WO2024093339A1 - Catalyst for slurry reactor residual oil hydrogenation, and application method therefor - Google Patents

Catalyst for slurry reactor residual oil hydrogenation, and application method therefor Download PDF

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WO2024093339A1
WO2024093339A1 PCT/CN2023/106015 CN2023106015W WO2024093339A1 WO 2024093339 A1 WO2024093339 A1 WO 2024093339A1 CN 2023106015 W CN2023106015 W CN 2023106015W WO 2024093339 A1 WO2024093339 A1 WO 2024093339A1
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catalyst
molybdenum
reactor
oil
reaction
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PCT/CN2023/106015
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French (fr)
Chinese (zh)
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施宗波
张青
黄晴雯
李邵洪
彭飞
卓润生
刘新生
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润和科华催化剂(上海)有限公司
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Publication of WO2024093339A1 publication Critical patent/WO2024093339A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/28—Molybdenum
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used

Definitions

  • the invention relates to the technical field of oil residue hydrogenation, and in particular to a catalyst for slurry bed oil residue hydrogenation and an application method thereof.
  • slurry bed residue oil hydrogenation technology is an important process for treating low-quality heavy oil raw materials with high metal content, high residual carbon content and high sulfur content.
  • the catalysts for slurry bed residue oil hydrogenation are mainly divided into solid particle catalysts and nano catalysts.
  • solid particle catalysts have low preparation costs and the catalysts can be partially recycled, but when used for high-density heavy oil, they are prone to excessive carbon deposition and pipeline clogging.
  • Nano catalysts have excellent dispersibility, high metal atom utilization, and less pipeline clogging.
  • the preparation process of this type of catalyst is complicated and the preparation cost is too high.
  • the object of the present invention is to provide a catalyst for slurry bed residue oil hydrogenation, which can not only avoid pipeline blockage when used, but also has low cost.
  • Another object of the present invention is to provide an application method of a catalyst for slurry bed residue oil hydrogenation, which can effectively improve the residue oil conversion rate and improve the slurry bed foaming distribution.
  • the present invention solves the technical problem by adopting the following technical solutions.
  • the present invention provides a catalyst for slurry bed residue oil hydrogenation, which is an aluminum-molybdenum alloy ball.
  • an oil-soluble molybdenum catalyst is also included, and the mass ratio of the oil-soluble molybdenum catalyst to the aluminum-molybdenum alloy ball is 100-10000:1.
  • the oil-soluble molybdenum catalyst includes any one of molybdenum isooctanoate, molybdenum cyclohexaneate, molybdenum hexacarbonyl, and molybdenum acetylacetonate.
  • the diameter of the aluminum-molybdenum alloy ball is 0.5-5 cm.
  • the molybdenum content in the aluminum-molybdenum alloy ball is 10-50%.
  • the present invention also provides an application method of the catalyst as described above, comprising the following steps: adding residual oil and the catalyst as described above into a reactor containing hydrogen, then stirring to mix the raw materials evenly, performing a catalytic hydrogenation reaction, and obtaining a light component oil after the reaction is completed.
  • the mass ratio of the above-mentioned residual oil to the above-mentioned catalyst is: 1000:0.05-5.
  • the reaction temperature in the reactor is 360-520° C.
  • the reaction pressure in the reactor is 10-25 MPa.
  • the reaction time in the above reactor is 2-4 hours.
  • the above-mentioned residue oil is any one of vacuum residue oil, catalytic cracking residue oil and hydroprocessing residue oil.
  • Such a catalyst has low cost, and it passes through the high temperature environment of the slurry bed reaction process, and under the collision between metals, the Mo element enters the reaction system in the form of atoms or nanoparticles with the assistance of elements such as N and Cl in the feed, which can avoid pipeline blockage, and then participate in the residue oil hydrogenation reaction, improve the residue oil conversion rate, improve the slurry bed boiling bed gas distribution, and make the bubble distribution smaller and more uniform.
  • the embodiment of the present invention also provides an application method of the catalyst for slurry bed residue oil hydrogenation, which has at least the following beneficial effects:
  • This method is used to achieve residual oil hydrogenation, which has a simple process and low cost, and the use of these catalysts can avoid pipeline blockage.
  • the present invention provides a catalyst for slurry bed residue oil hydrogenation, which is an aluminum-molybdenum alloy ball.
  • Such a catalyst has low cost, and it passes through the high temperature environment of the slurry bed reaction process, and under the collision between metals, the Mo element enters the reaction system in the form of atoms or nanoparticles with the assistance of elements such as N and Cl in the feed, which can avoid pipeline blockage, and then participate in the residue oil hydrogenation reaction, improve the residue oil conversion rate, improve the slurry bed boiling bed gas distribution, and make the bubble distribution smaller and more uniform.
  • an oil-soluble molybdenum catalyst is also included, and the mass ratio of the oil-soluble molybdenum catalyst to the aluminum-molybdenum alloy ball is 100-10000:1.
  • oil-soluble molybdenum catalyst can further increase the content of Mo element.
  • Mo element can better enter the reaction system in the form of atoms or nanoparticles with the assistance of elements such as N and Cl in the feed to produce catalytic effect.
  • the oil-soluble molybdenum catalyst includes any one of molybdenum isooctanoate, molybdenum cyclohexaneate, molybdenum hexacarbonyl, and molybdenum acetylacetonate.
  • the diameter of the aluminum-molybdenum alloy ball is 0.5-5 cm.
  • the use of aluminum-molybdenum alloy balls with such a diameter can improve the slurry state of the slurry bed and make the slurry more uniform.
  • the molybdenum content in the aluminum-molybdenum alloy ball is 10-50%.
  • the present invention also provides an application method of the catalyst as described above, comprising the following steps: adding residual oil and the catalyst as described above into a reactor containing hydrogen, then stirring to mix the raw materials evenly, performing a catalytic hydrogenation reaction, and obtaining a light component oil after the reaction is completed.
  • This method is used to achieve residual oil hydrogenation, which has a simple process and low cost, and the use of these catalysts can avoid pipeline blockage.
  • the mass ratio of the above-mentioned residual oil to the above-mentioned catalyst is: 1000:0.05-5.
  • Such a raw material ratio can make the catalytic effect of the catalyst on the reaction reach the best, and better achieve the effect of residue oil hydrogenation.
  • the reaction temperature in the reactor is 360-520°C.
  • reaction temperature will not cause loss of raw materials due to excessively high temperature, nor will the reaction rate be slow due to too low temperature, and the reaction can be efficient and sufficient.
  • the reaction pressure is 10-25 MPa.
  • the reaction time in the reactor is 2-4 hours, which allows the raw materials to react fully.
  • the above-mentioned residual oil is any one of vacuum residual oil, catalytic cracking residual oil and hydroprocessing residual oil, including but not limited to the above-mentioned residual oils, which can be subjected to hydrogenation reaction using this catalyst.
