A hydroprocessing method for producing aviation fuel

Abstract

The present invention relates to a hydroprocessing method for producing aviation kerosene, comprising contacting aviation kerosene raw materials with a hydrodesulfurization catalyst under aviation kerosene hydroprocessing conditions, wherein the hydrodesulfurization catalyst contains an alumina carrier and at least one metal component selected from group VIII and at least one metal component selected from group VIB loaded on the carrier, wherein the alumina carrier is prepared from pseudo-boehmite with high crystallinity and large grains, the pseudo-boehmite has a relative crystallinity of more than 65%, a grain size of 2-5 nm, and a sodium content calculated as oxide of not more than 0.08wt% based on the dry weight of the pseudo-boehmite. The catalyst used in the aviation kerosene hydroprocessing method provided by the present invention adopts a carrier with high pore volume, large pore size and high specific surface area, and compared with the prior art, the catalyst cost is greatly reduced, and when the catalyst of the present invention is applied to aviation kerosene hydroprocessing, the catalytic performance is better than the existing catalyst level.

Description

Technical Field

[0001] The invention belongs to the field of petroleum refining, and in particular relates to a hydrogenation treatment method for producing aviation kerosene. Background Art

[0002] At present, my country's aviation transportation industry maintains rapid development, and the annual consumption of aviation fuel exceeds 30 million tons. Considering the national energy strategic security, we should pay attention to the development of aviation fuel technology. Alumina carrier is an important part of the cost of aviation fuel hydrogenation catalyst. Improving the performance of the carrier and reducing the preparation cost of alumina carrier can greatly improve the market competitiveness of catalysts and aviation fuel production technology.

[0003] In the prior art, sodium aluminate (or sodium aluminate)-carbon dioxide method is usually used to prepare pseudo-boehmite and γ-alumina, which generally includes two processes: gelling and aging. Generally, pseudo-boehmite with high crystallinity is obtained by controlling the pH value of the gelling reaction to about 10.5, but the pore volume of the γ-alumina obtained after calcination is small, generally less than 0.5 ml / g, which greatly limits its application in distillate oil hydrogenation.

[0004] CN103449484A discloses a method for continuously producing pseudo-boehmite, which comprises continuously adding a sodium aluminate solution having a concentration of 15-80 g of aluminum oxide / liter into a reaction device, and simultaneously introducing an air-carbon dioxide mixed gas containing more than 30% by volume of carbon dioxide for sufficient mixing, controlling the flow of the mixed gas and the sodium aluminate solution so that the reaction temperature is 25-55°C and the pH value is 9.5-11, and aging the slurry after passing through a pipeline having a plurality of U-shaped tubes, the aging temperature being not less than 90°C, filtering the slurry after aging and heating, and washing it with water to neutrality, and drying the washed filter cake at 100-120°C to obtain pseudo-boehmite. In the embodiment provided by the method, the pore volume of the aluminum oxide obtained ranges from 0.30 to 0.33 ml / g.

[0005] CN1091428C discloses a method for preparing pseudo-boehmite, which uses a sodium aluminate solution with a concentration of 5-120 g aluminum oxide / liter and a gas with a carbon dioxide content greater than 20% by volume to form gel in an intermittent or continuous manner, with a gelling temperature of 10-100°C, a pH value of 6-9.5 at the gelling end (or process), and a gelling reaction time or residence time of no more than 40 minutes. After the gelling is completed, one or more of an inorganic alkali, an organic alkali and their aqueous solutions are added to raise the slurry pH to 9.5-11.5 or solid-liquid separation and washing are performed rapidly. The method can be used to prepare pseudo-boehmite in a fibrous shape and with high crystallinity, and the γ-alumina pore volume formed after calcination is between 0.5-2.0 ml / g. However, in order to avoid the formation of dawsonite at a lower pH value at the gelling end (or process), the method needs to add alkaline substances during the aging process or immediately perform solid-liquid separation and washing and then aging after gelling, which is a relatively harsh condition and is not suitable for industrial production.

