CN113462431B - Method for producing diesel oil and jet fuel - Google Patents
Method for producing diesel oil and jet fuel Download PDFInfo
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- CN113462431B CN113462431B CN202010245420.1A CN202010245420A CN113462431B CN 113462431 B CN113462431 B CN 113462431B CN 202010245420 A CN202010245420 A CN 202010245420A CN 113462431 B CN113462431 B CN 113462431B
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- 239000002283 diesel fuel Substances 0.000 title claims abstract description 38
- 239000000446 fuel Substances 0.000 title claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 title abstract description 11
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 180
- 239000003054 catalyst Substances 0.000 claims abstract description 120
- 238000000034 method Methods 0.000 claims abstract description 94
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 57
- 239000001257 hydrogen Substances 0.000 claims abstract description 57
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000011593 sulfur Substances 0.000 claims abstract description 42
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 42
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 116
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
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- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 6
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000003350 kerosene Substances 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910000480 nickel oxide Inorganic materials 0.000 description 4
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
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- 229930195733 hydrocarbon Natural products 0.000 description 3
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- WWZKQHOCKIZLMA-UHFFFAOYSA-N Caprylic acid Natural products CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
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- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- GONOPSZTUGRENK-UHFFFAOYSA-N benzyl(trichloro)silane Chemical compound Cl[Si](Cl)(Cl)CC1=CC=CC=C1 GONOPSZTUGRENK-UHFFFAOYSA-N 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
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- FUZZWVXGSFPDMH-UHFFFAOYSA-N n-hexanoic acid Natural products CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
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- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
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- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
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- 150000001298 alcohols Chemical class 0.000 description 1
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- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
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- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
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- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
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Classifications
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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
- 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
- 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
- C10G2300/4006—Temperature
-
- 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
- C10G2400/30—Aromatics
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
本发明涉及炼油化工领域，公开了一种生产柴油和喷气燃料的方法，包括：(1)将柴油原料油与氢气引入至装填有加氢精制催化剂I的第一加氢反应区中进行第一加氢反应，得到第一加氢物流；(2)将所述第一加氢物流与常一线原料油引入至装填有加氢精制催化剂II的第二加氢反应区中进行第二加氢反应，使得油料在所述第二加氢反应区以上行式的方式流过其中，得到第二加氢物流；(3)将所述第二加氢物流进行分离以得到精制柴油和精制喷气燃料。采用本发明提供的方法，能够在相对缓和的条件下，处理高硫直馏柴油或劣质二次加工柴油，生产硫含量小于10μg/g、双环以上芳烃含量小于7重量％的清洁柴油产品。
The invention relates to the field of oil refining and chemical industry, and discloses a method for producing diesel oil and jet fuel, comprising: (1) introducing diesel feedstock oil and hydrogen into a first hydrogenation reaction zone filled with a hydrotreating catalyst I to carry out the first hydrogenation reaction zone Hydrogenation reaction to obtain the first hydrogenation stream; (2) introducing the first hydrogenation stream and normal first-line feedstock oil into the second hydrogenation reaction zone filled with hydrofinishing catalyst II to carry out the second hydrogenation reaction , so that the oil material flows through it in an ascending manner in the second hydrogenation reaction zone to obtain a second hydrogenation stream; (3) separating the second hydrogenation stream to obtain refined diesel oil and refined jet fuel. By adopting the method provided by the invention, high-sulfur straight-run diesel oil or inferior secondary processed diesel oil can be processed under relatively moderate conditions to produce clean diesel products with a sulfur content of less than 10 μg/g and a content of bicyclic and above aromatics of less than 7% by weight.
Description
技术领域technical field
本发明涉及炼油化工领域，具体涉及一种生产柴油和喷气燃料的方法。The invention relates to the field of oil refining and chemical industry, in particular to a method for producing diesel oil and jet fuel.
背景技术Background technique
原油经过蒸馏得到的各种馏分油通常称为直馏馏分油(直接蒸馏得到的馏分油)，其中的直馏煤油馏分主要用于生产喷气燃料，直馏柴油馏分主要用于生产柴油。直馏煤油主要为140℃～280℃馏分，柴油馏分主要为200℃～350℃馏分。Various distillate oils obtained by distillation of crude oil are usually called straight-run distillate oil (distillate oil obtained by direct distillation), of which the straight-run kerosene fraction is mainly used for the production of jet fuel, and the straight-run diesel fraction is mainly used for the production of diesel oil. Straight-run kerosene is mainly 140°C-280°C fraction, and diesel fraction is mainly 200°C-350°C fraction.
随着人们环保意识的提高以及环保法规的日益严格，生产和使用清洁燃料越来越成为一种发展趋势。对于柴油的清洁化来讲，低硫和低芳烃含量是其清洁化的关键。With the improvement of people's awareness of environmental protection and the increasingly stringent environmental regulations, the production and use of clean fuels has increasingly become a development trend. For the cleanliness of diesel, low sulfur and low aromatics content is the key to cleanliness.
加氢技术作为一种有效的脱硫、脱氮、脱芳手段，在清洁燃料的生产中发挥着越来越重要的作用。加氢处理技术也多种多样，先后出现了单段加氢、单段串联加氢和两段加氢等工艺技术。现有技术的反应器大多为绝热反应器，由于反应物反应放热，反应器内存在较大温升，为了使反应在合理的反应温度内进行，通常反应器入口温度设计较低，随着反应的进行，床层温度逐渐提高，到反应器出口温度达到最高。随着炼油厂加工劣质柴油数量越来越多，柴油原料油质量越来越差，这就需要更高的反应温度来进行深度加氢脱硫。As an effective means of desulfurization, denitrogenation and dearomatization, hydrogenation technology is playing an increasingly important role in the production of clean fuels. There are also various hydroprocessing technologies, such as single-stage hydrogenation, single-stage series hydrogenation and two-stage hydrogenation. Most of the reactors in the prior art are adiabatic reactors. Due to the exothermic reaction of the reactants, there is a large temperature rise in the reactor. In order to make the reaction proceed within a reasonable reaction temperature, the inlet temperature of the reactor is usually designed to be low. As the reaction progresses, the temperature of the bed layer increases gradually until the outlet temperature of the reactor reaches the highest value. As refineries process more and more low-quality diesel oil, the quality of diesel feed oil is getting worse, which requires a higher reaction temperature for deep hydrodesulfurization.
工业上典型的柴油加氢精制反应器为绝热反应器，即从反应器顶部至底部，反应温度依次上升。对于直馏柴油加氢装置，反应器温升为30～40℃，在反应末期，反应器出口的温度高达380～400℃。在如此高的反应温度下，很难对其中的多环芳烃进行加氢饱和。并且直馏煤油馏分在如此高的反应温度下，属于过度加氢精制，会将其中属于天然抗磨剂的硫化物深度脱除。当催化剂运转到反应末期时，反应器出口温度能够达到400℃，此时在催化剂上主要进行难脱除的含硫化合物的反应以及多环芳烃饱和阶段，过高的温度又不利于这些反应的进行。The typical industrial diesel hydrotreating reactor is an adiabatic reactor, that is, the reaction temperature rises sequentially from the top to the bottom of the reactor. For the straight-run diesel hydrogenation unit, the temperature rise of the reactor is 30-40°C, and at the end of the reaction, the temperature at the outlet of the reactor is as high as 380-400°C. At such a high reaction temperature, it is difficult to hydrogenate the polycyclic aromatic hydrocarbons therein. Moreover, the straight-run kerosene fraction belongs to excessive hydrofining at such a high reaction temperature, and the sulfides belonging to natural anti-wear agents will be deeply removed. When the catalyst runs to the end of the reaction, the outlet temperature of the reactor can reach 400°C. At this time, the reaction of sulfur-containing compounds that are difficult to remove and the saturation stage of polycyclic aromatic hydrocarbons mainly proceed on the catalyst. Too high temperature is not conducive to the progress of these reactions. conduct.
在工业馏分油加氢精制装置上，如采用加氢精制固定床工艺来同时加工常一线和柴油原料油，在生产超低硫柴油产品的工况下，需要更高的反应温度；而采用混合进料，容易使柴油馏分中的过多的单环芳烃进入煤油馏分，这样就是会导致在不降低煤油馏分的液体收率下致使喷气燃料产品中的烟点降低。In the industrial distillate oil hydrofinishing unit, if the hydrofinishing fixed bed process is used to process regular first-line and diesel feedstock oil at the same time, a higher reaction temperature is required for the production of ultra-low sulfur diesel products; Feed, it is easy to make too much single-ring aromatics in the diesel fraction into the kerosene fraction, which will lead to a lower smoke point in the jet fuel product without reducing the liquid yield of the kerosene fraction.
并且现有技术中，通过采用劣质柴油原料来生产超低硫、低芳烃柴油的过程中，都存在反应苛刻度高，催化剂稳定性差，失活快，造成了装置整体运行周期短的问题。Moreover, in the prior art, in the process of producing ultra-low-sulfur and low-aromatic diesel by using inferior diesel raw materials, there are problems of high reaction severity, poor catalyst stability, and rapid deactivation, resulting in a short overall operation period of the device.
因此，如何在较缓和条件下长周期稳定生产超低硫柴油的生产方法是炼油工业最迫切的需求之一。Therefore, how to stably produce ultra-low sulfur diesel for a long period of time under moderate conditions is one of the most urgent needs of the oil refining industry.