  • the high-pressure reactors used in any of the following examples and any of the comparative examples are all high-pressure reactors for simulating slurry bed residue oil hydrogenation, in which oxygen is replaced by hydrogen and contains other materials in the residue oil hydrogenation reaction process such as sublimated sulfur powder.
  • the residue oil used in any of the following examples and any of the comparative examples is Venezuelan vacuum residue oil, and its properties are shown in the following Table 1:
  • the aluminum-molybdenum alloy ball has a diameter of 0.95 cm and a molybdenum content of 40%.
  • molybdenum isooctanoate It includes molybdenum isooctanoate and aluminum-molybdenum alloy balls.
  • the mass of the molybdenum isooctanoate is 0.4g
  • the mass ratio of the aluminum-molybdenum alloy balls is 250g
  • the diameter of the aluminum-molybdenum alloy balls is 1cm
  • the molybdenum content in the aluminum-molybdenum alloy balls is 30%.
  • molybdenum isooctanoate It includes molybdenum isooctanoate and aluminum-molybdenum alloy balls.
  • the mass of the molybdenum isooctanoate is 0.6 g
  • the mass of the aluminum-molybdenum alloy balls is 380 g.
  • the diameter of the aluminum-molybdenum alloy balls is 0.92 cm
  • the molybdenum content of the aluminum-molybdenum alloy balls is 45%.
  • molybdenum isooctanoate It includes molybdenum isooctanoate and aluminum-molybdenum alloy balls.
  • the mass of the molybdenum isooctanoate is 0.8 g
  • the mass of the aluminum-molybdenum alloy balls is 600 g
  • the diameter of the aluminum-molybdenum alloy balls is 1.08 cm
  • the molybdenum content of the aluminum-molybdenum alloy balls is 15%.
  • molybdenum isooctanoate It includes molybdenum isooctanoate and aluminum-molybdenum alloy balls.
  • the mass of the molybdenum isooctanoate is 1g
  • the mass of the aluminum-molybdenum alloy balls is 720g.
  • the diameter of the aluminum-molybdenum alloy balls is 1.12cm
  • the molybdenum content in the aluminum-molybdenum alloy balls is 10%.
  • molybdenum isooctanoate It includes molybdenum isooctanoate and aluminum-molybdenum alloy balls.
  • the mass of the molybdenum cyclohexaneate is 0.9 g
  • the mass of the aluminum-molybdenum alloy balls is 650 g.
  • the diameter of the aluminum-molybdenum alloy balls is 1 cm
  • the molybdenum content in the aluminum-molybdenum alloy balls is 13%.
  • molybdenum isooctanoate It includes molybdenum isooctanoate and aluminum-molybdenum alloy balls.
  • the mass of the molybdenum hexacarbonyl is 0.7 g, and the mass of the aluminum-molybdenum alloy balls is 700 g.
  • the diameter of the aluminum-molybdenum alloy balls is 1.5 cm, and the molybdenum content in the aluminum-molybdenum alloy balls is 12%.
  • molybdenum isooctanoate It includes molybdenum isooctanoate and aluminum-molybdenum alloy balls.
  • the mass of the molybdenum acetylacetonate is 1g
  • the mass of the aluminum-molybdenum alloy balls is 710g.
  • the diameter of the aluminum-molybdenum alloy balls is 2.5cm
  • the molybdenum content in the aluminum-molybdenum alloy balls is 11%.
  • molybdenum isooctanoate It includes molybdenum isooctanoate and aluminum-molybdenum alloy balls.
  • the mass of the molybdenum isooctanoate is 0.5 g
  • the mass of the aluminum-molybdenum alloy balls is 680 g.
  • the diameter of the aluminum-molybdenum alloy balls is 3.5 cm
  • the molybdenum content in the aluminum-molybdenum alloy balls is 12%.
  • molybdenum isooctanoate It includes molybdenum isooctanoate and aluminum-molybdenum alloy balls.
  • the mass of the molybdenum isooctanoate is 0.6 g, and the mass of the aluminum-molybdenum alloy balls is 690 g.
  • the diameter of the aluminum-molybdenum alloy balls is 5 cm, and the molybdenum content in the aluminum-molybdenum alloy balls is 12%.
  • the method comprises the following steps: adding 200 g of residual oil and 5.2 g of the catalyst of Example 1 into a 1 L high pressure reactor, and stirring to make the raw materials uniformly mixed;
  • the reaction temperature in the reactor was 360° C.
  • the reaction pressure in the reactor was 25 MPa
  • the reaction time was 3 h.
  • the reactor was cooled to room temperature to obtain hydrogenated residue oil.
  • the method comprises the following steps: adding 200 g of residual oil and 5.2 g of the catalyst of Example 2 into a 1 L high pressure reactor, and stirring to make the raw materials uniformly mixed;
  • the reaction temperature in the reactor was 520° C.
  • the reaction pressure in the reactor was 10 MPa
  • the reaction time was 4 hours.
  • the reactor was cooled to room temperature to obtain hydrogenated residue oil.
  • the method comprises the following steps: adding 200 g of residual oil and 4.9 g of the catalyst of Example 3 into a 1 L high pressure reactor, and stirring to make the raw materials uniformly mixed;
  • the reaction temperature in the reactor is 480° C.
  • the reaction pressure in the reactor is 20 MPa
  • the reaction time is 2 h.
  • the reactor is cooled to room temperature to obtain hydrogenated residue oil.
  • the method comprises the following steps: adding 200 g of residual oil and 5 g of the catalyst of Example 4 into a 1 L high pressure reactor, and stirring to make the raw materials uniformly mixed;
  • the reaction temperature in the reactor is 500° C.
  • the reaction pressure in the reactor is 15 MPa
  • the reaction time is 4 hours.
  • the reactor is cooled to room temperature to obtain hydrogenated residue oil.
  • the method comprises the following steps: adding 200 g of residual oil and 5 g of the catalyst of Example 5 into a 1 L high pressure reactor, and stirring to make the raw materials uniformly mixed;
  • the reaction temperature in the reactor is 400° C.
  • the reaction pressure in the reactor is 20 MPa
  • the reaction time is 2 h.
  • the reactor is cooled to room temperature to obtain hydrogenated residue oil.
  • the method comprises the following steps: adding 200 g of residual oil into a 1 L high pressure reactor, and stirring to make all raw materials uniformly mixed;
  • the reaction temperature in the reactor was 430° C.
  • the reaction pressure in the reactor was 20 MPa
  • the reaction time was 3 h.
  • the reactor was cooled to room temperature to obtain hydrogenated residue oil.
  • the method comprises the following steps: adding 200 g of residual oil and 400 ppm of molybdenum isooctanoate into a 1 L high pressure reactor, and stirring to make the raw materials uniformly mixed;
  • the reaction temperature in the reactor was 430° C.