[0006] The alumina prepared from pseudo-boehmite obtained by the existing preparation method has a small pore size and pore volume, resulting in the catalyst performance not meeting specific requirements, or the conditions are harsh, the cost is high, and it is not suitable for industrial production. Summary of the invention

[0007] The object of the present invention is to provide a hydroprocessing method for producing aviation kerosene, comprising contacting aviation kerosene feedstock with a hydrodesulfurization catalyst under aviation kerosene hydroprocessing conditions, wherein the aviation kerosene hydroprocessing conditions are: reaction temperature 200-400°C, hydrogen partial pressure 0.5-6 MPa, volume space velocity 1-10 h -1 , hydrogen-to-oil volume ratio of 30-300; the hydrodesulfurization catalyst contains an alumina carrier and at least one metal component selected from Group VIII and at least one metal component selected from Group VIB loaded on the carrier, wherein the alumina carrier is prepared from a pseudo-boehmite with high crystallinity and large grains, the pseudo-boehmite has a relative crystallinity of higher than 65%, a grain size of 2-5 nm, and a sodium content calculated as oxide of not higher than 0.08wt% based on the dry weight of the pseudo-boehmite.

[0008] The aviation kerosene hydroprocessing method provided by the present invention adopts a low-cost, high-performance hydrodesulfurization catalyst, which uses a carrier prepared from pseudo-boehmite with high crystallinity and large grains as a carrier. Compared with the prior art, the preparation costs of the carrier and the catalyst are greatly reduced. When the catalyst of the present invention is applied to aviation kerosene production, the desulfurization performance is better than the existing catalyst level, and aviation kerosene products with various indicators such as sulfur content that meet the requirements can be produced. DETAILED DESCRIPTION

[0009] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be regarded as specifically disclosed in this article. In the present invention, unless otherwise specified, room temperature refers to 25°C.

[0010] As described above, the present invention provides a hydroprocessing method for producing aviation kerosene, wherein there are no specific requirements for the aviation kerosene raw materials, and any aviation kerosene raw materials that meet the conventional index requirements can be used. Preferably, the aviation kerosene raw material has a sulfur content of 200-5000 μg / g, a mercaptan sulfur content of 20-200 μg / g, an initial distillation point of 120-180°C, and a final distillation point of 220-280°C; preferably, the aviation kerosene raw material has a sulfur content of 300-4000 μg / g, a mercaptan sulfur content of 40-180 μg / g, an initial distillation point of 140-180°C, and a final distillation point of 240-260°C.

[0011] According to the method of the present invention, under the premise that the hydrodesulfurization catalyst carrier meets the requirements of the present invention, the metal components, additives and contents thereof are all conventionally selected in the art. For example, the metal component of Group VIII may be cobalt and / or nickel, and the metal component of Group VIB may be molybdenum and / or tungsten; the carrier and metal content in the catalyst are conventional contents, generally, the content of the metal component of Group VIII is 1-10% by weight, preferably 1.5-5% by weight, calculated as oxide and based on the catalyst, the content of the metal component of Group VIII is 4-50% by weight, preferably 6-35% by weight, and the balance is the balance of the carrier and the optional additives.

[0012] According to the present invention, further controlling the performance parameters of pseudo-boehmite can make the catalyst performance better and obtain higher quality jet fuel, for example, lower sulfur content. Preferably, the relative crystallinity of the pseudo-boehmite in the present invention is 65-95%, preferably 70-90%, the grain size is 3-4.5nm, preferably 3.3-4nm, and the sodium content based on the dry weight of the pseudo-boehmite and calculated as oxide is not higher than 0.06wt%, preferably 0.01-0.05wt%; further, the pseudo-boehmite can also contain various additives for improving product performance, such as metal additives, non-metallic additives, etc. Preferably, the additive is one or more of phosphorus, boron, titanium, and magnesium, and the additive content based on the dry weight of the pseudo-boehmite and calculated as oxide is 0.3-8wt%, preferably 0.4-6wt%.

[0013] On the premise of providing pseudo-boehmite that meets the requirements of the present invention, the present invention does not particularly limit the method for preparing the pseudo-boehmite. The present invention provides a preferred embodiment. Specifically, the preparation method of the pseudo-boehmite may include the following steps:

[0014] (1) Gelation: contacting a solution of sodium metaaluminate and / or sodium aluminate with a gas containing carbon dioxide to carry out a gelation reaction to obtain a solid gelation product;

[0015] (2) aging: subjecting the solid gelled product to a first aging and a second aging in sequence to obtain an aged mixture; the temperature of the second aging is higher than the temperature of the first aging;

[0016] (3) Separation and drying: The aged mixture is subjected to solid-liquid separation to obtain a solid aged product, and the solid aged product is dried to obtain the pseudo-boehmite.