发明内容Contents of the invention
本发明的目的是为了克服现有技术的低硫柴油生产工艺中存在的催化剂使用中末期反应条件苛刻而导致产品质量变差的缺陷。The object of the present invention is to overcome the defect of poor product quality caused by severe reaction conditions at the end of catalyst use in the low-sulfur diesel production process in the prior art.
为了实现上述目的，本发明提供一种生产柴油和喷气燃料的方法，该方法包括：In order to achieve the above object, the present invention provides a method for producing diesel oil and jet fuel, the method comprising:
(1)将柴油原料油与氢气引入至装填有加氢精制催化剂I的第一加氢反应区中进行第一加氢反应，得到第一加氢物流；(1) Introducing diesel feed oil and hydrogen into the first hydrogenation reaction zone filled with hydrotreating
(2)将所述第一加氢物流与常一线原料油引入至装填有加氢精制催化剂II的第二加氢反应区中进行第二加氢反应，使得油料在所述第二加氢反应区以上行式的方式流过其中，得到第二加氢物流；(2) The first hydrogenation stream and the normal first-line feed oil are introduced into the second hydrogenation reaction zone filled with the hydrofinishing catalyst II to carry out the second hydrogenation reaction, so that the oil is The zone flows through it in an ascending manner to obtain the second hydrogenation stream;
(3)将所述第二加氢物流进行分离以得到精制柴油和精制喷气燃料；(3) separating the second hydrogenated stream to obtain refined diesel oil and refined jet fuel;
所述第二加氢反应区中的反应温度低于所述第一加氢反应区中的反应温度；The reaction temperature in the second hydrogenation reaction zone is lower than the reaction temperature in the first hydrogenation reaction zone;
所述加氢精制催化剂II中含有载体和负载在所述载体上的第一元素和第二元素，所述第一元素为钼元素和/或钨元素，所述第二元素为钴元素和/或镍元素。The hydrotreating catalyst II contains a carrier and a first element and a second element supported on the carrier, the first element is molybdenum and/or tungsten, and the second element is cobalt and/or or nickel.
采用本发明提供的方法，能够处理高硫直馏柴油或劣质二次加工柴油，在相对缓和的条件下，生产硫含量小于10μg/g、双环以上芳烃含量小于7重量％的清洁柴油产品，并且能够同时生产各项指标满足3号喷气燃料质量标准的产品。The method provided by the invention can process high-sulfur straight-run diesel oil or low-quality secondary processed diesel oil, and produce clean diesel products with a sulfur content of less than 10 μg/g and a content of more than double-ring aromatics of less than 7% by weight under relatively mild conditions, and It can simultaneously produce products whose various indicators meet the quality standards of No. 3 jet fuel.
相比于现有技术，本发明的方法中的优选情况下的整个催化剂体系具有更为良好的稳定性，显著提高了装置的运转周期。同时，本发明提供的方法还能够克服现有技术的方法中存在的催化剂稳定性差导致的产品双环以上芳烃含量超标的缺陷。Compared with the prior art, the entire catalyst system in the method of the present invention has better stability, and the operating cycle of the device is significantly improved. Simultaneously, the method provided by the invention can also overcome the defects in the prior art method that the content of aromatic hydrocarbons with double rings or more exceeds the standard caused by the poor stability of the catalyst.
本发明的方法对设备要求不高且工艺流程简洁，即便是在常规的固定床反应器上，通过设置两个加氢反应区，也能获得高品质的精制柴油产品和喷气燃料产品。The method of the present invention has low equipment requirements and simple process flow, and can obtain high-quality refined diesel products and jet fuel products even by setting two hydrogenation reaction zones on a conventional fixed-bed reactor.
按照本发明的方法，第一加氢反应区的反应流出物和馏分较轻的常一线原料油进行混合，常一线原料油的进料温度为50-80℃，以此能够降低进入第二加氢反应区内的反应物流的反应温度，调整至合适反应温度后，以上行式流经第二加氢反应区的催化剂床层，在较高的空速下完成超深度加氢脱硫反应和双环以上芳烃进一步加氢饱和。因此，本发明的方法还具有节省能耗的优势。According to the method of the present invention, the reaction effluent in the first hydrogenation reaction zone is mixed with the normal first-line raw material oil with a lighter fraction, and the feed temperature of the normal first-line raw material oil is 50-80° C. After the reaction temperature of the reactant flow in the hydrogen reaction zone is adjusted to a suitable reaction temperature, it flows through the catalyst bed in the second hydrogenation reaction zone in an ascending manner, and completes the ultra-deep hydrodesulfurization reaction and double-ring reaction at a relatively high space velocity. The above aromatics are further hydrogenated and saturated. Therefore, the method of the present invention also has the advantage of saving energy consumption.
附图说明Description of drawings
图1是本发明的一种优选实施方式的生产柴油和喷气燃料的方法的工艺流程图。Figure 1 is a process flow diagram of a method for producing diesel and jet fuel in a preferred embodiment of the present invention.
附图标记说明Explanation of reference signs
1、柴油原料油 2、氢气1.
3、第一加氢反应区 4、第一加氢物流3. The first
5、常一线原料油 6、第二加氢反应区5. Often first-line raw material oil 6. Second hydrogenation reaction zone
7、第二加氢物流 8、气液分离器7.
9、富氢气体 10、循环氢压缩单元9. Hydrogen-
11、循环氢 12、冷氢11. Circulating hydrogen 12. Cold hydrogen
13、液相物流 14、分馏塔13.
15、精制柴油 16、精制喷气燃料15. Refined
17、轻烃产品17. Light hydrocarbon products
具体实施方式Detailed ways
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。Neither the endpoints nor any values of the ranges disclosed herein are limited to such precise ranges or values, and these ranges or values are understood to include values approaching these ranges or values. For numerical ranges, between the endpoints of each range, between the endpoints of each range and individual point values, and between individual point values can be combined with each other to obtain one or more new numerical ranges, these values Ranges should be considered as specifically disclosed herein.
在没有特别说明的情况下，本发明所述的常压表示一个标准大气压。Unless otherwise specified, the normal pressure described in the present invention means a standard atmospheric pressure.
在没有特别说明的情况下，元素以氧化物计的含量均表示元素的最稳定价态的氧化物。Unless otherwise specified, the contents of elements in terms of oxides represent oxides in the most stable valence state of the elements.
在没有特别说明的情况下，本发明所述的压力均为表压。Unless otherwise specified, the pressures mentioned in the present invention are all gauge pressures.
如前所述，本发明提供了一种生产柴油和喷气燃料的方法，该方法包括：As previously stated, the present invention provides a method of producing diesel and jet fuel comprising:
(1)将柴油原料油与氢气引入至装填有加氢精制催化剂I的第一加氢反应区中进行第一加氢反应，得到第一加氢物流；(1) Introducing diesel feed oil and hydrogen into the first hydrogenation reaction zone filled with
(2)将所述第一加氢物流与常一线原料油引入至装填有加氢精制催化剂II的第二加氢反应区中进行第二加氢反应，使得油料在所述第二加氢反应区以上行式的方式流过其中，得到第二加氢物流；(2) The first hydrogenation stream and the normal first-line feed oil are introduced into the second hydrogenation reaction zone filled with the hydrofinishing catalyst II to carry out the second hydrogenation reaction, so that the oil is The zone flows through it in an ascending manner to obtain the second hydrogenation stream;
(3)将所述第二加氢物流进行分离以得到精制柴油和精制喷气燃料；(3) separating the second hydrogenated stream to obtain refined diesel oil and refined jet fuel;
所述第二加氢反应区中的反应温度低于所述第一加氢反应区中的反应温度；The reaction temperature in the second hydrogenation reaction zone is lower than the reaction temperature in the first hydrogenation reaction zone;
所述加氢精制催化剂II中含有载体和负载在所述载体上的第一元素和第二元素，所述第一元素为钼元素和/或钨元素，所述第二元素为钴元素和/或镍元素。The hydrotreating catalyst II contains a carrier and a first element and a second element supported on the carrier, the first element is molybdenum and/or tungsten, and the second element is cobalt and/or or nickel.
根据本发明，对所述第一元素和所述第二元素的具体负载方式没有特别的限制。特别优选地，所述第一元素和所述第二元素的负载是通过浸渍法将所述第一元素和所述第二元素负载到载体上。According to the present invention, there is no particular limitation on the specific loading manner of the first element and the second element. Particularly preferably, the loading of the first element and the second element is loading the first element and the second element on a support by an impregnation method.
需要说的是，本发明的方法将第一加氢反应区获得的全部物料(固定装填的催化剂除外)均引入至第二加氢反应区中。What needs to be said is that, in the method of the present invention, all the materials obtained in the first hydrogenation reaction zone (except the fixedly loaded catalyst) are introduced into the second hydrogenation reaction zone.
在本发明中，由于常一线原料油主要为140℃～260℃馏分，相比于柴油馏分具有较高的汽化率。因此，当常一线原料油和经过第一加氢反应区的物流混合后，采用上行式的方式经过第二加氢反应区的催化剂床层，能够有效的将溶解在油品中的硫化氢带到气相中去。从而使得液相物流中的硫化氢浓度在第二加氢反应区内自下至上依次降低。由于能够大幅度降低第二加氢反应区液相物流中的硫化氢浓度，既能够提高超深度加氢脱硫速率，也有利于反应物流在第二加氢反应区内进行深度芳烃加氢饱和。In the present invention, since the first-line raw material oil is mainly a fraction at 140° C. to 260° C., it has a higher vaporization rate than the diesel fraction. Therefore, when the first-line raw material oil is mixed with the stream passing through the first hydrogenation reaction zone, it passes through the catalyst bed in the second hydrogenation reaction zone in an ascending manner, which can effectively remove the hydrogen sulfide dissolved in the oil. into the gas phase. As a result, the concentration of hydrogen sulfide in the liquid phase stream decreases sequentially from bottom to top in the second hydrogenation reaction zone. Since the concentration of hydrogen sulfide in the liquid phase stream in the second hydrogenation reaction zone can be greatly reduced, the ultra-deep hydrodesulfurization rate can be increased, and it is also conducive to the deep aromatics hydrogenation saturation of the reactant stream in the second hydrogenation reaction zone.
