A deoxidation catalyst, a method for preparing the same, and an application thereof

Abstract

The application provides a deoxygenation catalyst and a preparation method and application thereof. The catalyst comprises an active component and a carrier, the active component comprises metal Cu and metal Ni, and the carrier is alumina, activated carbon, silicon oxide, an alumina-silicon oxide composite carrier or an alumina molecular sieve. The catalyst has a good deoxygenation effect on oxygen, is good in selectivity, and is stable. When the catalyst is applied to the purification of dry gas in a petrochemical field with a high hydrogen content, the purification efficiency and recovery rate of olefins are improved.

Description

A deoxygenation catalyst, its preparation method and application Technical Field

[0001] This invention relates to the field of catalyst technology, and more specifically, to a deoxygenation catalyst, its preparation method, and its application. Background Technology

[0002] Refinery dry gas contains trace amounts of oxygen and nitric oxide, with nitric oxide easily oxidized to nitrogen dioxide. In the cold box of an ethylene plant (temperatures below -102°C), nitrogen dioxide forms solid nitrogen peroxide (N₂O₄). Nitrogen peroxide can further react with dienes at this low temperature to form nitrated gums. Nitrated gums are unstable and can explode upon heating or impact. Simultaneously, a small amount of oxygen entering the ethylene system can not only cause substandard ethylene products but also pose safety hazards. Therefore, deoxygenation purification of various enriched gases entering ethylene plants is essential in the petrochemical industry. On the other hand, dry gas may also contain a large amount of hydrogen. Hydrogen readily reacts with olefins in the dry gas to form alkanes. This not only results in olefin loss but also generates significant heat during the hydrogen-olefin reaction, potentially causing temperature runaway in the reactor catalyst bed. Therefore, in petrochemical purification processes with high hydrogen content, the selectivity of the purification catalyst is particularly important.

[0003] Generally, catalytic deoxygenation is used to remove O2 from the system. Existing dry gas recovery processes in refineries require deoxygenation catalysts. Most existing deoxygenation catalysts are either precious metal catalysts or non-precious metal catalysts. Among them, precious metal catalysts are mainly palladium-based catalysts, which are expensive, and impurities such as sulfur and carbon monoxide in the gas can easily poison and deactivate the catalyst. The main active components of non-precious metal catalysts are molybdenum, cobalt, nickel, tungsten, etc. The active metal components of these fresh catalysts and regenerated catalysts exist in the oxidized form. They need to be sulfided to convert the active metal components from the oxidized state to the sulfidized state before they can have good hydrodeoxygenation activity, selectivity and stability.

[0004] Chinese patent CN1087655C discloses a high-strength, heat-resistant, and poison-resistant deoxidation catalyst that uses precious metals such as Pt and Pd as active components. This type of catalyst exhibits high activity and can be used at room temperature. However, it has strict requirements for raw materials, as sulfides and other substances can poison the catalyst.

[0005] Chinese patent CN101165030A provides a Mn-Ag dual-active component deoxidizer, its preparation method, and its application. It is used to remove trace amounts of oxygen from ethylene and propylene, and can remove oxygen to below 0.05 ppm. However, this deoxidizer catalyst requires repeated reduction and regeneration during use to ensure stable deoxidation activity, and the deoxidizer has a low processing capacity per unit time, which will increase costs when used in the polyolefin industry.

[0006] Chinese patent CN101391224A discloses a catalyst for removing nitrogen oxides and its application. The catalyst support is modified γ-alumina, and the active components include Mo, W, or Cr, Ni, or Co, and P or citric acid. It is used for the removal of oxygen and nitrogen oxides from hydrocarbon-containing gases and / or inert gases. However, the catalyst exhibits good performance in removing oxygen and nitrogen oxides when in a sulfurized state and at a reaction temperature of 120–260°C; while its activity and stability are poor when sulfur-free.

[0007] Meanwhile, the catalysts mentioned above require a relatively high hydrogen content in the system during use. When the hydrogen content is high, the olefins in the system are prone to react with hydrogen, causing the bed temperature to rise rapidly, which can lead to a runaway temperature of the catalyst bed in the reactor.

