %, S 0.32
N 1.11
0 (差减法) 5.91
实沸点蒸馏结果, wt %
0.4
12. 6
> 280°C 87.0
本试验将预处理后的煤基油品全馏分油做为悬浮床加氢反应器的 原料油进行加氢裂化轻质化反应。
本实施例所用催化剂为一种钼铁复合型悬浮床加氢催化剂,所用催 化剂包括高活性金属组分钼与低活性金属组分铁,其中高活性组分金属 钼与低活性组分金属铁的重量比为 1: 500, 催化剂水含量低于 0.5 wt%, 粒子直径为 1-100 μηι粉状颗粒。 该催化剂是将铁含量为 58wt%赤铁矿 (主要成份为 Fe203 )粉碎成小于 ΙΟΟμηι的粉状颗粒, 然后将 10%的钼 酸铵水溶液均勾地喷淋在颗粒上, 喷淋量大约为钼:铁重量比等于 1: 500, 经 100°C下烘干 1小时, 得到含水量小于 0.5 wt %的粉状颗粒 催化剂,
本实施例的悬浮床加氢工艺过程为:首先将脱除了催化剂的循环油 和 /或煤基油品全馏分油的一小部分与催化剂粒度小于 100 μηι 的粉状 颗粒钼铁复合型悬浮床加氢催化剂 (且金属钼:铁重量比为 1: 500 )及 硫化剂二甲基二硫醚一起在 80 °C的搅拌条件下充分混合均匀制得催化 剂油浆, 控制催化剂油浆的固体浓度在 25wt%左右。 然后催化剂油浆与 其余大部分煤基油品全馏分油原料及悬浮床加氢反应生成物经常压塔 分愤后的含有催化剂的循环油(即约五分之四的常底重油)混和, 经原 料泵升压、混氢升温后依次进入两个串联的悬浮床加氢反应器进行加氢 裂化反应, 工艺条件如表 11所示, 催化剂的加入量以控制活性组分的 金属与煤基油品原料重量之比为 3.0: 100, 悬浮床反应器反应流出物经 过高温分离器、低温分离器后得到液固相高低分油混合物流和富氢气体 二部分。 富氢气体用作循环氢。 液固相高低分油混合物流经常压塔分愤 后, 塔顶得到小于 37CTC轻馏分油, 塔底得到含有催化剂的常底重油, 其中大部分(大约五分之四)常底重油作为循环油直接循环到悬浮床加 氢反应器内进一步进行加氢轻质化反应; 其余小部分(大约五分之一) 的常底重油采用过滤的方法进行固液分离,分离后得到催化剂残渣和悬 浮床加氢重馏分油,这部分重馏分油或者直接和悬浮床的反应原料混合 或者作为催化剂油浆制备的部分溶剂,循环进入悬浮床加氢反应器内进 一步进行加氢轻质化反应, 脱出的催化剂外甩或再生。 其所得部分产物 产率分布于表 12所示。
本实施例在 1. 0千克原料油 /小时的连续悬浮床试验装置上进行, 表 11 实施例 4的工艺条件
Figure imgf000017_0001
表 12所得部分产物产率分布
Figure imgf000017_0002
可见, 采用本发明的悬浮床加氢工艺处理煤基油品的方法, 可使轻 质油产率达到 90. lwt%。 试验得到的轻质油可采用现有的加工技术进行 提质加工生产燃料油和化工原料。其中的石脑油馏分可采用催化重整或 催化重整-芳烃抽提联合工艺技术汽油或芳烃产品, 其中的煤柴馏分可 采用加氢精制或选择性加氢裂化技术生产航空煤油、 柴油产品。 工业应用性
对于较重的煤基油品原料,本发明可以解决煤基油品的重馏分油的 输送问题, 还可以提高重油悬浮床加氢裂化产物中柴油馏分的十六烷 值, 提高产品的质量, 同时也降低了煤基油品轻质油中杂质如硫、 氮、 芳烃、胶质和沥青质含量, 降低了轻质油固定床加氢精制反应系统的操 作可刻度。

Claims

权 利 要 求
1、 一种非均相煤基油品悬浮床加氢方法, 包括下列步骤:
1 )将催化剂、 硫化剂和溶剂油混合, 于常压、 80°C ~ 200°C温度条 件下充分混合均勾制成催化剂油浆;
2)催化剂油浆与煤基油品全馏分或重质馏分油、 循环油混合后, 进入悬浮床加氢反应器进行加氢裂化反应,其中催化剂的加入量以控制 活性组分的金属总量与煤基油品原料重量之比为 0.1: 100至 4: 100, 反 应器内的反应温度 320 ~ 480°C, 反应压力 8~25MPa, 体积空速 0.3~ 3.0 h"1, 氢油体积比 500 ~ 2000, 悬浮床加氢反应器反应流出物经过分 离后得到液固相混合物流和富氢气体;液固相混合物流作为循环油继续 进行加氢裂化反应或经处理得到循环油, 继续进行加氢裂化反应; 所述催化剂为煤基油品悬浮床加氢催化剂;
所述的重质馏分油的切割点为 160 ~ 360 °C。
2、 根据权利要求 1所述的方法, 其特征在于, 所述溶剂油包括煤 基油品全馏分或重馏分油、脱除了催化剂的悬浮床加氢重馏分油中的一 种或多种; 所述硫化剂为在反应条件下可生成硫化氢的物质。
3、 根据权利要求 1 ~2任一所述的方法, 其特征在于, 所述硫化剂 为硫磺或二甲基硫醚。
4、 根据权利要求 1所述的方法, 其特征在于, 所述催化剂油浆的 固体浓度为 25_40wt%。
5、 根据权利要求 1所述的方法, 其特征在于, 所述步骤 2) 中加 氢裂化反应温度为 350 ~ 450°C, 反应压力为 10~17MPa, 体积空速为 0.5~2.0 h"1, 氢油体积比为 800 ~ 1500, 催化剂加入量以控制活性组分 的金属与煤基油品原料重量之比为 0.5: 100至 2: 100。
6、 根据权利要求 1或 5所述的方法, 其特征在于, 所述步骤 2) 中液固相混合物流分离得到轻质馏分油和含有催化剂的常底重油,部分 常底重油作为循环油直接循环到悬浮床加氢反应器内进一步进行加氢 轻质化反应, 其余常底重油进入固液分离系统进行固液分离, 得到催化 剂残渣和悬浮床加氢重馏分油。
7、 根据权利要求 1或 5所述的方法, 其特征在于, 所述步骤 2) 中液固相混合物流大部分直接环进入悬浮床加氢反应器内进一步进行 加氢轻质化反应, 其余部分进行固液的分离, 脱固的反应产物循环进入 悬浮床加氢反应器内进一步进行加氢轻质化反应,脱出的催化剂外甩或 再生。
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