[0017] When the pseudo-boehmite is required to contain an additive, the step (1) and / or (2) also includes the step of adding the additive, wherein the additive comprises one or more of phosphorus, boron, titanium and magnesium, and the additive is used in such an amount that the final additive content based on the pseudo-boehmite on a dry basis and calculated as oxide is 0.3-8wt%, preferably 0.4-6wt%.

[0018] The various additives are introduced by adding compounds containing the above-mentioned additive elements in step (1) and / or step (2), for example, compounds selected from boric acid, borax, ammonium borate, phosphoric acid, ammonium hydrogen phosphate, ammonium phosphate, sodium phosphate, and the magnesium-containing compound is selected from one or more of magnesium-containing oxides, alkalis and salts, titanium oxide, and titanates.

[0019] The inventors of the present invention have found that, without adding additives (such as soluble cellulose derivatives, soluble starch derivatives), by changing the aging process on the basis of the prior art, that is, subjecting the solid gelled product to two-stage aging, a pseudo-boehmite with better quality can be obtained. The two-stage aging described in the present invention includes subjecting the solid gelled product to a first aging at a relatively low temperature, and then subjecting the solid gelled product to a second aging at a higher temperature. The pseudo-boehmite obtained by this method is obtained by calcining an alumina having a larger pore volume and pore diameter. The carrier prepared with the pseudo-boehmite as a raw material has a high specific surface area and a large pore diameter, and is particularly suitable for a carrier of a heavy oil and residual oil hydrogenation catalyst. The catalyst of the present invention is compared with a catalyst prepared by similar pseudo-boehmite or alumina obtained by other methods in the prior art. The performance of the present invention is not only superior to that of the prior art, but the cost of preparing the pseudo-boehmite of the present invention is lower and the conditions are more relaxed.

[0020] According to the present invention, preferably, the gelling reaction in step (1) is carried out in a continuous or intermittent manner. Further preferably, the gelling reaction is carried out in a continuous manner. On the one hand, the gelling reaction carried out in a continuous manner is more conducive to controlling the pH of the gelling reaction process, thereby being more conducive to improving the quality of the pseudo-boehmite. On the other hand, continuous operation can increase the processing volume per unit time and improve production efficiency. The present invention does not particularly limit the equipment for the gelling reaction, which can be a conventional choice in the field. Specifically, for example, it can be carried out in a gelling tank. According to a preferred specific embodiment of the present invention, the process of carrying out the gelling reaction in a continuous manner in the present invention includes: adding a certain amount of deionized water in advance to the gelling tank, introducing the gas containing carbon dioxide from the bottom of the gelling tank, and introducing the sodium aluminate and / or sodium aluminate solution from the top of the gelling tank, so that the sodium aluminate and / or sodium aluminate solution is continuously in countercurrent contact with the gas containing carbon dioxide, and the slurry generated by the gelling reaction continuously flows out of the gelling tank, and the liquid level in the gelling tank is controlled to remain unchanged.

[0021] In order to further improve the performance of pseudo-boehmite, the preparation conditions can be further optimized as follows:

[0022] A low pH value in the gelling reaction of step (1) is likely to lead to the formation of dawsonite, which is insoluble in water and cannot be removed in the subsequent process, thus causing a high content of sodium oxide in pseudo-boehmite, thereby affecting the quality of the product; the pH value of the gelling reaction process should not be too high, for example, not higher than 10. Since a higher pH value in the gelling reaction process is likely to lead to the formation of alumina trihydrate seeds, which will continue to grow in the subsequent aging process, the alumina trihydrate content of the product is relatively high, resulting in low pore volume and specific surface area of ​​the alumina product, thereby affecting the quality of the product. The solution of sodium metaaluminate and / or sodium aluminate is continuously contacted with a gas containing carbon dioxide in countercurrent, and the preferred conditions for the gelling reaction include: a pH value of 7-10, preferably 7.5-9.5; a residence time of 2-60 min, preferably 7-50 min; a temperature of 30-95°C, preferably 35-85°C.