[0008] Chinese patent CN101745391A discloses a catalyst for removing trace amounts of oxygen from catalytic cracking dry gas. Pd is the main active component, with Ag, Au, Co, and Cr as co-catalytic active components. When used in the deoxygenation process of catalytic cracking dry gas, it exhibits strong resistance to poisoning and minimal bed temperature runaway. However, during use, this catalyst suffers from poor selectivity, inevitably resulting in a loss of 0.5% to 1.7% of ethylene gas. Summary of the Invention

[0009] To address the aforementioned problems, this invention provides a deoxygenation catalyst and its preparation method. The catalyst of this invention exhibits good oxygen removal efficiency and selectivity, and can be applied to the purification of dry gas in petrochemical fields with high hydrogen content. It significantly improves the purification efficiency and recovery rate of olefins, reduces production costs, and increases enterprise profits.

[0010] Firstly, one objective of this invention is to provide a deoxygenation catalyst. The catalyst comprises an active component and a support, wherein the active component comprises metallic Cu and metallic Ni; the support is one or a combination of alumina, activated carbon, silica, an alumina-silica composite support, and alumina molecular sieves.

[0011] Preferably, the content of Cu metal in the catalyst is 0.01-4.5 wt%, more preferably 0.5-4 wt%, and even more preferably 0.5-2.5 wt%; the content of Ni metal is 0.01-4.5 wt%, more preferably 0.5-4 wt%, and even more preferably 0.5-2.5 wt%.

[0012] Preferably, in the active component of the catalyst, the weight ratio of metallic Cu to metallic Ni is 1:(0.01-100), more preferably 1:(0.1-20), and even more preferably 1:(0.1-10).

[0013] Preferably, the carrier of the present invention is one or a combination of aluminum oxide and silicon dioxide; more preferably, it is one or a combination of γ-Al2O3 and α-Al2O3; wherein, aluminum oxide can appear in a variety of forms, not limited to any shape among spheres, strips, clover shapes, and columns.

[0014] Furthermore, the carrier possesses the following physical properties: the pore volume of the carrier is 0.2–0.5 cm³. 3 / g; the pore size distribution of the carrier is 1–12 nm, preferably 1–10 nm; the average pore size of the carrier is 3–8 nm, preferably 3–5 nm; the specific surface area of ​​the carrier is 50–200 m² / g. 2 / g, preferably 100-150m 2 / g.

[0015] The catalyst support of the present invention can be selected from one or a combination of alumina, activated carbon, silica, alumina-silica composite support, and alumina molecular sieve that are already available in the prior art; or the above-mentioned support can be prepared by existing preparation methods.

[0016] Secondly, another objective of this invention is to provide a method for preparing the deoxygenation catalyst that is one of the objectives of this invention.

[0017] Specifically, the method involves loading the active component onto a support, followed by drying and calcination to obtain a deoxygenation catalyst.

[0018] More specifically, the method includes the following steps:

[0019] Step 1: Dissolve the water-soluble copper compound and the water-soluble nickel compound separately or together in water to obtain the impregnation solution;

[0020] Step 2: Immerse the carrier in the impregnation solution of Step 1 or spray the impregnation solution of Step 1 onto the carrier;

[0021] Step 3: Dry and calcine to obtain the deoxygenation catalyst.

[0022] It is worth mentioning that the present invention can load the active components onto the carrier by impregnation or spraying, or load two active components onto the carrier simultaneously or separately. The concentration of the impregnation solution or spraying solution is not limited, as long as the fully dissolved active components can be fully impregnated or sprayed onto the carrier.

[0023] Preferably, in step one, the water-soluble copper compound and the water-soluble nickel compound can be derived from water-soluble metal oxides or metal salts; wherein the metal salt can be any one of nitrates, sulfates, chlorides, acetates, and carbonic acids.

[0024] More preferably, the water-soluble copper compound is derived from one or a combination of copper chloride, copper nitrate, copper sulfate, and copper acetate; and the water-soluble nickel compound is derived from one or a combination of nickel nitrate, nickel sulfate, and basic nickel carbonate.