与传统的加氢脱硫、深度脱芳烃方法相比，本发明的方法不仅减少了催化剂的使用量，有效的降低了第二加氢反应区中液相硫化氢的浓度，减少了设备投资。Compared with traditional hydrodesulfurization and deep dearomatization methods, the method of the present invention not only reduces the amount of catalyst used, but also effectively reduces the concentration of liquid-phase hydrogen sulfide in the second hydrogenation reaction zone, reducing equipment investment.
优选情况下，所述柴油原料油与所述常一线原料油的进料重量比为1：0.2-0.8；更优选为1：0.4-0.6。Preferably, the feed weight ratio of the diesel feedstock oil to the normal first-line feedstock oil is 1:0.2-0.8; more preferably 1:0.4-0.6.
优选地，在所述加氢精制催化剂II中，以催化剂的总重量计，所述第一元素以氧化物计的含量为4-60重量％，所述第二元素以氧化物计的含量为1-40重量％。更优选地，在所述加氢精制催化剂II中，以催化剂的总重量计，所述第一元素以氧化物计的含量为20-60重量％，所述第二元素以氧化物计的含量为10-40重量％。Preferably, in the hydrotreating catalyst II, based on the total weight of the catalyst, the content of the first element as an oxide is 4-60% by weight, and the content of the second element as an oxide is 1-40% by weight. More preferably, in the hydrotreating catalyst II, based on the total weight of the catalyst, the content of the first element as an oxide is 20-60% by weight, and the content of the second element as an oxide is It is 10-40% by weight.
本发明的所述加氢精制催化剂II中还可以含有助剂元素，例如P等，对助剂元素的含量没有特定的要求，可以为本领域的常规助剂含量，例如助剂元素以氧化物计的含量为1-10重量％。The hydrorefining catalyst II of the present invention may also contain auxiliary elements, such as P, etc., and there is no specific requirement on the content of auxiliary elements, which can be the conventional auxiliary content in this field, such as auxiliary elements in the form of oxides The calculated content is 1-10% by weight.
优选地，在所述加氢精制催化剂II中，所述载体选自氧化铝、氧化硅、氧化铝-氧化硅、氧化钛、氧化镁、氧化硅-氧化镁、氧化硅-氧化锆、氧化硅-氧化钍、氧化硅-氧化铍、氧化硅-氧化钛、氧化钛-氧化锆、氧化硅-氧化铝-氧化钍、氧化硅-氧化铝-氧化钛和氧化硅-氧化铝-氧化镁和氧化硅-氧化铝-氧化锆中的至少一种。Preferably, in the hydrorefining catalyst II, the carrier is selected from the group consisting of alumina, silica, alumina-silica, titania, magnesia, silica-magnesia, silica-zirconia, silica - thorium oxide, silica-beryllia, silica-titania, titania-zirconia, silica-alumina-thoria, silica-alumina-titania and silica-alumina-magnesia and At least one of silicon-alumina-zirconia.
为了获得一种适用于本发明的方法的，适合在中低压情况下抗硫化氢深度芳烃饱和的加氢精制催化剂，根据一种优选的具体实施方式，所述加氢精制催化剂II为由包括以下步骤的操作制备得到的催化剂：In order to obtain a hydrofinishing catalyst suitable for the method of the present invention, which is suitable for resisting deep aromatic saturation of hydrogen sulfide under medium and low pressure conditions, according to a preferred embodiment, the hydrofinishing catalyst II comprises the following The catalyst that the operation of step prepares:
(a)将第一浸渍液与载体接触以进行第一浸渍处理，并将经所述第一浸渍处理后的固体物质依次进行干燥和焙烧，得到第一中间体；(a) contacting the first impregnation liquid with the carrier to perform the first impregnation treatment, and sequentially drying and roasting the solid matter after the first impregnation treatment to obtain the first intermediate;
(b)将第二浸渍液与所述第一中间体接触以进行第二浸渍处理，并将经所述第二浸渍处理后的固体物质进行焙烧，得到催化剂；(b) contacting the second impregnation liquid with the first intermediate to perform a second impregnation treatment, and roasting the solid material after the second impregnation treatment to obtain a catalyst;
所述第一浸渍液为含有第一元素、第二元素和有机络合剂的酸性水溶液；The first immersion liquid is an acidic aqueous solution containing the first element, the second element and an organic complexing agent;
所述第二浸渍液为含有有机络合剂的碱性水溶液。The second immersion liquid is an alkaline aqueous solution containing an organic complexing agent.
由本发明所提供的方法制得的催化剂具有更高的馏分油芳烃加氢饱和活性。The catalyst prepared by the method provided by the invention has higher hydrogenation saturation activity of distillate aromatics.
优选地，在步骤(a)中，控制焙烧的条件，使得所述第一中间体中的炭含量为0.03-0.5重量％，更优选使得所述第一中间体中的炭含量为0.04-0.4重量％；进一步优选使得所述第一中间体中的炭含量为0.05-0.35重量％。Preferably, in step (a), the roasting conditions are controlled so that the carbon content in the first intermediate is 0.03-0.5% by weight, more preferably the carbon content in the first intermediate is 0.04-0.4 % by weight; further preferably, the carbon content in the first intermediate is 0.05-0.35% by weight.
优选情况下，在步骤(a)中，所述焙烧的温度为350-500℃，优选为360-450℃，焙烧的时间为0.5-8h，优选为1-6h。Preferably, in step (a), the calcination temperature is 350-500°C, preferably 360-450°C, and the calcination time is 0.5-8h, preferably 1-6h.
优选情况下，在步骤(b)中，所述焙烧的温度为400-550℃，优选为450-550℃，焙烧的时间为0.5-8h，优选为2-4h。Preferably, in step (b), the calcination temperature is 400-550°C, preferably 450-550°C, and the calcination time is 0.5-8h, preferably 2-4h.
优选情况下，在步骤(a)和步骤(b)中，所述有机络合剂的种类相同或不同，各自独立地选自有机醇、有机酸、有机胺、有机铵盐中的至少一种。示例性地，所述有机络合剂选自乙二醇、草酸、柠檬酸、乙二胺四乙酸、氨三乙酸中的至少一种。Preferably, in step (a) and step (b), the type of the organic complexing agent is the same or different, each independently selected from at least one of organic alcohols, organic acids, organic amines, and organic ammonium salts . Exemplarily, the organic complexing agent is selected from at least one of ethylene glycol, oxalic acid, citric acid, ethylenediaminetetraacetic acid and nitrilotriacetic acid.
更优选地，在步骤(a)和步骤(b)中，所述有机络合剂各自独立地选自C2-7的有机胺、C2-7的有机铵盐中的至少一种。More preferably, in step (a) and step (b), the organic complexing agents are each independently selected from at least one of C 2-7 organic amines and C 2-7 organic ammonium salts.
根据本发明，所述浸渍法可以为等体积浸渍，也可以为过饱和浸渍，对所述浸渍的温度没有特别限定，可以是浸渍液所能达到的各种温度，对浸渍的时间没有特别限定，只要能负载上所需量的所需组分即可，例如：浸渍的温度可以为15-60℃，浸渍时间可以为0.5-5h。According to the present invention, the impregnation method can be equal-volume impregnation or supersaturated impregnation, the temperature of the impregnation is not particularly limited, it can be various temperatures that the impregnation solution can reach, and the impregnation time is not particularly limited , as long as the required amount of required components can be loaded, for example: the temperature of immersion can be 15-60°C, and the immersion time can be 0.5-5h.
优选情况下，所述第一浸渍液的pH值为2-6，更优选所述第一浸渍液的pH值为3-5。Preferably, the pH value of the first immersion liquid is 2-6, more preferably the pH value of the first immersion liquid is 3-5.
优选地，所述第二浸渍液的pH值为8-11。Preferably, the pH value of the second soaking liquid is 8-11.
在第一浸渍液和第二浸渍液中，对于加入含有第一元素和第二元素的盐和有机络合剂之后的水溶液，若酸碱性不符合要求，可通过常用方法调节水溶液的酸碱性，如加入酸性物质或碱性物质。In the first immersion liquid and the second immersion liquid, for the aqueous solution after adding the salt containing the first element and the second element and the organic complexing agent, if the acidity and alkalinity do not meet the requirements, the acidity and alkalinity of the aqueous solution can be adjusted by common methods properties, such as adding acidic or alkaline substances.
优选地，在所述加氢精制催化剂II中，孔径为2nm-40nm的孔体积占总孔体积的75-90％，孔径为100nm-300nm的孔体积占总孔体积的5-15％。Preferably, in the hydrotreating catalyst II, the pore volume with a pore diameter of 2nm-40nm accounts for 75-90% of the total pore volume, and the pore volume with a pore diameter of 100nm-300nm accounts for 5-15% of the total pore volume.