  • the reaction pressure in the reactor was 20 MPa
  • the reaction time was 3 h.
  • the reactor was cooled to room temperature to obtain hydrogenated residue oil.
  • the catalysts in Examples 2-5 were added to Examples 12, 13, 14, and 15, respectively, and the residual oil conversion rate was increased, the total light component content of C1-520°C was significantly increased, the components >520°C were reduced, and the coke content was further reduced, proving that the additive in the present invention can achieve more significant effects by using aluminum-molybdenum alloy balls and molybdenum isooctanoate.
  • the use of the catalyst provided by the present invention in the hydrogenation of residual oil can obtain more light component oil and less heavy component (>520°C), which can bring more profits to the slurry bed residual oil hydrogenation.
  • the cost is low, the residual oil conversion rate and light oil yield can be improved, the coke yield can be reduced, and more economic benefits can be generated for the slurry bed residual oil hydrogenation.
  • molybdenum alloy steel beads can improve the gas distribution in the fluidized bed and make the bubble distribution smaller and more uniform.
  • such a catalyst has low cost, and through the high temperature environment of the slurry bed reaction process, and under the collision between metals, the Mo element enters the reaction system in the form of atoms or nanoparticles with the assistance of elements such as N and Cl in the feed, which can avoid pipeline blockage, and then participate in the residue oil hydrogenation reaction, improve the residue oil conversion rate, improve the slurry bed boiling bed gas distribution, and make the bubble distribution smaller and more uniform.
  • the embodiment of the present invention also provides an application method of the catalyst for slurry bed residue oil hydrogenation, which has at least the following beneficial effects:
  • This method is used to achieve residual oil hydrogenation, which has a simple process and low cost, and the use of these catalysts can avoid pipeline blockage.

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Abstract

Provided are a catalyst for slurry reactor residual oil hydrogenation, and an application method therefor. The present invention relates to the technical field of residual oil hydrogenation. The catalyst for slurry reactor residual oil hydrogenation is aluminum-molybdenum alloy pellets. When the catalyst is used, not only can the pipeline be prevented from being blocked, but the cost is also low. The application method for the catalyst for slurry reactor residual oil hydrogenation comprises: adding residual oil and the catalyst to a high-pressure reactor, then stirring same to uniformly mix the raw materials, next replacing air in the reactor with hydrogen for reaction, and after the reaction is finished, cooling the reactor to room temperature to obtain hydrogenated residual oil. The catalyst can effectively improve the conversion rate of the residual oil, and improve the bubble distribution of the slurry reactor.

Description

一种用于浆态床渣油加氢的催化剂及其应用方法A catalyst for slurry bed residue oil hydrogenation and its application method 技术领域Technical Field
本发明涉及油渣加氢的技术领域，具体而言，涉及一种用于浆态床渣油加氢的催化剂及其应用方法。The invention relates to the technical field of oil residue hydrogenation, and in particular to a catalyst for slurry bed oil residue hydrogenation and an application method thereof.
背景技术Background technique
随着原油的重质化和劣质化，浆态床渣油加氢技术是处理高金属、高残炭、高硫的劣质重油原料的重要过程。With the heavier and inferior quality of crude oil, slurry bed residue oil hydrogenation technology is an important process for treating low-quality heavy oil raw materials with high metal content, high residual carbon content and high sulfur content.
国外诸家公司均开展了重油浆态床加氢裂化技术的研究，主要有意大利ENI公司的EST工艺、委内瑞拉Intevep与法国Axens合作开发的HDHPLUS-SHP工艺、Chevron公司的VRSH工艺、KBR和BP公司合作开发的VCC工艺、UOP公司的Uniflex工艺和Headwater公司的(HCAT/HC3)工艺等。Many foreign companies have carried out research on heavy oil slurry bed hydrocracking technology, mainly including the EST process of Italy's ENI, the HDHPLUS-SHP process jointly developed by Venezuela's Intevep and France's Axens, Chevron's VRSH process, the VCC process jointly developed by KBR and BP, UOP's Uniflex process and Headwater's (HCAT/HC3) process.
浆态床渣油加氢的催化剂主要分为固体颗粒催化剂和纳米催化剂，其中固体颗粒催化剂制备成本低，催化剂可部分回用，但是用于高密度重质油时，容易发生过渡积碳和堵塞管道现象。纳米催化剂具有优异的分散性，获悉金属原子利用率高，堵塞管道现象较少，但是，该类型催化剂制备工艺复杂，制备成本太高。The catalysts for slurry bed residue oil hydrogenation are mainly divided into solid particle catalysts and nano catalysts. Among them, solid particle catalysts have low preparation costs and the catalysts can be partially recycled, but when used for high-density heavy oil, they are prone to excessive carbon deposition and pipeline clogging. Nano catalysts have excellent dispersibility, high metal atom utilization, and less pipeline clogging. However, the preparation process of this type of catalyst is complicated and the preparation cost is too high.
发明内容Summary of the invention
本发明的目的在于提供一种用于浆态床渣油加氢的催化剂，其在使用的时候不仅可以避免管道堵塞，而且成本低。The object of the present invention is to provide a catalyst for slurry bed residue oil hydrogenation, which can not only avoid pipeline blockage when used, but also has low cost.
本发明的另一目的在于提供一种用于浆态床渣油加氢的催化剂的应用方法，其可以有效提高渣油转化率，改善浆态床起泡分布。Another object of the present invention is to provide an application method of a catalyst for slurry bed residue oil hydrogenation, which can effectively improve the residue oil conversion rate and improve the slurry bed foaming distribution.
本发明解决其技术问题是采用以下技术方案来实现的。The present invention solves the technical problem by adopting the following technical solutions.
本发明提出一种用于浆态床渣油加氢的催化剂，其为铝钼合金球。The present invention provides a catalyst for slurry bed residue oil hydrogenation, which is an aluminum-molybdenum alloy ball.
进一步的，在本发明的一些实施例中，还包括油溶性钼催化剂，上述油溶性钼催化剂与铝钼合金球的质量比例为100-10000：1。Furthermore, in some embodiments of the present invention, an oil-soluble molybdenum catalyst is also included, and the mass ratio of the oil-soluble molybdenum catalyst to the aluminum-molybdenum alloy ball is 100-10000:1.
进一步的，在本发明的一些实施例中，上述油溶性钼催化剂包括异辛酸钼、环烷酸钼、六羰基钼、乙酰丙酮钼中的任意一种。Furthermore, in some embodiments of the present invention, the oil-soluble molybdenum catalyst includes any one of molybdenum isooctanoate, molybdenum cyclohexaneate, molybdenum hexacarbonyl, and molybdenum acetylacetonate.
进一步的，在本发明的一些实施例中，上述铝钼合金球的直径为0.5-5cm。Furthermore, in some embodiments of the present invention, the diameter of the aluminum-molybdenum alloy ball is 0.5-5 cm.