[0023] In terms of alumina, the concentration of the solution of sodium metaaluminate and / or sodium aluminate is 5-40g / L, preferably 8-35g / L; in the gas containing carbon dioxide, the volume content of carbon dioxide is greater than 20 volume%, preferably greater than 30 volume%. In the present invention, the content of carbon dioxide in the gas containing carbon dioxide is selected in a wide range, for example, the content of carbon dioxide in the gas containing carbon dioxide can be greater than 5 volume%. In order to improve the reaction efficiency, preferably, in the gas containing carbon dioxide, the volume content of carbon dioxide is greater than 20 volume%, preferably greater than 30 volume%, and more preferably 30-100 volume%. In the embodiment of the present invention, 99 volume% is used as an example for exemplary description, and the present invention is not limited thereto. In addition, in addition to carbon dioxide, the gas containing carbon dioxide may also contain an inert gas or air, and the inert gas includes but is not limited to at least one of nitrogen, argon and helium.

[0024] According to the present invention, after the gelling reaction, step (1) further comprises subjecting the product of the gelling reaction to solid-liquid separation to obtain the solid gelling product. In the present invention, the solid-liquid separation is a conventional operation in the art, specifically, for example, it can be at least one of sedimentation, filtration and centrifugal separation. Those skilled in the art can select as needed according to actual needs.

[0025] Step (2) includes: subjecting the solid gelled product to a first aging to obtain a first aged product, and subjecting the first aged product to a second aging by slurrying with water to obtain an aged mixture; or, step (2) includes: subjecting the solid gelled product to a slurrying with water, and subjecting it to a first aging to obtain a first aged product, and subjecting the first aged product to a second aging to obtain an aged mixture.

[0026] The temperature of the second aging is 10-100°C higher than the temperature of the first aging, preferably 25-85°C higher, and more preferably 45-60°C higher. The conditions of the first aging include: temperature of 0-45°C, preferably 10-40°C; time of 2-240h, preferably 4-120h; the conditions of the second aging include: temperature of 50-100°C, preferably 65-95°C; time of 1-24h, preferably 2-12h. The inventors of the present invention have found that by controlling the conditions of the first aging including temperature and time, the average pore diameter and pore volume of alumina obtained by calcining the obtained pseudo-boehmite can be better regulated, and the use of a preferred embodiment is more conducive to further improving the pore volume and pore diameter of alumina obtained from the obtained pseudo-boehmite.

[0027] In order to avoid the introduction of impurities and thus the influence on the subsequently obtained alumina and catalyst, preferably, the water used in the preparation process of the present invention is deionized water.

[0028] In the present invention, the solid-liquid separation in step (3) is not particularly limited. Specifically, for example, it can be at least one of sedimentation, filtration and centrifugal separation. Those skilled in the art can make a selection according to actual needs.

[0029] According to the present invention, preferably, before the drying, step (3) further comprises washing the solid aged product. In the present invention, the washing operation can be a conventional operation in the art, and those skilled in the art can select it as needed according to actual needs, as long as the content of impurity ions in the solid aged product can be reduced, for example, the content of sodium oxide in the alumina obtained by roasting the pseudo-boehmite is less than 0.1% by weight, preferably less than 0.06% by weight, and more preferably 0.01-0.05% by weight.

[0030] In the present invention, the drying is a conventional operation in the art, as long as the free water contained in the pseudo-boehmite can be removed. The present invention has a wide range of drying conditions, and the drying temperature can be between room temperature and the crystal transformation temperature of the pseudo-boehmite. Preferably, the drying temperature is 60-200°C, and more preferably 100-180°C.

[0031] The pseudo-boehmite prepared by the method of the present invention has a larger grain size and a lower sodium oxide content. Preferably, no dawsonite is detected in the pseudo-boehmite prepared by the method of the present invention, indicating that the pseudo-boehmite prepared by the method of the present invention does not contain or contains a very small amount (less than the minimum detection value) of dawsonite.

[0032] Therefore, the relative crystallinity of the pseudo-boehmite obtained in step (3) (based on the commercial SB powder of Condea Company) is preferably 65-95% by weight, more preferably 70-90% by weight, and the grain size is 3-4.5 nm; the grain size of the pseudo-boehmite is preferably 3.3-4 nm.