优选地，在所述加氢精制催化剂II中，比表面积为50-200m2/g；孔体积为0.2-0.4mL/g，平均孔径为5nm-40nm。Preferably, in the hydrotreating catalyst II, the specific surface area is 50-200m 2 /g; the pore volume is 0.2-0.4mL/g, and the average pore diameter is 5nm-40nm.
根据本发明一种优选的实施方式，所述加氢精制催化剂II的形状优选为圆柱形、三叶草形、四叶草形或蜂窝形。According to a preferred embodiment of the present invention, the shape of the hydrotreating catalyst II is preferably cylindrical, clover, four-leaf or honeycomb.
本发明中，为了降低加工超低硫柴油的反应苛刻度，减少反应干扰物对加氢超深度脱硫过程的影响，采用了两个串联的加氢反应区，在第一加氢反应区装填加氢精制催化剂I，优选该加氢精制催化剂I具有较高的超深度加氢脱硫的反应性能。在第二加氢反应区装填本发明优选的加氢精制催化剂II，该加氢精制催化剂II有较高的低温脱芳烃的反应性能。In the present invention, in order to reduce the reaction severity of processing ultra-low sulfur diesel oil and reduce the influence of reaction interferers on the hydrogenation ultra-deep desulfurization process, two series-connected hydrogenation reaction zones are used, and the first hydrogenation reaction zone is filled with The hydrorefining catalyst I, preferably the hydrorefining catalyst I has relatively high ultra-deep hydrodesulfurization reaction performance. The preferred hydrofinishing catalyst II of the present invention is loaded in the second hydrogenation reaction zone, and the hydrofinishing catalyst II has relatively high low-temperature dearomatization reaction performance.
优选情况下，采用本发明优选情况下的加氢精制催化剂II，不仅加氢脱硫反应的氢气利用率更高，而且在超深度加氢脱硫时受H2S的抑制作用更小，能够在更低的氢油体积比下完成柴油超深度加氢脱硫和脱芳烃。Preferably, using the hydrorefining catalyst II in the preferred case of the present invention not only has a higher hydrogen utilization rate in the hydrodesulfurization reaction, but also is less inhibited by H 2 S during ultra-deep hydrodesulfurization, and can be used in a more Ultra-deep hydrodesulfurization and dearomatization of diesel oil are completed at a low hydrogen-to-oil volume ratio.
本发明优选情况下的加氢精制催化剂II可以采用CN108568305A中公开的相同方法制备，示例性地，本发明的制备例部分提供了本发明的催化剂的优选的制备工艺。本发明的发明人发现，本发明提供的方法配合CN108568305A中公开的催化剂作为本发明的加氢精制催化剂II能够明显提高装置及产品质量的稳定性，延长装置的运转周期。The hydrorefining catalyst II in the preferred case of the present invention can be prepared by the same method disclosed in CN108568305A. Exemplarily, the preparation example of the present invention provides a preferred preparation process of the catalyst of the present invention. The inventors of the present invention found that the method provided by the present invention combined with the catalyst disclosed in CN108568305A as the hydrogenation catalyst II of the present invention can significantly improve the stability of the device and product quality, and prolong the operation period of the device.
优选地，所述加氢精制催化剂I与所述加氢催化剂II相同或不同。Preferably, the hydrotreating catalyst I is the same as or different from the hydrogenation catalyst II.
更优选情况下，所述加氢精制催化剂I中含有载体和加氢金属活性组分，所述加氢金属活性组分含有至少一种选自第VIB族的金属元素和至少一种选自第VIII族的金属元素。More preferably, the hydrorefining catalyst I contains a carrier and a hydrogenation metal active component, and the hydrogenation metal active component contains at least one metal element selected from Group VIB and at least one metal element selected from Group VIB Metal elements of group VIII.
进一步优选地，在所述加氢精制催化剂I中，所述第VIB族的金属元素为钼和/或钨，所述第VIII族的金属元素为钴和/或镍。Further preferably, in the hydrotreating catalyst I, the metal element of Group VIB is molybdenum and/or tungsten, and the metal element of Group VIII is cobalt and/or nickel.
优选地，在所述加氢精制催化剂I中，以加氢精制催化剂I的总重量为基准，以氧化物计的第VIB族金属元素的含量为35-75重量％，优选为40-65重量％；第VIII族金属元素的含量为15-35重量％，优选为20-30重量％。Preferably, in the hydrorefining catalyst I, based on the total weight of the hydrorefining catalyst I, the content of Group VIB metal elements in terms of oxides is 35-75% by weight, preferably 40-65% by weight %; the content of Group VIII metal elements is 15-35% by weight, preferably 20-30% by weight.
本发明对所述加氢精制催化剂I中的载体种类没有特别的要求，可以采用本领域内常规的各种载体。示例性地，所述加氢精制催化剂I中的载体为氧化铝和大孔分子筛(即氧化铝-大孔分子筛)，其中氧化铝进一步优选为一种水合氧化铝(氢氧化铝)胶体复合物焙烧后得到的氧化铝。The present invention has no special requirements on the type of carrier in the hydrotreating catalyst I, and various conventional carriers in the field can be used. Exemplarily, the carrier in the hydrorefining catalyst I is alumina and macroporous molecular sieve (i.e. alumina-macroporous molecular sieve), wherein alumina is further preferably a hydrated alumina (aluminum hydroxide) colloidal composite Alumina obtained after calcination.
本发明的催化剂，优选在氢气存在下，于170-360℃的温度下用硫、硫化氢或含硫原料进行预硫化，这种预硫化可在器外进行也可在器内原位硫化，将其转化为硫化物型。The catalyst of the present invention is preferably presulfurized with sulfur, hydrogen sulfide or sulfur-containing raw materials at a temperature of 170-360 ° C in the presence of hydrogen. This presulfurization can be carried out outside the device or in situ in the device. Convert it to the sulfide form.
特别优选地，所述第二加氢反应区中的反应温度比所述第一加氢反应区中的反应温度低10-80℃；进一步优选地，所述第二加氢反应区中的反应温度比所述第一加氢反应区中的反应温度低20-80℃。Particularly preferably, the reaction temperature in the second hydrogenation reaction zone is 10-80°C lower than the reaction temperature in the first hydrogenation reaction zone; further preferably, the reaction in the second hydrogenation reaction zone The temperature is 20-80°C lower than the reaction temperature in the first hydrogenation reaction zone.
根据一种优选的具体实施方式，所述第一加氢反应区中的条件包括：反应温度为320-420℃，体积空速为1.0-3.0h-1，氢分压为4.0-10.0MPa，氢油体积比为100-1000:1；所述第二加氢反应区中的条件包括：反应温度为240-360℃，体积空速为2.0-10.0h-1，氢分压为2.0-8.0MPa，氢油体积比100-1000:1。According to a preferred embodiment, the conditions in the first hydrogenation reaction zone include: the reaction temperature is 320-420°C, the volume space velocity is 1.0-3.0h -1 , the hydrogen partial pressure is 4.0-10.0MPa, The volume ratio of hydrogen to oil is 100-1000:1; the conditions in the second hydrogenation reaction zone include: the reaction temperature is 240-360°C, the volume space velocity is 2.0-10.0h -1 , and the hydrogen partial pressure is 2.0-8.0 MPa, the volume ratio of hydrogen to oil is 100-1000:1.
根据另一种更优选的具体实施方式，所述第一加氢反应区中的条件包括：反应温度为340-420℃，体积空速为1.0-2.5h-1，氢分压为6.0-10.0MPa，氢油体积比为300-1000:1；所述第二加氢反应区中的条件包括：反应温度为260-320℃，体积空速为3.0-10.0h-1，氢分压为2.0-8.0MPa，氢油体积比300-1000:1。According to another more preferred embodiment, the conditions in the first hydrogenation reaction zone include: the reaction temperature is 340-420°C, the volume space velocity is 1.0-2.5h -1 , and the hydrogen partial pressure is 6.0-10.0 MPa, the volume ratio of hydrogen to oil is 300-1000:1; the conditions in the second hydrogenation reaction zone include: the reaction temperature is 260-320°C, the volume space velocity is 3.0-10.0h -1 , and the hydrogen partial pressure is 2.0 -8.0MPa, the volume ratio of hydrogen to oil is 300-1000:1.
优选地，在步骤(3)中，控制所述分离的条件，使得所述精制柴油中的硫含量小于10μg/g，双环以上芳烃含量小于7重量％。Preferably, in step (3), the separation conditions are controlled so that the sulfur content in the refined diesel is less than 10 μg/g, and the content of bicyclic and above aromatics is less than 7% by weight.
优选地，在步骤(3)中，控制所述分离的条件，使得所述精制柴油的颜色小于0.5号。Preferably, in step (3), the separation conditions are controlled so that the color of the refined diesel oil is less than No. 0.5.
优选地，在步骤(3)中，控制所述分离的条件，使得所述精制喷气燃料的赛氏比色>+25号。Preferably, in step (3), the separation conditions are controlled such that the Saybolt colorimetric value of the refined jet fuel is >+25.
优选情况下，在所述柴油原料油中，双环以上芳烃含量为10-70重量％；进一步优选双环以上芳烃含量为20-65重量％。Preferably, in the diesel stock oil, the content of double-ring and above aromatics is 10-70% by weight; more preferably, the content of double-ring and above aromatics is 20-65% by weight.