进一步的，在本发明的一些实施例中，上述铝钼合金球中的钼含量为10-50％。Furthermore, in some embodiments of the present invention, the molybdenum content in the aluminum-molybdenum alloy ball is 10-50%.
本发明还提供了一种如上所述的催化剂的应用方法，包括如下步骤：将渣油、如上所述的催化剂加入含有氢气的反应器中，然后搅拌使各原料混合均匀，进行催化加氢反应，反应结束后，得到轻组分油。 The present invention also provides an application method of the catalyst as described above, comprising the following steps: adding residual oil and the catalyst as described above into a reactor containing hydrogen, then stirring to mix the raw materials evenly, performing a catalytic hydrogenation reaction, and obtaining a light component oil after the reaction is completed.
进一步的，在本发明的一些实施例中，上述渣油与上述催化剂的质量比值为：1000：0.05-5。Furthermore, in some embodiments of the present invention, the mass ratio of the above-mentioned residual oil to the above-mentioned catalyst is: 1000:0.05-5.
进一步的，在本发明的一些实施例中，上述反应器内的反应温度为360～520℃，上述反应器内的反应压力为10-25MPa。Furthermore, in some embodiments of the present invention, the reaction temperature in the reactor is 360-520° C., and the reaction pressure in the reactor is 10-25 MPa.
进一步的，在本发明的一些实施例中，上述反应器内的反应时间为2-4h。Furthermore, in some embodiments of the present invention, the reaction time in the above reactor is 2-4 hours.
进一步的，在本发明的一些实施例中，上述渣油为：减压渣油、催化裂化渣油及加氢处理渣油中的任意一种。Furthermore, in some embodiments of the present invention, the above-mentioned residue oil is any one of vacuum residue oil, catalytic cracking residue oil and hydroprocessing residue oil.
本发明实施例提供的用于浆态床渣油加氢的催化剂，至少具有以下有益效果：The catalyst for slurry bed residue oil hydrogenation provided by the embodiment of the present invention has at least the following beneficial effects:
这样的催化剂成本低，且其通过浆态床反应过程中的高温环境，且在金属间的碰撞下，Mo元素在进料中N、Cl等元素的辅佐作用下，以原子或者纳米颗粒形式进入反应体系，可以避免管道堵塞，然后参与渣油加氢反应，提高渣油转化率，改善浆态床沸腾床气体分布，使气泡分布更细小和均匀。Such a catalyst has low cost, and it passes through the high temperature environment of the slurry bed reaction process, and under the collision between metals, the Mo element enters the reaction system in the form of atoms or nanoparticles with the assistance of elements such as N and Cl in the feed, which can avoid pipeline blockage, and then participate in the residue oil hydrogenation reaction, improve the residue oil conversion rate, improve the slurry bed boiling bed gas distribution, and make the bubble distribution smaller and more uniform.
本发明实施例还提供了用于浆态床渣油加氢的催化剂的应用方法，至少具有以下有益效果：The embodiment of the present invention also provides an application method of the catalyst for slurry bed residue oil hydrogenation, which has at least the following beneficial effects:
采用这种方法实现渣油加氢，工艺简单，成本低，且采用这些催化剂可以避免管道堵塞。This method is used to achieve residual oil hydrogenation, which has a simple process and low cost, and the use of these catalysts can avoid pipeline blockage.
具体实施方式Detailed ways
为使本发明实施例的目的、技术方案和优点更加清楚，下面将对本发明实施例中的技术方案进行清楚、完整地描述。实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市售购买获得的常规产品。In order to make the purpose, technical scheme and advantages of the embodiments of the present invention clearer, the technical scheme in the embodiments of the present invention will be described clearly and completely below. If the specific conditions are not specified in the embodiments, they are carried out according to conventional conditions or conditions recommended by the manufacturer. If the manufacturer of the reagents or instruments used is not specified, they are all conventional products that can be purchased commercially.
需要说明的是，在不冲突的情况下，本申请中的实施例及实施例中的特征可以相互组合。下面将参考具体实施例来详细说明本发明。It should be noted that, in the absence of conflict, the embodiments and features in the embodiments of the present application can be combined with each other. The present invention will be described in detail below with reference to specific embodiments.
本发明提出一种用于浆态床渣油加氢的催化剂，其为铝钼合金球。The present invention provides a catalyst for slurry bed residue oil hydrogenation, which is an aluminum-molybdenum alloy ball.
这样的催化剂成本低，且其通过浆态床反应过程中的高温环境，且在金属间的碰撞下，Mo元素在进料中N、Cl等元素的辅佐作用下，以原子或者纳米颗粒形式进入反应体系，可以避免管道堵塞，然后参与渣油加氢反应，提高渣油转化率，改善浆态床沸腾床气体分布，使气泡分布更细小和均匀。Such a catalyst has low cost, and it passes through the high temperature environment of the slurry bed reaction process, and under the collision between metals, the Mo element enters the reaction system in the form of atoms or nanoparticles with the assistance of elements such as N and Cl in the feed, which can avoid pipeline blockage, and then participate in the residue oil hydrogenation reaction, improve the residue oil conversion rate, improve the slurry bed boiling bed gas distribution, and make the bubble distribution smaller and more uniform.
进一步的，在本发明的一些实施例中，还包括油溶性钼催化剂，上述油溶性钼催化剂与铝钼合金球的质量比例为100-10000：1。Furthermore, in some embodiments of the present invention, an oil-soluble molybdenum catalyst is also included, and the mass ratio of the oil-soluble molybdenum catalyst to the aluminum-molybdenum alloy ball is 100-10000:1.
加入油溶性钼催化剂可以进一步的提高Mo元素的含量，Mo元素可以更好的在进料中N、Cl等元素的辅佐作用下，以原子或者纳米颗粒形式进入反应体系产生催化作用。The addition of oil-soluble molybdenum catalyst can further increase the content of Mo element. Mo element can better enter the reaction system in the form of atoms or nanoparticles with the assistance of elements such as N and Cl in the feed to produce catalytic effect.
进一步的，在本发明的一些实施例中，上述油溶性钼催化剂包括异辛酸钼、环烷酸钼、六羰基钼、乙酰丙酮钼中的任意一种。 Furthermore, in some embodiments of the present invention, the oil-soluble molybdenum catalyst includes any one of molybdenum isooctanoate, molybdenum cyclohexaneate, molybdenum hexacarbonyl, and molybdenum acetylacetonate.
进一步的，在本发明的一些实施例中，上述铝钼合金球的直径为0.5-5cm。采用这种直径的铝钼合金球可以改善浆态床的浆化状态，浆化更均匀。Furthermore, in some embodiments of the present invention, the diameter of the aluminum-molybdenum alloy ball is 0.5-5 cm. The use of aluminum-molybdenum alloy balls with such a diameter can improve the slurry state of the slurry bed and make the slurry more uniform.