[0033] In the present invention, the relative crystallinity and grain size of pseudo-boehmite and the content of dawsonite can be measured by X-ray diffraction (XRD).

[0034] Preferably, the sodium content calculated as oxide is 0.01-0.05% by weight based on the dry weight of the pseudo-boehmite. The dry weight of the pseudo-boehmite refers to the weight of the pseudo-boehmite calcined at 550° C. for 5 hours.

[0035] According to the present invention, the pseudo-boehmite as a carrier raw material can be calcined to obtain a high pore volume alumina, preferably γ alumina. The obtained alumina has a pore volume of 0.8-1.3 mL / g, an average pore diameter of more than 14 nm, and a specific surface area of ​​200-260 m 2 / g; preferably, the alumina pore volume obtained after the pseudo-boehmite is calcined is 0.9-1.2mL / g, the average pore diameter is greater than 15nm, and the specific surface area is 210-255m 2 / g; the calcination conditions include: a temperature of 500-1200°C and a time of 2-8 hours; preferably, the calcination conditions include: a temperature of 550-850°C and a time of 3-6 hours. In the prior art, without adding other additives, the pore volume of alumina obtained by calcining pseudo-boehmite obtained by the sodium aluminate (or sodium aluminate)-carbon dioxide method is generally less than 0.5 ml / g. According to a preferred embodiment of the present invention, the average pore diameter of the alumina is 16-20nm, and the specific surface area of ​​the alumina is 210-255m 2 / g. In this preferred case, the performance of the alumina is better, and the pseudo-boehmite as a raw material is more suitable as a raw material for a heavy oil hydroprocessing catalyst carrier. The pore volume, average pore diameter and specific surface area of ​​the alumina can be measured by a low-temperature nitrogen adsorption method.

[0036] The method of using the above-mentioned pseudo-boehmite to prepare the alumina carrier of the present invention is a conventional method, for example, the pseudo-boehmite is mixed with other substances and then extruded to form, or it may not be formed. In the present invention, the molding method can be conventionally selected in the art, such as the pseudo-boehmite can be mixed with an appropriate amount of water (preferably deionized water) and extruded to form, or the pseudo-boehmite can be mixed with an appropriate amount of extrusion aid and / or adhesive and an appropriate amount of water (preferably deionized water), and then extruded to form. In the present invention, the extrusion aid and peptizing agent can be of the types and amounts commonly used in the art.

[0037] The alumina carrier obtained by the method of the present invention has the characteristics of large specific surface area and high pore volume. Generally, the specific surface area of ​​the alumina carrier is 200-300m 2 / g, preferably 220-280m 2 / g, the pore volume is above 0.6mL / g, preferably 0.65-0.75mL / g, and the most probable pore diameter is 7.5-12nm, preferably 8-11nm.

[0038] The catalyst provided by the present invention can be prepared by conventional methods in the art. For example, the preparation method comprises: preparing a molded alumina carrier, and introducing at least one metal component selected from Group VIII and at least one metal component selected from Group VIB into the alumina carrier. The molding can be carried out according to conventional methods, such as tableting, ball rolling, extrusion and the like. In order to ensure the smooth molding, it is usually necessary to introduce additives and water into the material (here, pseudo-boehmite) during molding. For example, when the extrusion method is used for molding, the pseudo-boehmite is mixed with an appropriate amount of water, a peptizing agent (such as one or more selected from nitric acid, acetic acid and citric acid), and an extrusion aid (such as one or more selected from sesbania powder and cellulose), and then extruded. The molded product is dried and calcined to obtain a carrier. The drying is a conventional method, such as drying in an oven, a mesh belt kiln and a fluidized bed. When drying is carried out by heating, the preferred drying temperature is 50-200°C and the drying time is 0.3-6 hours. It is further preferred that the drying temperature is 60-150°C and the drying time is 0.5-2 hours. The calcination method and conditions are the conventional methods and conditions used in the preparation of catalyst carriers, such as using a mesh belt kiln, a vertical furnace and a converter for calcination. The calcination conditions are preferably calcined at a temperature of 400-1200°C for 1-6 hours, and more preferably calcined at a temperature of 500-1100°C for 2-4 hours.