[0025] Preferably, in step three, the carrier loaded with the active component needs to be dried before calcination. The drying conditions are: temperature 80-120℃, time 2-10h; the calcination conditions are: temperature 300-800℃, time 2-10h; preferably, temperature 400-600℃, time 3-8h.

[0026] Thirdly, a third objective of the present invention is to provide the application of the deoxygenation catalyst for one of the objectives of the present invention.

[0027] Specifically, the deoxygenation catalyst provided by this invention can be used for the purification of petrochemical dry gas, especially for the deoxygenation purification of petrochemical dry gas with a high hydrogen content. When the hydrogen content in the dry gas is 1-40%, preferably 1-20%, and the oxygen content is 10-10000ppm, preferably 10-400ppm, the deoxygenation catalyst provided by this invention can purify the oxygen in the dry gas to below 2ppm.

[0028] More specifically, when the deoxygenation catalyst of the present invention is used for the purification of petrochemical dry gas, the catalyst is placed in a fixed-bed reactor, and the application conditions for the catalytic deoxygenation reaction are as follows: reaction temperature of 100–200°C; reaction pressure of 1.0–3.0 MPa; and feed space velocity of 1000–5000 h⁻¹. -1 The dry gas contains 20-50% ethylene and 1-40% hydrogen.

[0029] It is worth mentioning that the reaction temperature can be adjusted at any time according to the progress of the reaction, and the increase in reaction temperature is conducive to the purification reaction.

[0030] Furthermore, before the catalyst of the present invention is used in the purification and deoxygenation reaction of petrochemical dry gas, it needs to be reduced first, that is, the catalyst is brought into contact with a mixture of hydrogen and nitrogen gas to reduce the catalyst.

[0031] Specifically, in this invention, the reduction conditions of the catalyst are as follows:

[0032] Preferably, the reduction temperature is 100–300°C.

[0033] Preferably, the reducing agent is a mixture of hydrogen and nitrogen. More preferably, the volume ratio of hydrogen to nitrogen in the mixture is 1:0.1 to 100, and more preferably 1:1 to 10.

[0034] Preferably, the space velocity of the reduction reaction is 100–1000 h⁻¹. -1 .

[0035] Preferably, the reduction time is 5 to 20 hours.

[0036] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0037] 1. The catalyst provided by this invention can effectively remove oxygen from refinery gas and has good selectivity for oxygen. It does not cause hydrogenation of olefins during deoxygenation, thus avoiding side reactions and reducing olefin loss. It also has good stability and can be used for a long time without reducing its activity.

[0038] 2. The catalyst provided by this invention uses non-precious metals and does not contain precious metals in its components, which greatly reduces the cost of application.

[0039] 3. The catalyst provided by this invention has mild activity and does not require a high hydrogen content in the raw materials. Even when the hydrogen content in the raw materials is high (e.g., when the hydrogen content is higher than 20%), it will not cause the reactor to overheat. Detailed Implementation

[0040] The present invention will now be described in detail with reference to specific embodiments. It should be noted that the following embodiments are only used to further illustrate the present invention and should not be construed as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the content of the present invention are still within the scope of protection of the present invention.

[0041] In the following examples and comparative examples, the raw materials were all commercially available products.

[0042] In the test methods of the following embodiments, the pore volume, pore size distribution, average pore size and specific surface area of ​​the support were measured by N2 adsorption method GB / T5816-1995; the copper and nickel contents in the catalyst were measured by X-ray photoelectron spectroscopy (XPS).

[0043] Example 1

[0044] This example illustrates the preparation of the catalyst support.

[0045] Aluminum hydroxide produced by the nitric acid method and phosphorus-containing aluminum hydroxide produced by the sulfuric acid method were mixed at a mass ratio of 1:20. Specifically, 10g of nitric acid-processed aluminum hydroxide powder and 200g of phosphorus-containing aluminum hydroxide powder were added to a mill and mixed for 20 minutes. Then, a gelling agent made from 6g of guar gum powder, 4g of concentrated nitric acid, and 150g of deionized water was added, and the mixture was kneaded for 30 minutes before being extruded into 2.0mm clover-shaped strips. The wet strips were then dried at 80℃ for 4 hours, 120℃ for 4 hours, and calcined at 500℃ for 4 hours to obtain an alumina carrier with the following physical properties: pore volume of 0.4cm³. 3 / g, pore size distribution of 1-10nm, average pore size of 4nm, specific surface area of ​​180m² 2 / g.