进一步的，在本发明的一些实施例中，上述铝钼合金球中的钼含量为10-50％。Furthermore, in some embodiments of the present invention, the molybdenum content in the aluminum-molybdenum alloy ball is 10-50%.
采用这个钼含量的铝钼合金球，不会因为钼含量过高而导致钼合金的熔点过高，溶钼难度变大，合金强度变低，也不会因为钼含量过低而导致钼进入浆态床的量减少，避免合金表面生成氧化层而抑制钼的熔出。Using aluminum-molybdenum alloy balls with this molybdenum content will not cause the melting point of the molybdenum alloy to be too high due to the molybdenum content being too high, which will increase the difficulty of dissolving molybdenum and reduce the alloy strength. It will not cause the amount of molybdenum entering the slurry bed to be reduced due to the molybdenum content being too low, thus avoiding the formation of an oxide layer on the alloy surface and inhibiting the melting of molybdenum.
本发明还提供了一种如上上述的催化剂的应用方法，包括如下步骤：将渣油、如上上述的催化剂加入含有氢气的反应器中，然后搅拌使各原料混合均匀，进行催化加氢反应，反应结束后，得到轻组分油。The present invention also provides an application method of the catalyst as described above, comprising the following steps: adding residual oil and the catalyst as described above into a reactor containing hydrogen, then stirring to mix the raw materials evenly, performing a catalytic hydrogenation reaction, and obtaining a light component oil after the reaction is completed.
采用这种方法实现渣油加氢，工艺简单，成本低，且采用这些催化剂可以避免管道堵塞。This method is used to achieve residual oil hydrogenation, which has a simple process and low cost, and the use of these catalysts can avoid pipeline blockage.
进一步的，在本发明的一些实施例中，上述渣油与上述催化剂的质量比值为：1000：0.05-5。Furthermore, in some embodiments of the present invention, the mass ratio of the above-mentioned residual oil to the above-mentioned catalyst is: 1000:0.05-5.
这样的原料比例可以使催化剂对反应的催化效果达到最佳，更好的达到渣油加氢的效果。Such a raw material ratio can make the catalytic effect of the catalyst on the reaction reach the best, and better achieve the effect of residue oil hydrogenation.
进一步的，在本发明的一些实施例中，上述反应器内的反应温度为360～520℃。Furthermore, in some embodiments of the present invention, the reaction temperature in the reactor is 360-520°C.
这样的反应温度不会因为温度过高耗损原料，也不会因为温度过低反应速率慢，可以高效且充分反应。Such a reaction temperature will not cause loss of raw materials due to excessively high temperature, nor will the reaction rate be slow due to too low temperature, and the reaction can be efficient and sufficient.
进一步的，在本发明的一些实施例中，上述反应压力为10-25MPa。Furthermore, in some embodiments of the present invention, the reaction pressure is 10-25 MPa.
这样的压力相较于常压更容易实现渣油加氢，压力过高造成设备负荷增加，压力过低造成加氢转化率下降。Such pressure makes it easier to achieve residue oil hydrogenation than normal pressure. Too high pressure will increase the equipment load, while too low pressure will cause a decrease in the hydrogenation conversion rate.
进一步的，在本发明的一些实施例中，上述反应器内的反应时间为2-4h。这样的反应时间可以使原料充分反应。Furthermore, in some embodiments of the present invention, the reaction time in the reactor is 2-4 hours, which allows the raw materials to react fully.
进一步的，在本发明的一些实施例中，上述渣油为：减压渣油、催化裂化渣油及加氢处理渣油中的任意一种。包括但不限于上述渣油均可以采用这个催化剂进行加氢反应。Furthermore, in some embodiments of the present invention, the above-mentioned residual oil is any one of vacuum residual oil, catalytic cracking residual oil and hydroprocessing residual oil, including but not limited to the above-mentioned residual oils, which can be subjected to hydrogenation reaction using this catalyst.
以下结合实施例对本发明的特征和性能作进一步的详细描述。以下任意一个实施例及任意一个对比例采用的高压反应器均为模拟浆态床渣油加氢的高压反应器，该反应器中氧气置换为氢气，且含有升华硫粉等渣油加氢反应过程的其他物料。以下任意一个实施例及任意一个对比例采用的渣油均为委内瑞拉减压渣油，其各项性质如下表1所示：The features and performance of the present invention are further described in detail below in conjunction with the examples. The high-pressure reactors used in any of the following examples and any of the comparative examples are all high-pressure reactors for simulating slurry bed residue oil hydrogenation, in which oxygen is replaced by hydrogen and contains other materials in the residue oil hydrogenation reaction process such as sublimated sulfur powder. The residue oil used in any of the following examples and any of the comparative examples is Venezuelan vacuum residue oil, and its properties are shown in the following Table 1:
表1：
Table 1:
实施例1Example 1
本实施例提供了一种用于浆态床渣油加氢的催化剂：This embodiment provides a catalyst for slurry bed residue oil hydrogenation:
其为铝钼合金球，上述铝钼合金球的直径为0.95cm，上述铝钼合金球中的钼含量为40％。The aluminum-molybdenum alloy ball has a diameter of 0.95 cm and a molybdenum content of 40%.
实施例2Example 2
本实施例提供了一种用于浆态床渣油加氢的催化剂：This embodiment provides a catalyst for slurry bed residue oil hydrogenation:
其包括异辛酸钼和铝钼合金球，上述异辛酸钼的质量为0.4g，上述铝钼合金球的质量比例为250g，上述铝钼合金球的直径为1cm，上述铝钼合金球中的钼含量为30％。It includes molybdenum isooctanoate and aluminum-molybdenum alloy balls. The mass of the molybdenum isooctanoate is 0.4g, the mass ratio of the aluminum-molybdenum alloy balls is 250g, the diameter of the aluminum-molybdenum alloy balls is 1cm, and the molybdenum content in the aluminum-molybdenum alloy balls is 30%.
实施例3Example 3
本实施例提供了一种用于浆态床渣油加氢的催化剂：This embodiment provides a catalyst for slurry bed residue oil hydrogenation:
其包括异辛酸钼和铝钼合金球，上述异辛酸钼的质量为0.6g，与铝钼合金球的质量为380g，上述铝钼合金球的直径为0.92cm，上述铝钼合金球中的钼含量为45％。It includes molybdenum isooctanoate and aluminum-molybdenum alloy balls. The mass of the molybdenum isooctanoate is 0.6 g, and the mass of the aluminum-molybdenum alloy balls is 380 g. The diameter of the aluminum-molybdenum alloy balls is 0.92 cm, and the molybdenum content of the aluminum-molybdenum alloy balls is 45%.