[0039] Under the premise that the metal components selected from at least one of the VIB group and at least one of the VIII group are loaded on the alumina, any known method for preparing hydrogenation catalysts can be used for preparation. For example, under conditions sufficient to deposit an effective amount of nickel and / or cobalt metal components selected from the VIII group on the carrier, the carrier is contacted with a solution containing an effective amount of a compound containing nickel and / or cobalt metal components selected from the VIII group, such as by impregnation, coprecipitation and the like, preferably impregnation, followed by drying, calcination or non-calcination. The drying conditions are the conditions commonly used in the preparation of such catalysts, such as a drying temperature of 80-350°C, preferably 100-300°C, and a drying time of 1-24 hours, preferably 2-12 hours. When the catalyst needs to be calcined, the temperature is preferably 100-700°C, and the calcination time is 1-6 hours. The further preferred temperature is preferably 200-500°C, and the calcination time is 2-4 hours.

[0040] The Group VIII metal compound is selected from one or more soluble compounds of Group VIII metals, such as one or more nitrates, acetates, soluble carbonates, chlorides, and soluble complexes of cobalt and / or nickel metals.

[0041] The VIB group metal compound is selected from one or more of the VIB group metal soluble compounds, such as one or more of molybdate, tungstate, metatungstate, and ethyl metatungstate.

[0042] The catalyst provided by the present invention may also contain any substance that does not affect the catalytic performance of the catalyst provided by the present invention or can improve the catalytic performance of the catalyst provided by the present invention. For example, components such as silicon may be introduced, and the amount of the above-mentioned auxiliary agent introduced is 0-10% by weight, preferably 0.5-5% by weight, calculated as an element and based on the catalyst.

[0043] When the catalyst also contains components such as silicon, the introduction method thereof may be to directly mix the compound containing the auxiliary agent with pseudo-boehmite, form and roast; or to prepare a mixed solution of the compound containing the auxiliary agent and the compound containing the hydrogenation active metal component and then contact the alumina carrier; or to prepare a solution of the compound containing the auxiliary agent separately and then contact the alumina carrier and roast. When the auxiliary agent and the second hydrogenation active metal are introduced into the alumina carrier separately, it is preferred that the solution containing the auxiliary agent compound is first contacted with the alumina carrier and roasted, and then contacted with the solution of the compound containing the hydrogenation active metal component, for example, by ion exchange, impregnation, coprecipitation and the like, preferably impregnation, the roasting temperature is 250-600°C, preferably 350-500°C, and the roasting time is 2-8 hours, preferably 3-6 hours.

[0044] The method of the present invention can be carried out in any reaction vessel sufficient to allow the jet fuel feedstock to contact and react with the hydrodesulfurization catalyst under reaction conditions, for example, in the fixed bed reactor, moving bed reactor or ebullating bed reactor.

[0045] According to conventional methods in the art, the hydrodesulfurization catalyst can be pre-sulfurized with sulfur, hydrogen sulfide or sulfur-containing raw materials in the presence of hydrogen at a temperature of 140-370°C before use. This pre-sulfurization can be carried out outside the device or in situ inside the device to convert the active metal components carried by it into metal sulfide components, and then the aviation kerosene hydrogenation reaction is carried out.

[0046] The following examples will further illustrate the present invention.

[0047] Unless otherwise specified, all reagents used in the examples are chemically pure.

[0048] In the following preparation examples, the crystallinity, grain size and content of pseudo-boehmite were determined by X-ray diffraction (XRD). The crystallinity of the pseudo-boehmite is relative crystallinity, and aluminum hydroxide produced by Condea of ​​Germany with a brand of SB is used as a standard sample. The SB crystallinity is 100%, and the measurement is performed on a D5005 diffractometer of Siemens of Germany. The sodium oxide content is measured by X-ray fluorescence spectrometry (XRF) on a 3271 X-ray fluorescence spectrometer of Rigaku Corporation of Japan. The specific surface area and pore volume are measured by an ASAP2420 nitrogen adsorption instrument produced by Micromeritics of the United States.

[0049] Preparation Examples 1-15 and Comparative Preparation Examples 1-4 describe the preparation methods of pseudo-boehmite and the obtained pseudo-boehmite.