[0046] Example 2

[0047] This example illustrates the preparation of the catalyst support.

[0048] The preparation method of the carrier in this embodiment is basically the same as that in Example 1, except that the alumina carrier in this embodiment is cylindrical, and its physical properties are: pore volume of 0.2 cm³. 3 / g, pore size distribution of 3-8nm, average pore size of 3nm, specific surface area of ​​100m² 2 / g.

[0049] Example 3

[0050] This example is used for the preparation of catalysts:

[0051] Weigh 30g of copper nitrate and 20g of basic nickel carbonate, dissolve them in water to prepare an impregnation solution. Impregnate the carrier prepared in Example 1 with the above impregnation solution using the equal-volume impregnation method. After uniform impregnation, dry at 80℃ for 2h, dry at 120℃ for 4h, and then calcine at 600℃ for 4h to obtain the catalyst.

[0052] The catalyst contains 1 wt% copper and 1 wt% nickel.

[0053] The following describes the reduction treatment of the catalyst obtained in this embodiment:

[0054] A mixture of hydrogen and nitrogen gas is brought into contact with the catalyst to reduce it. The ratio of hydrogen to nitrogen gas is 1:10, the reduction reaction temperature is 260℃, and the space velocity of the reactants is 500 h⁻¹. -1 The restoration time is 12 hours.

[0055] The following is used to illustrate the evaluation of the catalyst prepared in this example:

[0056] The deoxygenation performance of the reduced catalyst was investigated in a conventional small fixed-bed reactor. The catalyst loading was 10 ml, and the reaction was carried out at 120°C by introducing an oxygen-containing feed gas, namely ethylene, along with 10% hydrogen. The oxygen content in the feed gas was 100 ppm, and the gas hourly space velocity was 3000 h⁻¹. -1 The reaction pressure was 1.0 MPa. Detailed evaluation results of the catalyst in this embodiment are shown in Tables 1 and 2.

[0057] Example 4

[0058] This example is used for the preparation of catalysts:

[0059] Weigh 11g of copper chloride and 10g of basic nickel carbonate, dissolve them in water to prepare an impregnation solution. Impregnate the carrier prepared in Example 1 with the above impregnation solution using the equal volume impregnation method. After uniform impregnation, dry at 80℃ for 2h, dry at 120℃ for 4h, and then calcine at 500℃ for 5h to obtain the catalyst.

[0060] The catalyst contains 0.5 wt% copper and 0.5 wt% nickel.

[0061] The catalyst reduction treatment and evaluation method in this embodiment are the same as those in Example 3. The specific evaluation results are detailed in Table 1.

[0062] Example 5

[0063] This example is used for the preparation of catalysts:

[0064] Weigh 64g of copper acetate and 58g of nickel nitrate, dissolve them in water to prepare an impregnation solution. Impregnate the carrier prepared in Example 1 with the above impregnation solution using the equal-volume impregnation method. After uniform impregnation, dry at 80℃ for 2h, dry at 100℃ for 4h, and then calcine at 700℃ for 3h to obtain the catalyst.

[0065] The catalyst contains 2 wt% copper and 2 wt% nickel.

[0066] The catalyst reduction treatment and evaluation method in this embodiment are the same as those in Example 3. The specific evaluation results are detailed in Table 1.

[0067] Example 6

[0068] This example is used for the preparation of catalysts:

[0069] Weigh 60g of copper nitrate and 10g of basic nickel carbonate, dissolve them in water to prepare an impregnation solution. Impregnate the carrier prepared in Example 1 with the above impregnation solution using the equal-volume impregnation method. After uniform impregnation, dry at 80℃ for 2h, dry at 120℃ for 4h, and calcine at 450℃ for 8h to obtain the catalyst.