本发明的所述柴油原料油可以为通过常减压蒸馏工艺或者通过其他工艺产生的柴油馏分，或者是不同工艺产生的柴油馏分的混合物。The diesel feedstock oil in the present invention may be a diesel fraction produced by an atmospheric and vacuum distillation process or other processes, or a mixture of diesel fractions produced by different processes.
示例性地，本发明所述柴油原料油可以来自常压蒸馏装置、催化裂化装置、焦化装置。Exemplarily, the diesel feedstock oil in the present invention may come from an atmospheric distillation unit, a catalytic cracking unit, or a coking unit.
优选地，所述常一线原料油中的氮含量为10-40μg/g，更优选氮含量为15-40μg/g。Preferably, the nitrogen content in the normal first-line raw material oil is 10-40 μg/g, more preferably the nitrogen content is 15-40 μg/g.
示例性地，本发明所述常一线原料油可以来自常压蒸馏装置。Exemplarily, the normal-line raw material oil mentioned in the present invention may come from an atmospheric distillation unit.
本发明对进行所述方法的装置没有特别的要求，例如，所述第一加氢反应区中可以设置一个加氢反应器或多个加氢反应器，也可以在一个加氢反应器内设置多个催化剂床层。优选的情况下，当第一加氢反应区设置多个加氢反应器时，各反应器之间设置换热器，以调节单个反应器的入口温度。The present invention has no special requirements on the device for carrying out the method, for example, one hydrogenation reactor or multiple hydrogenation reactors can be set in the first hydrogenation reaction zone, or can be set in one hydrogenation reactor multiple catalyst beds. Preferably, when multiple hydrogenation reactors are arranged in the first hydrogenation reaction zone, a heat exchanger is arranged between each reactor to adjust the inlet temperature of a single reactor.
以下结合图1所示的工艺流程对本发明的方法的一种优选的具体实施方式进行详细描述。A preferred embodiment of the method of the present invention will be described in detail below in conjunction with the process flow shown in FIG. 1 .
本发明提供了一种生产柴油和喷气燃料的方法，该方法包括：The present invention provides a method of producing diesel and jet fuel, the method comprising:
(1)将柴油原料油1与氢气2引入至装填有加氢精制催化剂I的第一加氢反应区3中进行第一加氢反应，得到第一加氢物流；(1) Introduce
(2)将所述第一加氢物流4与常一线原料油5引入至装填有加氢精制催化剂II的第二加氢反应区6中进行第二加氢反应，使得油料在所述第二加氢反应区以上行式的方式流过其中，得到第二加氢物流；(2) The
(3)将所述第二加氢物流7引入至气液分离器8中进行分离，得到富氢气体9和液相物流13，富氢气体9经循环氢压缩单元10压缩增压后作为循环氢11使用，循环氢11中的一部分与新鲜进料的氢气2一起进入第一加氢反应区3中；另一部分作为冷氢12引入至第一加氢反应区3的床层之间；液相物流13进入分馏塔14中进行分馏，得到精制柴油15、精制喷气燃料16和可能少量存在的轻烃产品17。(3) The second hydrogenated stream 7 is introduced into the gas-
与现有技术相比较，本发明的方法具有如下具体的特点：Compared with the prior art, the method of the present invention has the following specific features:
(1)本发明的方法，通过在相邻的两个反应区之间设置进料口补充常一线喷气燃料原料能够实现在高空速下改善产品颜色，脱除硫醇硫；(1) The method of the present invention can realize improving product color at high space velocity by setting feed inlet between adjacent two reaction zones to supplement the normal first-line jet fuel raw material, and remove mercaptan sulfur;
(2)本发明的方法中，由于常一线原料气化率较高，能够在第二加氢反应区将溶解在柴油馏分中的硫化氢进行汽提，降低液相中的硫化氢浓度，进一步提高加氢脱硫反应速率；(2) In the method of the present invention, because the gasification rate of the first-line raw material is higher, the hydrogen sulfide dissolved in the diesel oil fraction can be stripped in the second hydrogenation reaction zone to reduce the concentration of hydrogen sulfide in the liquid phase, further Improve the hydrodesulfurization reaction rate;
(3)本发明的方法中降低了原料加热炉的负荷，减少了循环氢压缩机的负荷，并且与常规加氢精制装置相比，省去一套喷气燃料加氢装置，装置投资得以降低，流程变得简单，更节能。(3) In the method of the present invention, the load of the raw material heating furnace is reduced, the load of the circulating hydrogen compressor is reduced, and compared with the conventional hydrotreating unit, a set of jet fuel hydrogenation unit is saved, and the device investment is reduced, Processes become simpler and more energy efficient.
以下将通过实例对本发明进行详细描述。以下实例中，在没有特别说明的情况下，使用的原料均为普通市售品。The present invention will be described in detail below by way of examples. In the following examples, unless otherwise specified, the raw materials used are common commercially available products.
以下实施例中，催化剂的组成根据投料量计算得到。催化剂的比表面积以及其中的2nm-40nm的孔分布、孔径、孔体积采用低温氮气吸附法测定(符合GB/T5816-1995标准)，100nm-300nm的孔分布、孔径、孔体积采用压汞法测定。催化剂的平均孔径按照圆柱形孔模型进行计算(平均孔径＝总孔体积×4000/比表面积)。In the following examples, the composition of the catalyst is calculated according to the feeding amount. The specific surface area of the catalyst and the pore distribution, pore diameter, and pore volume of 2nm-40nm are measured by low-temperature nitrogen adsorption method (in accordance with GB/T5816-1995 standard), and the pore distribution, pore diameter, and pore volume of 100nm-300nm are measured by mercury porosimetry . The average pore diameter of the catalyst is calculated according to the cylindrical pore model (average pore diameter=total pore volume×4000/specific surface area).
柴油原料油硫含量采用XOS公司X射线荧光仪进行测定，测试方法为：ASTM-7039；The sulfur content of diesel raw material oil is measured by XOS X-ray fluorescence instrument, and the test method is ASTM-7039;
柴油产品硫含量采用耶拿公司生产的EA5000型号仪器进行测定，测试方法为：SH-0689；芳烃的含量采用近红外光谱法分析。The sulfur content of diesel products is measured by EA5000 instrument produced by Jena Company, the test method is: SH-0689; the content of aromatics is analyzed by near-infrared spectroscopy.
实例中所用的加氢精制催化剂I的商业牌号为RS-2100。The commercial designation of the hydrorefining catalyst I used in the example is RS-2100.
实例中商品牌号为RS-1000和RN-410的加氢精制催化剂II，均为中国石化催化剂分公司生产。In the examples, the commercial brands are RS-1000 and RN-410 hydrotreating catalyst II, both of which are produced by Sinopec Catalyst Company.
在实例中提及到的第一加氢反应区的反应温度、第二加氢反应区的反应温度都是对应的各个加氢反应区的加权平均反应温度。单个加氢反应区的加权平均反应温度的计算公式为：The reaction temperature of the first hydrogenation reaction zone and the reaction temperature of the second hydrogenation reaction zone mentioned in the examples are the weighted average reaction temperatures of the respective hydrogenation reaction zones. The formula for calculating the weighted average reaction temperature of a single hydrogenation reaction zone is:
加权平均反应温度＝Σ(反应区测温点权重因子×反应区测温点显示温度)Weighted average reaction temperature = Σ (weight factor of temperature measuring point in reaction zone × display temperature of temperature measuring point in reaction zone)
其中的权重因子定义如下：The weighting factors are defined as follows:
(1)从各个加氢反应区催化剂床层进口到第一层测温点的催化剂重量由第一层测温点代表；(1) The weight of the catalyst imported from the catalyst bed of each hydrogenation reaction zone to the temperature measuring point of the first layer is represented by the temperature measuring point of the first layer;
(2)各个加氢反应区相邻两层测温点之间的催化剂重量，一半由上层的测温点代表，另一半由下层测温点代表；(2) The catalyst weight between two adjacent temperature measuring points in each hydrogenation reaction zone, half is represented by the temperature measuring point of the upper layer, and the other half is represented by the temperature measuring point of the lower layer;
(3)从催化剂床层最低一层测温点到催化剂床层出口的催化剂重量由最低一层测温点代表；(3) The catalyst weight from the temperature measuring point of the lowest layer of the catalyst bed to the outlet of the catalyst bed is represented by the temperature measuring point of the lowest layer;
(4)每层测温点存在多支热电偶时，以该层所有热偶测温值的算平均值作为本层测温点的温度。(4) When there are multiple thermocouples at each temperature measurement point, the average value of the temperature measurement values of all thermocouples in this layer is used as the temperature of the temperature measurement point in this layer.
制备例1Preparation Example 1
制备加氢精制催化剂II，命名为S1。Hydrofining Catalyst II was prepared and named as S1.
(1)将市售白炭黑(比表面积为220m2/g，平均孔径为12.7nm)、碱式碳酸镍粉末混合均匀，然后在500℃下焙烧3h，获得含镍的无机耐火粉末。(1) Commercially available white carbon black (with a specific surface area of 220m 2 /g and an average pore diameter of 12.7nm) and basic nickel carbonate powder were uniformly mixed, and then calcined at 500°C for 3 hours to obtain nickel-containing inorganic refractory powder.
其中，碱式碳酸镍的用量对应催化剂中镍(以氧化镍计)的含量为16.0重量％。Wherein, the amount of basic nickel carbonate used corresponds to the content of nickel (calculated as nickel oxide) in the catalyst being 16.0% by weight.