实施例4Example 4
本实施例提供了一种用于浆态床渣油加氢的催化剂：This embodiment provides a catalyst for slurry bed residue oil hydrogenation:
其包括异辛酸钼和铝钼合金球，上述异辛酸钼的质量为0.8g，上述铝钼合金球的质量为600g，上述铝钼合金球的直径为1.08cm，上述铝钼合金球中的钼含量为15％。It includes molybdenum isooctanoate and aluminum-molybdenum alloy balls. The mass of the molybdenum isooctanoate is 0.8 g, the mass of the aluminum-molybdenum alloy balls is 600 g, the diameter of the aluminum-molybdenum alloy balls is 1.08 cm, and the molybdenum content of the aluminum-molybdenum alloy balls is 15%.
实施例5Example 5
本实施例提供了一种用于浆态床渣油加氢的催化剂：This embodiment provides a catalyst for slurry bed residue oil hydrogenation:
其包括异辛酸钼和铝钼合金球，上述异辛酸钼的质量为1g，与铝钼合金球的质量为720g，上述铝钼合金球的直径为1.12cm，上述铝钼合金球中的钼含量为10％。It includes molybdenum isooctanoate and aluminum-molybdenum alloy balls. The mass of the molybdenum isooctanoate is 1g, and the mass of the aluminum-molybdenum alloy balls is 720g. The diameter of the aluminum-molybdenum alloy balls is 1.12cm, and the molybdenum content in the aluminum-molybdenum alloy balls is 10%.
实施例6Example 6
本实施例提供了一种用于浆态床渣油加氢的催化剂：This embodiment provides a catalyst for slurry bed residue oil hydrogenation:
其包括异辛酸钼和铝钼合金球，上述环烷酸钼的质量为0.9g，与铝钼合金球的质量为650g，上述铝钼合金球的直径为1cm，上述铝钼合金球中的钼含量为13％。It includes molybdenum isooctanoate and aluminum-molybdenum alloy balls. The mass of the molybdenum cyclohexaneate is 0.9 g, and the mass of the aluminum-molybdenum alloy balls is 650 g. The diameter of the aluminum-molybdenum alloy balls is 1 cm, and the molybdenum content in the aluminum-molybdenum alloy balls is 13%.
实施例7Example 7
本实施例提供了一种用于浆态床渣油加氢的催化剂：This embodiment provides a catalyst for slurry bed residue oil hydrogenation:
其包括异辛酸钼和铝钼合金球，上述六羰基钼的质量为0.7g，与铝钼合金球的质量为700g，上述铝钼合金球的直径为1.5cm，上述铝钼合金球中的钼含量为12％。It includes molybdenum isooctanoate and aluminum-molybdenum alloy balls. The mass of the molybdenum hexacarbonyl is 0.7 g, and the mass of the aluminum-molybdenum alloy balls is 700 g. The diameter of the aluminum-molybdenum alloy balls is 1.5 cm, and the molybdenum content in the aluminum-molybdenum alloy balls is 12%.
实施例8Example 8
本实施例提供了一种用于浆态床渣油加氢的催化剂： This embodiment provides a catalyst for slurry bed residue oil hydrogenation:
其包括异辛酸钼和铝钼合金球，上述乙酰丙酮钼的质量为1g，与铝钼合金球的质量为710g，上述铝钼合金球的直径为2.5cm，上述铝钼合金球中的钼含量为11％。It includes molybdenum isooctanoate and aluminum-molybdenum alloy balls. The mass of the molybdenum acetylacetonate is 1g, and the mass of the aluminum-molybdenum alloy balls is 710g. The diameter of the aluminum-molybdenum alloy balls is 2.5cm, and the molybdenum content in the aluminum-molybdenum alloy balls is 11%.
实施例9Example 9
本实施例提供了一种用于浆态床渣油加氢的催化剂：This embodiment provides a catalyst for slurry bed residue oil hydrogenation:
其包括异辛酸钼和铝钼合金球，上述异辛酸钼的质量为0.5g，与铝钼合金球的质量为680g，上述铝钼合金球的直径为3.5cm，上述铝钼合金球中的钼含量为12％。It includes molybdenum isooctanoate and aluminum-molybdenum alloy balls. The mass of the molybdenum isooctanoate is 0.5 g, and the mass of the aluminum-molybdenum alloy balls is 680 g. The diameter of the aluminum-molybdenum alloy balls is 3.5 cm, and the molybdenum content in the aluminum-molybdenum alloy balls is 12%.
实施例10Example 10
本实施例提供了一种用于浆态床渣油加氢的催化剂：This embodiment provides a catalyst for slurry bed residue oil hydrogenation:
其包括异辛酸钼和铝钼合金球，上述异辛酸钼的质量为0.6g，与铝钼合金球的质量为690g，上述铝钼合金球的直径为5cm，上述铝钼合金球中的钼含量为12％。It includes molybdenum isooctanoate and aluminum-molybdenum alloy balls. The mass of the molybdenum isooctanoate is 0.6 g, and the mass of the aluminum-molybdenum alloy balls is 690 g. The diameter of the aluminum-molybdenum alloy balls is 5 cm, and the molybdenum content in the aluminum-molybdenum alloy balls is 12%.
实施例11Embodiment 11
本实施例提供了一种用于浆态床渣油加氢的催化剂的应用方法：This embodiment provides an application method of a catalyst for slurry bed residue oil hydrogenation:
包括如下步骤：将200g渣油、5.2g实施例1的催化剂加入1L的高压反应器中，搅拌使各原料混合均匀；The method comprises the following steps: adding 200 g of residual oil and 5.2 g of the catalyst of Example 1 into a 1 L high pressure reactor, and stirring to make the raw materials uniformly mixed;
然后将反应器内的空气置换为氢气后进行反应，上述反应器内的反应温度为360℃，上述反应器内的反应压力为25MPa，反应时间为3h，反应结束后，待反应器冷却至室温，得到加氢渣油。Then, the air in the reactor was replaced with hydrogen and then the reaction was carried out. The reaction temperature in the reactor was 360° C., the reaction pressure in the reactor was 25 MPa, and the reaction time was 3 h. After the reaction was completed, the reactor was cooled to room temperature to obtain hydrogenated residue oil.
实施例12Example 12
本实施例提供了一种用于浆态床渣油加氢的催化剂的应用方法：This embodiment provides an application method of a catalyst for slurry bed residue oil hydrogenation:
包括如下步骤：将200g渣油、5.2g实施例2的催化剂加入1L的高压反应器中，搅拌使各原料混合均匀；The method comprises the following steps: adding 200 g of residual oil and 5.2 g of the catalyst of Example 2 into a 1 L high pressure reactor, and stirring to make the raw materials uniformly mixed;
然后将反应器内的空气置换为氢气后进行反应，上述反应器内的反应温度为520℃，上述反应器内的反应压力为10MPa，反应时间为4h，反应结束后，待反应器冷却至室温，得到加氢渣油。Then, the air in the reactor was replaced with hydrogen and then the reaction was carried out. The reaction temperature in the reactor was 520° C., the reaction pressure in the reactor was 10 MPa, and the reaction time was 4 hours. After the reaction was completed, the reactor was cooled to room temperature to obtain hydrogenated residue oil.