[0070] The catalyst contains 2 wt% copper and 0.5 wt% nickel.

[0071] The catalyst reduction treatment and evaluation method in this embodiment are the same as those in Example 3. The specific evaluation results are detailed in Table 1.

[0072] Example 7

[0073] This example is used for the preparation of catalysts:

[0074] 11g of copper chloride and 58g of nickel nitrate were weighed and dissolved in water to prepare an impregnation solution. The carrier prepared in Example 1 was impregnated with the above impregnation solution using the equal-volume impregnation method. After uniform impregnation, it was dried at 80°C for 2 hours, dried at 120°C for 4 hours, and then calcined at 600°C for 4 hours to obtain the catalyst.

[0075] The catalyst contains 0.5 wt% copper and 2 wt% nickel.

[0076] The catalyst reduction treatment and evaluation method in this embodiment are the same as those in Example 3. The specific evaluation results are detailed in Table 1.

[0077] Example 8

[0078] This example is used for the preparation of catalysts:

[0079] Weigh 64g of copper acetate and 2g of basic nickel carbonate, dissolve them in water to prepare an impregnation solution. Impregnate the carrier prepared in Example 1 with the above impregnation solution using the equal-volume impregnation method. After uniform impregnation, dry at 80℃ for 2h, dry at 120℃ for 4h, and then calcine at 600℃ for 4h to obtain the catalyst.

[0080] The catalyst contains 2 wt% copper and 0.1 wt% nickel.

[0081] The catalyst reduction treatment and evaluation method in this embodiment are the same as those in Example 3. The specific evaluation results are detailed in Table 1.

[0082] Example 9

[0083] This example is used for the preparation of catalysts:

[0084] Weigh out 3g of copper nitrate and 58g of nickel nitrate, dissolve them in water to prepare an impregnation solution. Impregnate the carrier prepared in Example 1 with the above impregnation solution using the equal-volume impregnation method. After uniform impregnation, dry at 80℃ for 2h, dry at 120℃ for 4h, and then calcine at 600℃ for 4h to obtain the catalyst.

[0085] The catalyst contains 0.1 wt% copper and 2 wt% nickel.

[0086] The catalyst reduction treatment and evaluation method in this embodiment are the same as those in Example 3. The specific evaluation results are detailed in Table 1.

[0087] Example 10

[0088] This example is used for the preparation of catalysts:

[0089] Weigh 2g of copper chloride and 2g of basic nickel carbonate, dissolve them in water to prepare an impregnation solution. Impregnate the carrier prepared in Example 1 with the above impregnation solution using the equal-volume impregnation method. After uniform impregnation, dry at 80℃ for 2h, dry at 120℃ for 4h, and then calcine at 600℃ for 4h to obtain the catalyst.

[0090] The catalyst contains 0.1 wt% copper and 0.1 wt% nickel.

[0091] The catalyst reduction treatment and evaluation method in this embodiment are the same as those in Example 3. The specific evaluation results are detailed in Table 1.

[0092] Example 11

[0093] This example is used for the preparation of catalysts:

[0094] Weigh 30g of copper sulfate and 65g of nickel sulfate, dissolve them in water to prepare an impregnation solution. Impregnate the carrier prepared in Example 1 with the above impregnation solution using the equal-volume impregnation method. After uniform impregnation, dry at 80℃ for 2h, dry at 100℃ for 6h, and then calcine at 400℃ for 5h to obtain the catalyst.

[0095] The catalyst contains 1 wt% copper and 2.5 wt% nickel.

[0096] The catalyst obtained in this embodiment was subjected to reduction treatment:

[0097] A mixture of hydrogen and nitrogen gas is brought into contact with the catalyst to reduce it. The ratio of hydrogen to nitrogen gas is 1:10, the reduction reaction temperature is 260℃, and the space velocity of the reactants is 500 h⁻¹. -1 The restoration time is 12 hours.