(2)将MoO3、碱式碳酸镍、丁醇分别加入含磷酸的水溶液中，在加热搅拌下至完全溶解，然后加入酒石酸，至完全溶解，获得含活性金属元素的浸渍溶液。(2) Add MoO 3 , basic nickel carbonate, and butanol into the phosphoric acid-containing aqueous solution, heat and stir until they are completely dissolved, and then add tartaric acid until they are completely dissolved to obtain an impregnating solution containing active metal elements.
其中，丁醇的摩尔数与无机耐火组分的重量比值为0.02，酒石酸重量为无机耐火组分重量的5重量％。Wherein, the weight ratio of the molar number of butanol to the inorganic refractory component is 0.02, and the weight of tartaric acid is 5% by weight of the weight of the inorganic refractory component.
(3)将浸渍溶液与所述无机耐火组分混合均匀，然后将其挤条成型。经过在150℃下干燥8h，制备得到粒径为1.6mm的氧化态催化剂。(3) Mix the impregnating solution and the inorganic refractory components evenly, and then extrude them into strips. After drying at 150° C. for 8 hours, an oxidized catalyst with a particle size of 1.6 mm was prepared.
其中，将浸渍溶液与所述含镍的无机耐火粉末的混合比例使得，以催化剂的干基重量为基准并以氧化物计，催化剂中氧化钼的含量为47.0重量％，氧化镍的含量为25.0重量％，P2O5含量为8.0重量％，无机耐火组分的含量为20.0重量％。Wherein, the mixing ratio of the impregnation solution and the nickel-containing inorganic refractory powder is such that, based on the dry weight of the catalyst and calculated as oxides, the content of molybdenum oxide in the catalyst is 47.0% by weight, and the content of nickel oxide is 25.0% by weight. % by weight, the content of P 2 O 5 is 8.0% by weight, and the content of inorganic refractory components is 20.0% by weight.
催化剂经400℃焙烧2h后，得到第一中间体Z1-S1，Z1-S1的炭含量见表1；将5克EDTA加入150克去离子水中，加入氨水调节溶液pH值至10.5，搅拌得到澄清溶液，采用饱和浸渍法用上述溶液浸渍Z1-S1，浸渍时间为2h，然后，在500℃焙烧3h，得到催化剂S1。以S1的总量为基准，以氧化物计，加氢金属活性组分的含量见表1。After the catalyst was calcined at 400°C for 2 hours, the first intermediate Z1-S1 was obtained. The carbon content of Z1-S1 is shown in Table 1; 5 grams of EDTA was added to 150 grams of deionized water, and ammonia water was added to adjust the pH value of the solution to 10.5, and stirred to obtain clarification solution, impregnating Z1-S1 with the above solution by saturated impregnation method for 2 hours, and then calcining at 500° C. for 3 hours to obtain catalyst S1. Based on the total amount of S1 and in terms of oxides, the content of hydrogenation metal active components is shown in Table 1.
加氢精制催化剂S1的比表面积为155m2/g，孔径分布在2nm-40nm和100nm-300nm，其中，2nm-40nm的孔体积占总孔体积的比例为89.3％(其中，2nm-4nm的孔体积占总孔体积的比例为6.7％)，100-300nm的孔体积占总孔体积的比例为7.4％，孔体积为0.31mL/g，平均孔径为8.0nm。The specific surface area of the hydrofining catalyst S1 is 155m 2 /g, and the pore size distribution is between 2nm-40nm and 100nm-300nm, wherein the pore volume of 2nm-40nm accounts for 89.3% of the total pore volume (among them, the pore volume of 2nm-4nm The ratio of the volume to the total pore volume is 6.7%), the ratio of the 100-300nm pore volume to the total pore volume is 7.4%, the pore volume is 0.31mL/g, and the average pore diameter is 8.0nm.
制备例2Preparation example 2
制备加氢精制催化剂II，命名为S2。Hydrofining Catalyst II was prepared and named as S2.
(1)将市售氢氧化锆粉(比表面积为180m2/g，平均孔径为13.3nm)、碱式碳酸镍粉末混合均匀，然后在400℃下焙烧3h，获得含镍的无机耐火粉末。(1) Commercially available zirconium hydroxide powder (specific surface area: 180m 2 /g, average pore diameter: 13.3nm) and basic nickel carbonate powder were uniformly mixed, then calcined at 400°C for 3 hours to obtain nickel-containing inorganic refractory powder.
其中，碱式碳酸镍的用量对应催化剂中镍(以氧化镍计)的含量为28.0重量％。Wherein, the amount of basic nickel carbonate used corresponds to the content of nickel (calculated as nickel oxide) in the catalyst being 28.0% by weight.
(2)将偏钨酸铵、碱式碳酸镍、丙三醇分别加入含磷酸的水溶液中，在加热搅拌下至完全溶解，然后加入己酸，至完全溶解，获得含活性金属的浸渍溶液。(2) Add ammonium metatungstate, basic nickel carbonate, and glycerol into the aqueous solution containing phosphoric acid, and heat and stir until they are completely dissolved, and then add hexanoic acid until they are completely dissolved to obtain an impregnating solution containing active metals.
其中，丙三醇的摩尔数与无机耐火组分的重量比值为0.01，己酸重量为无机耐火组分重量的2.5重量％。Wherein, the weight ratio of the molar number of glycerol to the inorganic refractory component is 0.01, and the weight of hexanoic acid is 2.5% by weight of the inorganic refractory component.
(3)将浸渍溶液与所述无机耐火组分混合均匀，然后将其挤条成型。经过在180℃下干燥5h，制备得到粒径为1.6mm的氧化态催化剂。(3) Mix the impregnating solution and the inorganic refractory components evenly, and then extrude them into strips. After drying at 180° C. for 5 h, an oxidized catalyst with a particle size of 1.6 mm was prepared.
其中，将浸渍溶液与所述含镍的无机耐火粉末的混合比例使得，以催化剂的干基重量为基准并以氧化物计，催化剂中氧化钨的含量为45.0％，氧化镍的含量为32.0重量％，P2O5含量为3.0重量％，无机耐火组分的含量为20.0重量％。Wherein, the mixing ratio of the impregnation solution and the nickel-containing inorganic refractory powder is such that, based on the dry basis weight of the catalyst and calculated as oxides, the content of tungsten oxide in the catalyst is 45.0%, and the content of nickel oxide is 32.0% by weight %, the content of P 2 O 5 is 3.0% by weight, and the content of inorganic refractory components is 20.0% by weight.
催化剂经400℃焙烧2h后，得到第一中间体Z1-S2，Z1-S2的炭含量见表1；将10克乙二胺放入150克去离子水中，搅拌得到澄清溶液，加入氨水溶液调节pH值至9.5。采用饱和浸渍法用上述溶液浸渍Z1-S2，浸渍时间为2h，然后，在450℃焙烧6h，得到催化剂S2。以S2的总量为基准，以氧化物计，加氢金属活性组分的含量见表1。After the catalyst was calcined at 400°C for 2 hours, the first intermediate Z1-S2 was obtained. The carbon content of Z1-S2 is shown in Table 1; put 10 grams of ethylenediamine into 150 grams of deionized water, stir to obtain a clear solution, and add ammonia solution to adjust pH to 9.5. Z1-S2 was impregnated with the above solution by a saturated impregnation method for 2 hours, and then calcined at 450° C. for 6 hours to obtain catalyst S2. Based on the total amount of S2 and in terms of oxides, the content of hydrogenation metal active components is shown in Table 1.
加氢精制催化剂S2的比表面积为109m2/g，孔径分布在2nm-40nm和100nm-300nm，其中，2nm-40nm的孔体积占总孔体积的比例为85.6％(其中，2nm-4nm的孔体积占总孔体积的比例为6.8％)，100nm-300nm的孔体积占总孔体积的比例为12.3％，孔体积为0.29mL/g，平均孔径为10.6nm。The specific surface area of the hydrofining catalyst S2 is 109m2 /g, and the pore size distribution is between 2nm-40nm and 100nm-300nm, wherein the pore volume of 2nm-40nm accounts for 85.6% of the total pore volume (among them, the pore volume of 2nm-4nm The ratio of the volume to the total pore volume is 6.8%), the ratio of the pore volume of 100nm-300nm to the total pore volume is 12.3%, the pore volume is 0.29mL/g, and the average pore diameter is 10.6nm.
制备例3Preparation example 3
制备加氢精制催化剂II，命名为S3。Hydrofining Catalyst II was prepared and named as S3.
采用与制备例1相同的工艺流程，所不同的是，控制原料的加入量不同。得到催化剂S3。以S3的总量为基准，以氧化物计，加氢金属活性组分的含量见表1。Adopt the same technical process as Preparation Example 1, the difference is that the addition of control raw materials is different. Catalyst S3 is obtained. Based on the total amount of S3 and in terms of oxides, the content of hydrogenation metal active components is shown in Table 1.
加氢精制催化剂S3的比表面积为149m2/g，孔径分布在2nm-40nm和100nm-300nm，其中，2nm-40nm的孔体积占总孔体积的比例为87.6％(其中，2nm-4nm的孔体积占总孔体积的比例为7.2％)，100nm-300nm的孔体积占总孔体积的比例为10.3％，孔体积为0.30mL/g，平均孔径为7.6nm。The specific surface area of the hydrofining catalyst S3 is 149m 2 /g, and the pore size distribution is between 2nm-40nm and 100nm-300nm, wherein the pore volume of 2nm-40nm accounts for 87.6% of the total pore volume (among them, the pore volume of 2nm-4nm The ratio of the volume to the total pore volume is 7.2%), the ratio of the pore volume of 100nm-300nm to the total pore volume is 10.3%, the pore volume is 0.30mL/g, and the average pore diameter is 7.6nm.