实施例13Example 13
本实施例提供了一种用于浆态床渣油加氢的催化剂的应用方法：This embodiment provides an application method of a catalyst for slurry bed residue oil hydrogenation:
包括如下步骤：将200g渣油、4.9g实施例3的催化剂加入1L的高压反应器中，搅拌使各原料混合均匀；The method comprises the following steps: adding 200 g of residual oil and 4.9 g of the catalyst of Example 3 into a 1 L high pressure reactor, and stirring to make the raw materials uniformly mixed;
然后将反应器内的空气置换为氢气后进行反应，上述反应器内的反应温度为480℃，上述反应器内的反应压力为20MPa，反应时间为2h，反应结束后，待反应器冷却至室温，得到加氢渣油。 Then, the air in the reactor is replaced with hydrogen and the reaction is carried out. The reaction temperature in the reactor is 480° C., the reaction pressure in the reactor is 20 MPa, and the reaction time is 2 h. After the reaction is completed, the reactor is cooled to room temperature to obtain hydrogenated residue oil.
实施例14Embodiment 14
本实施例提供了一种用于浆态床渣油加氢的催化剂的应用方法：This embodiment provides an application method of a catalyst for slurry bed residue oil hydrogenation:
包括如下步骤：将200g渣油、5g实施例4的催化剂加入1L的高压反应器中，搅拌使各原料混合均匀；The method comprises the following steps: adding 200 g of residual oil and 5 g of the catalyst of Example 4 into a 1 L high pressure reactor, and stirring to make the raw materials uniformly mixed;
然后将反应器内的空气置换为氢气后进行反应，上述反应器内的反应温度为500℃，上述反应器内的反应压力为15MPa，反应时间为4h，反应结束后，待反应器冷却至室温，得到加氢渣油。Then, the air in the reactor is replaced with hydrogen and the reaction is carried out. The reaction temperature in the reactor is 500° C., the reaction pressure in the reactor is 15 MPa, and the reaction time is 4 hours. After the reaction is completed, the reactor is cooled to room temperature to obtain hydrogenated residue oil.
实施例15Embodiment 15
本实施例提供了一种用于浆态床渣油加氢的催化剂的应用方法：This embodiment provides an application method of a catalyst for slurry bed residue oil hydrogenation:
包括如下步骤：将200g渣油、5g实施例5的催化剂加入1L的高压反应器中，搅拌使各原料混合均匀；The method comprises the following steps: adding 200 g of residual oil and 5 g of the catalyst of Example 5 into a 1 L high pressure reactor, and stirring to make the raw materials uniformly mixed;
然后将反应器内的空气置换为氢气后进行反应，上述反应器内的反应温度为400℃，上述反应器内的反应压力为20MPa，反应时间为2h，反应结束后，待反应器冷却至室温，得到加氢渣油。Then, the air in the reactor is replaced with hydrogen and the reaction is carried out. The reaction temperature in the reactor is 400° C., the reaction pressure in the reactor is 20 MPa, and the reaction time is 2 h. After the reaction is completed, the reactor is cooled to room temperature to obtain hydrogenated residue oil.
对比例1Comparative Example 1
本实施例提供了一种用于浆态床渣油加氢的催化剂的应用方法：This embodiment provides an application method of a catalyst for slurry bed residue oil hydrogenation:
包括如下步骤：将200g渣油加入1L的高压反应器中，搅拌使各原料混合均匀；The method comprises the following steps: adding 200 g of residual oil into a 1 L high pressure reactor, and stirring to make all raw materials uniformly mixed;
然后将反应器内的空气置换为氢气后进行反应，上述反应器内的反应温度为430℃，上述反应器内的反应压力为20MPa，反应时间为3h，反应结束后，待反应器冷却至室温，得到加氢渣油。Then, the air in the reactor was replaced with hydrogen and then the reaction was carried out. The reaction temperature in the reactor was 430° C., the reaction pressure in the reactor was 20 MPa, and the reaction time was 3 h. After the reaction was completed, the reactor was cooled to room temperature to obtain hydrogenated residue oil.
对比例2Comparative Example 2
本实施例提供了一种用于浆态床渣油加氢的催化剂的应用方法：This embodiment provides an application method of a catalyst for slurry bed residue oil hydrogenation:
包括如下步骤：将200g渣油、400ppm异辛酸钼加入1L的高压反应器中，搅拌使各原料混合均匀；The method comprises the following steps: adding 200 g of residual oil and 400 ppm of molybdenum isooctanoate into a 1 L high pressure reactor, and stirring to make the raw materials uniformly mixed;
然后将反应器内的空气置换为氢气后进行反应，上述反应器内的反应温度为430℃，上述反应器内的反应压力为20MPa，反应时间为3h，反应结束后，待反应器冷却至室温，得到加氢渣油。Then, the air in the reactor was replaced with hydrogen and then the reaction was carried out. The reaction temperature in the reactor was 430° C., the reaction pressure in the reactor was 20 MPa, and the reaction time was 3 h. After the reaction was completed, the reactor was cooled to room temperature to obtain hydrogenated residue oil.
试验例Test example
分别收集上述实施例11-15、对比例1、对比例2的反应产物进行减压蒸馏，分别计算转化率、C1-C4气体、C5-200℃馏分收率、200～360℃馏分收率、360～520℃馏分收率和>520℃馏分收率。蒸留残渣用甲苯洗涤，离心、干燥后称重计算结焦率。渣油加氢效果见表2： The reaction products of Examples 11-15, Comparative Example 1 and Comparative Example 2 were collected and subjected to vacuum distillation, and the conversion rate, C1-C4 gas, C5-200°C fraction yield, 200-360°C fraction yield, 360-520°C fraction yield and >520°C fraction yield were calculated. The distillation residue was washed with toluene, centrifuged, dried and weighed to calculate the coking rate. The residual oil hydrogenation effect is shown in Table 2:
表2
Table 2
从表2可知，与对比例1相比，实施例11-15中添加了实施例1-5中的催化剂，渣油转化率更高，C1-C4、C5-200℃、200-360℃、360-520℃等轻组分含量明显增多，焦炭含量明显下降，证明本发明提供的催化剂有显著的催化效果。As can be seen from Table 2, compared with Comparative Example 1, the catalysts in Examples 1-5 are added to Examples 11-15, and the residue conversion rate is higher, the contents of light components such as C1-C4, C5-200°C, 200-360°C, and 360-520°C are significantly increased, and the coke content is significantly decreased, which proves that the catalyst provided by the present invention has a significant catalytic effect.