[0098] The deoxygenation performance of the catalyst was investigated in a conventional small-scale fixed-bed reactor. The catalyst loading was 10 ml, and the reaction was carried out at 100°C by introducing an oxygen-containing feed gas (ethylene) with 20% hydrogen added. The oxygen content in the feed gas was 350 ppm, and the gas hourly space velocity (GHSV) was 2000 h⁻¹. -1 The reaction pressure was 2.5 MPa. Detailed evaluation results of the catalyst in this embodiment are shown in Table 1.

[0099] Example 12

[0100] This example is used for the preparation of catalysts:

[0101] In this embodiment, the carrier is silicon dioxide, whose physical properties are: pore volume of 0.3 cm³. 3 / g, pore size distribution of 3-8nm, average pore size of 3nm, specific surface area of ​​150m² 2 / g.

[0102] Weigh 15g of copper nitrate and 80g of basic nickel carbonate, dissolve them in water to prepare an impregnation solution. Impregnate the silica support with the above impregnation solution using the equal volume impregnation method. After uniform impregnation, dry at 80℃ for 2 hours, dry at 120℃ for 4 hours, and then calcine at 600℃ for 5 hours to obtain the catalyst.

[0103] The catalyst contains 0.5 wt% copper and 4 wt% nickel.

[0104] The catalyst reduction treatment and evaluation method in this embodiment are the same as those in Example 11. The specific evaluation results are detailed in Table 1.

[0105] Example 13

[0106] This example is used for the preparation of catalysts:

[0107] The activated carbon carrier in this embodiment has the following physical properties: pore volume of 0.5 cm³. 3 / g, pore size distribution of 5-12nm, average pore size of 8nm, specific surface area of ​​180m² 2 / g.

[0108] Weigh out 80g of copper chloride and 44g of nickel nitrate, dissolve them in water to prepare an impregnation solution. Impregnate the activated carbon support with the above impregnation solution using the equal volume impregnation method. After uniform impregnation, dry at 80℃ for 2h, dry at 120℃ for 4h, and then calcine at 400℃ for 8h to obtain the catalyst.

[0109] The catalyst contains 4 wt% copper and 1.5 wt% nickel.

[0110] The catalyst reduction treatment and evaluation method in this embodiment are the same as those in Example 11. The specific evaluation results are detailed in Table 1.

[0111] Comparative Example 1

[0112] This comparative example is used for catalyst preparation:

[0113] 30g of copper nitrate was dissolved in water to prepare an impregnation solution. The carrier prepared in Example 1 was impregnated with the above impregnation solution using the equal-volume impregnation method. After uniform impregnation, it was dried at 80℃ for 2 hours, dried at 120℃ for 4 hours, and then calcined at 600℃ for 4 hours to obtain the catalyst.

[0114] The catalyst contains 1 wt% copper.

[0115] The catalyst reduction treatment and evaluation method in this comparative example are the same as those in Example 3. The specific evaluation results are detailed in Table 1.

[0116] Comparative Example 2

[0117] This comparative example is used for catalyst preparation:

[0118] 20g of basic nickel carbonate was dissolved in water to prepare an impregnation solution. The carrier prepared in Example 1 was impregnated with the above impregnation solution using the equal-volume impregnation method. After uniform impregnation, it was dried at 80℃ for 2h, dried at 100℃ for 4h, and then calcined at 500℃ for 4h to obtain the catalyst.

[0119] The catalyst contains 1 wt% nickel.

[0120] The catalyst reduction treatment and evaluation method in this comparative example are the same as those in Example 3. The specific evaluation results are detailed in Table 1.

[0121] Comparative Example 3

[0122] This comparative example is used for catalyst preparation:

[0123] 100g of basic nickel carbonate was dissolved in water to prepare an impregnation solution. The carrier prepared in Example 1 was impregnated with the above impregnation solution using the equal-volume impregnation method. After uniform impregnation, it was dried at 80℃ for 2h, dried at 120℃ for 4h, and then calcined at 600℃ for 4h to obtain the catalyst.

[0124] The catalyst contains 5 wt% nickel.

[0125] The catalyst reduction treatment and evaluation method in this comparative example are the same as those in Example 3. The specific evaluation results are detailed in Table 1.