实施例1Example 1
采用柴油A为原料油，是以一种中东高硫直馏柴油馏分掺炼20重量％催化柴油得到的混合油。Diesel A is used as raw material oil, which is a mixed oil obtained by blending 20% by weight of catalytic diesel oil with a Middle East high-sulfur straight-run diesel fraction.
柴油A升压后和含氢物流混合后进入加氢反应器，首先通过第一加氢反应区，与加氢精制催化剂I接触，进行加氢精制，然后与常一线A进行混合后进第二加氢反应区，与加氢精制催化剂S1接触，进行深度加氢脱硫、脱芳反应。Diesel A is pressurized and mixed with the hydrogen-containing stream and then enters the hydrogenation reactor. First, it passes through the first hydrogenation reaction zone, contacts with the hydrofinishing catalyst I for hydrofinishing, and then mixes with the normal line A before entering the second hydrogenation reactor. The hydrogen reaction zone is in contact with the hydrorefining catalyst S1 to carry out deep hydrodesulfurization and dearomatization reactions.
柴油A与常一线A的用量重量比为1：0.4。The weight ratio of diesel oil A to regular line A is 1:0.4.
第一加氢反应区的反应器入口氢分压6.4MPa，第一加氢反应区的反应温度为340℃，第一加氢反应区的液时体积空速为1.5h-1。The hydrogen partial pressure at the reactor inlet of the first hydrogenation reaction zone is 6.4MPa, the reaction temperature of the first hydrogenation reaction zone is 340°C, and the liquid hourly volume space velocity of the first hydrogenation reaction zone is 1.5h -1 .
第二加氢反应区的反应温度260℃，第二反应区的反应器入口氢分压3.2MPa，第二加氢反应区的液时体积空速为6h-1。The reaction temperature of the second hydrogenation reaction zone is 260°C, the hydrogen partial pressure at the reactor inlet of the second reaction zone is 3.2MPa, and the liquid hourly volume space velocity of the second hydrogenation reaction zone is 6h -1 .
第一加氢反应区和第二加氢反应区的氢油体积比均为500。The volume ratio of hydrogen to oil in the first hydrogenation reaction zone and the second hydrogenation reaction zone is both 500.
单位时间内总加工油品体积相对于催化剂总装填体积为1.56。The total processed oil volume per unit time relative to the total catalyst loading volume is 1.56.
装置持续运转8400h后，第一加氢反应器反应温度为352℃，第二加氢反应器反应温度264℃，其他工艺条件不变。After 8400 hours of continuous operation of the device, the reaction temperature of the first hydrogenation reactor is 352°C, the reaction temperature of the second hydrogenation reactor is 264°C, and other process conditions remain unchanged.
第二加氢反应器流出物在低压分离器进行气液分离，经过低压分离器分离所得的气相物流经过脱硫后循环回反应器入口，所得的液相物流进入分馏塔进行分馏，塔顶产出轻烃馏分、塔中抽出喷气燃料组分、塔底为超低硫低芳柴油馏分。The effluent from the second hydrogenation reactor is subjected to gas-liquid separation in the low-pressure separator, and the gas phase stream separated by the low-pressure separator is desulfurized and then recycled back to the reactor inlet, and the obtained liquid stream enters the fractionation tower for fractionation, and the top output The light hydrocarbon fraction, the jet fuel component extracted from the tower, and the ultra-low sulfur and low aromatic diesel fraction at the bottom of the tower.
产品主要性质如表4所示。The main properties of the product are shown in Table 4.
对比例1Comparative example 1
以柴油A为原料油，工艺流程为常规单段精制工艺流程，即只有一个加氢反应区，催化剂为RS-2100，其反应器入口氢分压为6.4MPa，反应温度为338℃，总加工油品体积相对于催化剂总装填体积为1.56，氢油体积比500。Diesel oil A is used as the raw material oil, and the process is a conventional single-stage refining process, that is, there is only one hydrogenation reaction zone, the catalyst is RS-2100, the hydrogen partial pressure at the reactor inlet is 6.4MPa, and the reaction temperature is 338°C. The oil volume is 1.56 relative to the total catalyst loading volume, and the hydrogen-oil volume ratio is 500.
运转8400h后，加氢反应器反应温度355℃，其他工艺条件不变。After 8400 hours of operation, the reaction temperature of the hydrogenation reactor was 355°C, and other process conditions remained unchanged.
产品主要性质如表4所示。The main properties of the product are shown in Table 4.
实施例2Example 2
采用柴油B为原料油，是以一种中东高硫直馏柴油馏分掺炼50重量％催化柴油得到的混合油。Diesel B is used as raw material oil, which is a mixed oil obtained by blending 50% by weight of catalytic diesel oil with a middle-east high-sulfur straight-run diesel fraction.
柴油B升压后和含氢物流混合后进入加氢反应器，首先通过第一加氢反应区，与加氢精制催化剂I接触，进行加氢精制，然后与常一线B进行混合后进第二加氢反应区，与加氢精制催化剂S2接触，进行深度加氢脱硫、脱芳反应。Diesel oil B is pressurized and mixed with hydrogen-containing stream and then enters the hydrogenation reactor. First, it passes through the first hydrogenation reaction zone and contacts with the hydrofinishing catalyst I for hydrofinishing. The hydrogen reaction zone is in contact with the hydrorefining catalyst S2 to carry out deep hydrodesulfurization and dearomatization reactions.
柴油B与常一线B的用量重量比为1：0.5。The weight ratio of diesel oil B to regular line B is 1:0.5.
第一加氢反应区的反应器入口氢分压6.4MPa，第一加氢反应区的反应温度为353℃，第一加氢反应区的液时体积空速为1.2h-1。The hydrogen partial pressure at the reactor inlet of the first hydrogenation reaction zone is 6.4MPa, the reaction temperature of the first hydrogenation reaction zone is 353°C, and the liquid hourly volume space velocity of the first hydrogenation reaction zone is 1.2h -1 .
第二加氢反应区的反应温度280℃，第二反应区的反应器入口氢分压4.8MPa，第二加氢反应区的液时体积空速为4h-1。The reaction temperature of the second hydrogenation reaction zone is 280°C, the hydrogen partial pressure at the reactor inlet of the second reaction zone is 4.8MPa, and the liquid hourly volume space velocity of the second hydrogenation reaction zone is 4h -1 .
第一加氢反应区和第二加氢反应区的氢油体积比均为800。The volume ratio of hydrogen to oil in the first hydrogenation reaction zone and the second hydrogenation reaction zone is both 800.
单位时间内总加工油品体积相对于催化剂总装填体积为1.38。The total processed oil volume per unit time relative to the total catalyst loading volume is 1.38.
装置持续运转8400h后，第一加氢反应器反应温度为366℃，第二加氢反应器反应温度282℃，其他工艺条件不变。After 8400 hours of continuous operation of the device, the reaction temperature of the first hydrogenation reactor is 366°C, the reaction temperature of the second hydrogenation reactor is 282°C, and other process conditions remain unchanged.
气液分离和液相物流分馏流程与实施例1相同。The process of gas-liquid separation and fractionation of liquid stream is the same as that of Example 1.
产品主要性质如表5所示。The main properties of the product are shown in Table 5.
实施例3Example 3
采用柴油C为原料油，其为催化柴油。Adopt diesel oil C as raw material oil, which is catalytic diesel oil.
柴油C升压后和含氢物流混合后进入加氢反应器，首先通过第一加氢反应区，与加氢精制催化剂I接触，进行加氢精制，然后与常一线A进行混合后进第二加氢反应区，与加氢精制催化剂S3接触，进行深度加氢脱硫、脱芳反应。After the diesel oil C is boosted and mixed with the hydrogen-containing stream, it enters the hydrogenation reactor. First, it passes through the first hydrogenation reaction zone, contacts with the hydrofinishing catalyst I, performs hydrofinishing, and then mixes with the normal line A before entering the second hydrogenation reactor. The hydrogen reaction zone is in contact with the hydrorefining catalyst S3 to carry out deep hydrodesulfurization and dearomatization reactions.
柴油C与常一线A的用量重量比为1：0.6。The weight ratio of diesel oil C to regular line A is 1:0.6.
第一加氢反应区的反应器入口氢分压6.4MPa，第一加氢反应区的反应温度为360℃，第一加氢反应区的液时体积空速为1.0h-1。The hydrogen partial pressure at the reactor inlet of the first hydrogenation reaction zone is 6.4MPa, the reaction temperature of the first hydrogenation reaction zone is 360°C, and the liquid hourly volume space velocity of the first hydrogenation reaction zone is 1.0h -1 .
第二加氢反应区的反应温度300℃，第二反应区的反应器入口氢分压6.4MPa，第二加氢反应区的液时体积空速为3h-1。The reaction temperature in the second hydrogenation reaction zone is 300°C, the hydrogen partial pressure at the reactor inlet of the second reaction zone is 6.4MPa, and the liquid hourly volume space velocity in the second hydrogenation reaction zone is 3h -1 .
第一加氢反应区和第二加氢反应区的氢油体积比均为1000。The volume ratio of hydrogen to oil in the first hydrogenation reaction zone and the second hydrogenation reaction zone is both 1000.
单位时间内总加工油品体积相对于催化剂总装填体积为0.95。The total processed oil volume per unit time relative to the total catalyst loading volume is 0.95.