与对比例2相比，实施例12、13、14、15中分别添加了实施例2-5中的催化剂，渣油转化率增加，C1-520℃总轻组分含量明显增多，>520℃组分减少，焦炭含量进一步降低，证明本发明中的添加剂采用铝钼合金球与异辛酸钼配伍能到达到更加显著的效果。Compared with Comparative Example 2, the catalysts in Examples 2-5 were added to Examples 12, 13, 14, and 15, respectively, and the residual oil conversion rate was increased, the total light component content of C1-520°C was significantly increased, the components >520°C were reduced, and the coke content was further reduced, proving that the additive in the present invention can achieve more significant effects by using aluminum-molybdenum alloy balls and molybdenum isooctanoate.
由上述实验可知，采用本发明提供的催化剂应用在渣油加氢中，可以得到更多的轻组分油，更少的重组分(>520℃)，这样可以为浆态床渣油加氢带来更多的利润。这样成本低，就可以提高渣油转化率和轻油收率，降低了焦炭收率，为浆态床渣油加氢产生更多的经济效益。From the above experiments, it can be seen that the use of the catalyst provided by the present invention in the hydrogenation of residual oil can obtain more light component oil and less heavy component (>520°C), which can bring more profits to the slurry bed residual oil hydrogenation. In this way, the cost is low, the residual oil conversion rate and light oil yield can be improved, the coke yield can be reduced, and more economic benefits can be generated for the slurry bed residual oil hydrogenation.
此外，钼合金钢珠可以改善沸腾床气体分布，使气泡分布更细小和均匀。In addition, molybdenum alloy steel beads can improve the gas distribution in the fluidized bed and make the bubble distribution smaller and more uniform.
综上上述，这样的催化剂成本低，且其通过浆态床反应过程中的高温环境，且在金属间的碰撞下，Mo元素在进料中N、Cl等元素的辅佐作用下，以原子或者纳米颗粒形式进入反应体系，可以避免管道堵塞，然后参与渣油加氢反应，提高渣油转化率，改善浆态床沸腾床气体分布，使气泡分布更细小和均匀。In summary, such a catalyst has low cost, and through the high temperature environment of the slurry bed reaction process, and under the collision between metals, the Mo element enters the reaction system in the form of atoms or nanoparticles with the assistance of elements such as N and Cl in the feed, which can avoid pipeline blockage, and then participate in the residue oil hydrogenation reaction, improve the residue oil conversion rate, improve the slurry bed boiling bed gas distribution, and make the bubble distribution smaller and more uniform.
本发明实施例还提供了用于浆态床渣油加氢的催化剂的应用方法，至少具有以下有益效果：The embodiment of the present invention also provides an application method of the catalyst for slurry bed residue oil hydrogenation, which has at least the following beneficial effects:
采用这种方法实现渣油加氢，工艺简单，成本低，且采用这些催化剂可以避免管道堵塞。This method is used to achieve residual oil hydrogenation, which has a simple process and low cost, and the use of these catalysts can avoid pipeline blockage.
以上所描述的实施例是本发明一部分实施例，而不是全部的实施例。本发明的实施例的 详细描述并非旨在限制要求保护的本发明的范围，而是仅仅表示本发明的选定实施例。基于本发明中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。 The embodiments described above are only part of the embodiments of the present invention, but not all of the embodiments. The detailed description is not intended to limit the scope of the claimed invention, but merely represents selected embodiments of the invention. Based on the embodiments of the invention, all other embodiments obtained by ordinary technicians in the field without creative work are within the scope of protection of the invention.

Claims (10)

  1. 一种用于浆态床渣油加氢的催化剂，其特征在于：其为铝钼合金球。A catalyst for slurry bed residue oil hydrogenation, characterized in that it is an aluminum-molybdenum alloy ball.
  2. 根据权利要求1所述的催化剂，其特征在于：还包括油溶性钼催化剂，所述油溶性钼催化剂与铝钼合金球的质量比例为100-10000：1。The catalyst according to claim 1 is characterized in that it also includes an oil-soluble molybdenum catalyst, and the mass ratio of the oil-soluble molybdenum catalyst to the aluminum-molybdenum alloy ball is 100-10000:1.
  3. 根据权利要求2所述的催化剂，其特征在于：所述油溶性钼催化剂包括异辛酸钼、环烷酸钼、六羰基钼、乙酰丙酮钼中的任意一种。The catalyst according to claim 2 is characterized in that the oil-soluble molybdenum catalyst includes any one of molybdenum isooctanoate, molybdenum cyclohexaneate, molybdenum hexacarbonyl, and molybdenum acetylacetonate.
  4. 根据权利要求1-3中任意一项所述的催化剂，其特征在于：所述铝钼合金球的直径为0.5-5cm。The catalyst according to any one of claims 1 to 3, characterized in that the diameter of the aluminum-molybdenum alloy ball is 0.5-5 cm.
  5. 根据权利要求4所述的催化剂，其特征在于：所述铝钼合金球中的钼含量为10-50％。The catalyst according to claim 4 is characterized in that the molybdenum content in the aluminum-molybdenum alloy ball is 10-50%.
  6. 一种如权利要求1-5中任一项所述的催化剂的应用方法，其特征在于：包括如下步骤：A method for using the catalyst according to any one of claims 1 to 5, characterized in that it comprises the following steps:
    将渣油、如权利要求1-5中任一项所述的催化剂加入含有氢气的反应器中，然后搅拌使各原料混合均匀，进行催化加氢反应，反应结束后，得到轻组分油。Add the residual oil and the catalyst as claimed in any one of claims 1 to 5 into a reactor containing hydrogen, then stir to make the raw materials evenly mixed, and carry out catalytic hydrogenation reaction. After the reaction is completed, light component oil is obtained.
  7. 根据权利要求6所述的化剂的应用方法，其特征在于：所述渣油与所述催化剂的质量比值为：1000：0.05-5。The application method of the chemical agent according to claim 6 is characterized in that the mass ratio of the residual oil to the catalyst is: 1000:0.05-5.
  8. 根据权利要求6所述的化剂的应用方法，其特征在于：所述反应器内的反应温度为360～520℃，所述反应器内的反应压力为10-25MPa。The method for applying the chemical agent according to claim 6 is characterized in that the reaction temperature in the reactor is 360-520°C and the reaction pressure in the reactor is 10-25MPa.
  9. 根据权利要求6所述的化剂的应用方法，其特征在于：所述反应器内的反应时间为2-4h。The method for applying the chemical agent according to claim 6 is characterized in that the reaction time in the reactor is 2-4 hours.
  10. 根据权利要求6所述的化剂的应用方法，其特征在于：所述渣油为：减压渣油、催化裂化渣油及加氢处理渣油中的任意一种。 The application method of the chemical agent according to claim 6 is characterized in that the residual oil is any one of vacuum residue oil, catalytic cracking residue oil and hydroprocessing residue oil.
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