[0126] Comparative Example 4

[0127] This comparative example is used for catalyst preparation:

[0128] 150g of copper nitrate was dissolved in water to prepare an impregnation solution. The carrier prepared in Example 1 was impregnated with the above impregnation solution using the equal-volume impregnation method. After uniform impregnation, it was dried at 80℃ for 2 hours, dried at 120℃ for 4 hours, and then calcined at 700℃ for 4 hours to obtain the catalyst.

[0129] The catalyst contains 5 wt% copper.

[0130] The catalyst reduction treatment and evaluation method in this comparative example are the same as those in Example 3. The specific evaluation results are detailed in Table 1.

[0131] Comparative Example 5

[0132] This comparative example is used for catalyst preparation:

[0133] Weigh 150g of copper nitrate and 100g of basic nickel carbonate, dissolve them in water to prepare an impregnation solution. Impregnate the carrier prepared in Example 1 with the above impregnation solution using the equal volume impregnation method. After uniform impregnation, dry at 80℃ for 2h, dry at 120℃ for 4h, and then calcine at 400℃ for 4h to obtain the catalyst.

[0134] The catalyst contains 5 wt% copper and 5 wt% nickel.

[0135] The catalyst reduction treatment and evaluation method in this comparative example are the same as those in Example 3. The specific evaluation results are detailed in Table 1.

[0136] Table 1 shows the data on the deoxygenation reaction after reduction of the catalysts of Examples 3-13 and Comparative Examples 1-5.

[0137] Catalyst No. | Outlet Oxygen Content (ppm) | Outlet Ethylene Loss (%) | Example 3 | 0.5 | 0.2 | Example 4 | 0.8 | 0.1 | Example 5 | 0.2 | 0.3 | Example 6 | 0.3 | 0.3 | Example 7 | 0.3 | 0.3 | Example 8 | 0.8 | 0.3 | Example 9 | 0.7 | 0.2 | Example 10 | 20.1 | Example 11 | 0.4 | 0.3 | Example 12 | 0.5 | 0.3 | Example 13 | 0.4 | 0.3 | Comparative Example 1 | 12 | 0.2 | Comparative Example 2 | 15 | 0.2 | Comparative Example 3 | 3 | 2.5 | Comparative Example 4 | 5 | 2.8 | Comparative Example 5 | 0.3 | 3.0 surface

[0138] Table 2 shows the data for the deoxygenation reaction of the catalyst in Example 3 at different times.

[0139] Reaction time (h) Outlet oxygen content (ppm): 5000.5, 8000.4, 10000.6, 18000.3, 20000.5, 25000.4 surface

[0140] As can be seen from the evaluation results in Table 1, the catalyst provided in this application has better deoxygenation activity and selectivity compared with the catalyst in the comparative example.

[0141] Specifically, as can be seen from Comparative Examples 1-2 and Example 3, when Comparative Examples 1 and 2 used individual active metal components, the deoxidation effect was significantly less than that of the combination of copper and nickel in Example 1.

[0142] Furthermore, when the content of the active component in the catalyst was increased in Comparative Examples 3 and 4, although the deoxidation effect was increased, it was still not as good as the combination of copper and nickel, and the loss rate of olefins was also increased.

[0143] Furthermore, although the catalyst in Comparative Example 5 used a combination of copper and nickel, when the active component in the catalyst was too high, although the deoxygenation effect was obvious, the loss rate of olefins also increased.

[0144] As can be seen from the data structure in Table 2, the fresh catalyst in Example 3 maintained almost the same continuous deoxygenation effect after 500 hours and more, demonstrating the good stability and durability of the catalyst.

[0145] Furthermore, as can be seen from Examples 11-13, when the hydrogen content in the raw material is high, it also has a good deoxygenation effect, and the reaction process is stable with no temperature runaway phenomenon observed.

[0146] 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 inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. An application of a deoxygenation catalyst, comprising an active component and a support, wherein the active component comprises metallic Cu and metallic Ni; the support is one or a combination of alumina, activated carbon, silica, an alumina-silica composite support, and alumina molecular sieve; the support has the following physical properties: a pore volume of 0.2–0.5 cm³. 3 / g; pore size distribution: 1–12 nm; average pore size: 3–8 nm; specific surface area: 50–200 m² 2 / g; The catalyst is used for deoxygenation and purification of petrochemical dry gas, wherein the ethylene content in the dry gas is 20-50%.