装置持续运转8400h后，第一加氢反应器反应温度为375℃，第二加氢反应器反应温度310℃，其他工艺条件不变。After 8400 hours of continuous operation of the device, the reaction temperature of the first hydrogenation reactor is 375°C, the reaction temperature of the second hydrogenation reactor is 310°C, and other process conditions remain unchanged.
气液分离和液相物流分馏流程与实施例1相同。The process of gas-liquid separation and fractionation of liquid stream is the same as that of Example 1.
产品主要性质如表6所示。The main properties of the product are shown in Table 6.
实施例4Example 4
采用柴油A为原料油，是以一种中东高硫直馏柴油馏分掺炼20重量％催化柴油得到的混合油。Diesel A is used as raw material oil, which is a mixed oil obtained by blending 20% by weight of catalytic diesel oil with a Middle East high-sulfur straight-run diesel fraction.
柴油A升压后和含氢物流混合后进入加氢反应器，首先通过第一加氢反应区，与加氢精制催化剂I接触，进行加氢精制，然后与常一线A进行混合后进第二加氢反应区，与加氢精制催化剂RN-410接触，进行深度加氢脱硫、脱芳反应。Diesel A is pressurized and mixed with the hydrogen-containing stream and then enters the hydrogenation reactor. First, it passes through the first hydrogenation reaction zone, contacts with the hydrofinishing catalyst I for hydrofinishing, and then mixes with the normal line A before entering the second hydrogenation reactor. The hydrogen reaction zone is in contact with the hydrorefining catalyst RN-410 to carry out deep hydrodesulfurization and dearomatization reactions.
柴油A与常一线A的用量重量比为1：0.3。The weight ratio of diesel oil A to regular line A is 1:0.3.
第一加氢反应区的反应器入口氢分压6.4MPa，第一加氢反应区的反应温度为340℃，第一加氢反应区的液时体积空速为1.5h-1。The hydrogen partial pressure at the reactor inlet of the first hydrogenation reaction zone is 6.4MPa, the reaction temperature of the first hydrogenation reaction zone is 340°C, and the liquid hourly volume space velocity of the first hydrogenation reaction zone is 1.5h -1 .
第二加氢反应区的反应温度270℃，第二反应区的反应器入口氢分压3.2MPa，第二加氢反应区的液时体积空速为6h-1。The reaction temperature of the second hydrogenation reaction zone is 270°C, the hydrogen partial pressure at the reactor inlet of the second reaction zone is 3.2MPa, and the liquid hourly volume space velocity of the second hydrogenation reaction zone is 6h -1 .
第一加氢反应区和第二加氢反应区的氢油体积比均为500。The volume ratio of hydrogen to oil in the first hydrogenation reaction zone and the second hydrogenation reaction zone is both 500.
单位时间内总加工油品体积相对于催化剂总装填体积为1.56。The total processed oil volume per unit time relative to the total catalyst loading volume is 1.56.
装置持续运转8400h后，第一加氢反应器反应温度为352℃，第二加氢反应器反应温度270℃，其他工艺条件不变。After 8400 hours of continuous operation of the device, the reaction temperature of the first hydrogenation reactor is 352°C, the reaction temperature of the second hydrogenation reactor is 270°C, and other process conditions remain unchanged.
气液分离和液相物流分馏流程与实施例1相同。The process of gas-liquid separation and fractionation of liquid stream is the same as that of Example 1.
产品主要性质如表4所示。The main properties of the product are shown in Table 4.
实施例5Example 5
采用柴油B为原料油，是以一种中东高硫直馏柴油馏分掺炼50重量％催化柴油得到的混合油。Diesel B is used as raw material oil, which is a mixed oil obtained by blending 50% by weight of catalytic diesel oil with a middle-east high-sulfur straight-run diesel fraction.
柴油B升压后和含氢物流混合后进入加氢反应器，首先通过第一加氢反应区，与加氢精制催化剂I接触，进行加氢精制，然后与常一线B进行混合后进第二加氢反应区，与加氢精制催化剂RS-1000接触，进行深度加氢脱硫、脱芳反应。Diesel oil B is pressurized and mixed with hydrogen-containing stream and then enters the hydrogenation reactor. First, it passes through the first hydrogenation reaction zone and contacts with the hydrofinishing catalyst I for hydrofinishing. The hydrogen reaction zone is in contact with the hydrorefining catalyst RS-1000 to carry out deep hydrodesulfurization and dearomatization reactions.
柴油B与常一线B的用量重量比为1：0.4。The weight ratio of diesel oil B to regular line B is 1:0.4.
第一加氢反应区的反应器入口氢分压6.4MPa，第一加氢反应区的反应温度为353℃，第一加氢反应区的液时体积空速为1.2h-1。The hydrogen partial pressure at the reactor inlet of the first hydrogenation reaction zone is 6.4MPa, the reaction temperature of the first hydrogenation reaction zone is 353°C, and the liquid hourly volume space velocity of the first hydrogenation reaction zone is 1.2h -1 .
第二加氢反应区的反应温度280℃，第二反应区的反应器入口氢分压4.8MPa，第二加氢反应区的液时体积空速为4h-1。The reaction temperature of the second hydrogenation reaction zone is 280°C, the hydrogen partial pressure at the reactor inlet of the second reaction zone is 4.8MPa, and the liquid hourly volume space velocity of the second hydrogenation reaction zone is 4h -1 .
第一加氢反应区和第二加氢反应区的氢油体积比均为800。The volume ratio of hydrogen to oil in the first hydrogenation reaction zone and the second hydrogenation reaction zone is both 800.
单位时间内总加工油品体积相对于催化剂总装填体积为1.38。The total processed oil volume per unit time relative to the total catalyst loading volume is 1.38.
装置持续运转8400h后，第一加氢反应器反应温度为366℃，第二加氢反应器反应温度290℃，其他工艺条件不变。After 8400 hours of continuous operation of the device, the reaction temperature of the first hydrogenation reactor is 366°C, the reaction temperature of the second hydrogenation reactor is 290°C, and other process conditions remain unchanged.
气液分离和液相物流分馏流程与实施例1相同。The process of gas-liquid separation and fractionation of liquid stream is the same as that of Example 1.
产品主要性质如表5所示。The main properties of the product are shown in Table 5.
表1：加氢精制催化剂S1和S2的性质Table 1: Properties of Hydrofining Catalysts S1 and S2
表2：加氢精制催化剂RN-410和RS-1000的性质Table 2: Properties of Hydrofining Catalysts RN-410 and RS-1000
表3：原料油性质Table 3: Raw Oil Properties
表4：实施例1、实施例4、对比例1的产品性质Table 4: the product property of
表5：实施例2及实施例5的产品性质Table 5: Product properties of
表6：实施例3的产品性质Table 6: Product properties of Example 3
由上述结果可知，对于掺炼20重量％至50重量％的混合柴油、100重量％催化柴油的柴油原料油，以及两种高硫或高氮的常一线原料油，采用本发明的方法都能够在较为缓和的反应条件下生产硫含量很低的超低硫柴油产品和合格的喷气燃料产品。From the above results, it can be seen that for blending 20% by weight to 50% by weight of mixed diesel oil, diesel feedstock oil of 100% by weight catalytic diesel oil, and two kinds of high-sulfur or high-nitrogen constant first-line feedstock oils, the method of the present invention can be used Under relatively mild reaction conditions, ultra-low sulfur diesel products with very low sulfur content and qualified jet fuel products are produced.
由上述结果可知，本发明提供的方法具有装置和产品质量稳定性更优的效果。From the above results, it can be seen that the method provided by the present invention has the effect of better device and product quality stability.
并且，对比上述结果还能够看出，当产品硫含量相同时，采用本发明的方法，反应温度能够更低。即使加工纯的催化裂化柴油，采用本发明的方法也能够得到低硫、低芳烃的精制柴油产品和合格的喷气燃料产品。Moreover, comparing the above results, it can also be seen that when the sulfur content of the product is the same, the reaction temperature can be lower by adopting the method of the present invention. Even if pure catalytic cracking diesel oil is processed, low-sulfur, low-aromatic refined diesel products and qualified jet fuel products can also be obtained by adopting the method of the invention.
另外，采用本发明的方法，催化剂的稳定性更好，在相同的运转时间后，本发明的柴油产品硫含量远低于相应对比例中的产品硫含量，喷气燃料产品的赛氏比色优于相应对比例中的产品赛氏比色。In addition, by adopting the method of the present invention, the stability of the catalyst is better. After the same running time, the sulfur content of the diesel product of the present invention is far lower than that of the product in the corresponding comparative example, and the Saybolt color ratio of the jet fuel product is excellent. The product Saybolt colorimetry in the corresponding comparative example.
采用本发明所提供的方法能够在更缓和的反应条件下生产超低硫、低芳烃含量的柴油和合格的喷气燃料，并且催化剂的稳定性更好。The method provided by the invention can produce diesel with ultra-low sulfur and low aromatics content and qualified jet fuel under milder reaction conditions, and the stability of the catalyst is better.
以上详细描述了本发明的优选实施方式，但是，本发明并不限于此。在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，包括各个技术特征以任何其它的合适方式进行组合，这些简单变型和组合同样应当视为本发明所公开的内容，均属于本发明的保护范围。The preferred embodiments of the present invention have been described in detail above, however, the present invention is not limited thereto. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solution of the present invention, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the content disclosed in the present invention. All belong to the protection scope of the present invention.
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