2. The application of the deoxygenation catalyst according to claim 1, characterized in that, In the catalyst, the content of the metal Cu is 0.01 to 4.5 wt%; and / or, the content of the metal Ni is 0.01 to 4.5 wt%.

3. The application of the deoxygenation catalyst according to claim 2, characterized in that, In the catalyst, the content of the metal Cu is 0.5 to 4 wt%; and / or, the content of the metal Ni is 0.5 to 4 wt%.

4. The application of the deoxygenation catalyst according to claim 2, characterized in that, In the catalyst, the content of the metal Cu is 0.5~2.5wt%; and / or, the content of the metal Ni is 0.5~2.5wt%.

5. The application of the deoxygenation catalyst according to claim 1, characterized in that, In the active component, the weight ratio of the metal Cu to the metal Ni is 1:(0.01 to 100).

6. The application of the deoxygenation catalyst according to claim 5, characterized in that, In the active component, the weight ratio of the metal Cu to the metal Ni is 1:(0.1 to 20).

7. The application of the deoxygenation catalyst according to claim 5, characterized in that, In the active component, the weight ratio of the metal Cu to the metal Ni is 1:(0.1 to 10).

8. The application of the deoxygenation catalyst according to claim 1, characterized in that, The carrier is one or a combination of aluminum oxide and silicon dioxide.

9. The application of the deoxygenation catalyst according to claim 8, characterized in that, The aluminum oxide is one or a combination of γ-Al2O3 and α-Al2O3; and / or the aluminum oxide is one or a combination of spherical, strip-shaped, clover-shaped, and columnar shapes.

10. The application of the deoxygenation catalyst according to claim 1, characterized in that, The carrier has the following physical properties: a pore size distribution of 1–10 nm; and / or an average pore size of 3–5 nm; and / or a specific surface area of ​​100–150 m². 2 / g.

11. The application of the deoxygenation catalyst according to any one of claims 1 to 10, wherein the preparation method of the deoxygenation catalyst comprises the following steps: The active component is loaded onto the support, and the deoxygenation catalyst is obtained after drying and calcination.

12. The application of the deoxygenation catalyst according to claim 11, characterized in that, The method includes the following steps: Step 1, dissolving water-soluble copper compound and water-soluble nickel compound separately or together in water to obtain an impregnation solution; Step 2, impregnating the carrier in the impregnation solution of Step 1 or spraying the impregnation solution of Step 1 onto the carrier; Step 3, drying and calcining to obtain the deoxygenation catalyst.

13. The application of the deoxygenation catalyst according to claim 12, characterized in that, In step one, the water-soluble copper compound and the water-soluble nickel compound are derived from one or a combination of water-soluble metal oxides or metal salts.

14. The application of the deoxygenation catalyst according to claim 12, characterized in that, In step one, the water-soluble copper compound is derived from one or a combination of copper chloride, copper nitrate, copper sulfate, and copper acetate; and / or, the water-soluble nickel compound is derived from one or a combination of nickel nitrate, nickel sulfate, and basic nickel carbonate.

15. The application of the deoxygenation catalyst according to claim 12, characterized in that, In step three, the drying conditions are: temperature 80-120℃, time 2-10h; and / or the calcination conditions are: temperature 300-800℃, time 2-10h.

16. The application of the deoxygenation catalyst according to claim 15, characterized in that, In step three, the calcination conditions are: temperature of 400~600℃ and time of 3~8h.

17. The application of the deoxygenation catalyst according to any one of claims 1 to 10, characterized in that, When the catalyst is used for the purification of petrochemical dry gas, the conditions for the catalytic deoxygenation reaction are: a reaction temperature of 100~200℃; and / or a reaction pressure of 1.0~3.0MPa; and / or a feed space velocity of 1000~5000h⁻¹. -1 ; and / or, the hydrogen content is 1~40%.