[0050] Preparation Example 1

[0051] According to the method provided by the present invention, pseudo-boehmite and alumina are prepared, and the specific steps are as follows:

[0052] (1) 3 L of deionized water is added to the gelling tank in advance, and a carbon dioxide-containing gas (a mixture of carbon dioxide and air with a carbon dioxide content of 99% by volume) is introduced from the bottom of the gelling tank, and a sodium aluminate solution is introduced from the top of the gelling tank, so that the sodium aluminate solution and the carbon dioxide-containing gas are in countercurrent contact to perform a gelling reaction, and the slurry after the gelling reaction flows out from the overflow pipe of the gelling tank, and the liquid level in the gelling tank remains unchanged. When the deionized water added in advance is replaced by the slurry after the gelling reaction, the slurry is collected, and then filtered to obtain a filter cake (solid gelling product);

[0053] The concentration of sodium aluminate solution (calculated as alumina) is 30 g / L, the flow rate is 60 mL / min, and the residence time is 50 minutes. The pH value of the gelling reaction process is about 7.5 by adjusting the gas dosage. The temperature of the gelling reaction is 35°C.

[0054] (2) subjecting the filter cake to a first aging process at a temperature of 35° C. for 24 h to obtain a first aging product, adding the first aging product to deionized water for slurrying to obtain a slurry, wherein the concentration of the slurry is 100 g / L based on alumina, and then subjecting the filter cake to a second aging process at a temperature of 90° C. for 2 h to obtain an aged mixture;

[0055] (3) filtering and washing the aged mixture in sequence (the amount of washing water (deionized water) is 100 times the mass of the product obtained by filtration), and then drying at 120° C. for 8 h;

[0056] Pseudo-boehmite N1 was obtained; the obtained pseudo-boehmite was calcined at 550°C for 5h to obtain alumina A1. The specific physicochemical properties are listed in Table 1.

[0057] Preparation Comparative Example 1

[0058] Pseudo-boehmite and alumina were prepared according to the method of Preparation Example 1, except that in step (2), the first aging was not performed, and the filter cake was directly mixed with deionized water and slurried to obtain a slurry with a concentration of 100 g / L based on alumina. The slurry was then aged at 90° C. for 2 h to obtain pseudo-boehmite DN1 and alumina DA1. The specific physicochemical properties are listed in Table 1.

[0059] Preparation Example 2

[0060] According to the method provided by the present invention, pseudo-boehmite and alumina are prepared, and the specific steps are as follows:

[0061] (1) The same as step (1) of Preparation Example 1;

[0062] (2) subjecting the filter cake to a first aging process at a temperature of 30° C. for 240 h to obtain a first aging product, adding the first aging product to deionized water for slurrying to obtain a slurry, wherein the concentration of the slurry is 100 g / L based on alumina, and then subjecting the filter cake to a second aging process at a temperature of 90° C. for 2 h to obtain an aged mixture;

[0063] (3) The same as step (3) of Preparation Example 1;

[0064] Pseudo-boehmite N2 was obtained; the obtained pseudo-boehmite was calcined at 550°C for 5h to obtain alumina A2. The specific physicochemical properties are listed in Table 1.

[0065] Preparation Example 3

[0066] According to the method provided by the present invention, pseudo-boehmite and alumina are prepared, and the specific steps are as follows:

[0067] (1) The same as step (1) of Preparation Example 1;

[0068] (2) adding deionized water to the filter cake to obtain a slurry, wherein the concentration of the slurry is 100 g / L in terms of alumina, and then performing a first aging process at a temperature of 45° C. for 12 h to obtain a first aging product; and then performing a second aging process at a temperature of 90° C. for 2 h to obtain an aging mixture;

[0069] (3) The same as step (3) of Preparation Example 1;

[0070] Pseudo-boehmite N3 was obtained; the obtained pseudo-boehmite was calcined at 550°C for 5h to obtain alumina A3, and the specific physicochemical properties are listed in Table 1.

[0071] Preparation Example 4

[0072] According to the method provided by the present invention, pseudo-boehmite and alumina are prepared, and the specific steps are as follows:

[0073] (1) 3 L of deionized water is added to the gelling tank in advance, and a carbon dioxide-containing gas (a mixture of carbon dioxide and air with a carbon dioxide content of 99% by volume) is introduced from the bottom of the gelling tank, and a sodium aluminate solution is introduced from the top of the gelling tank, so that the sodium aluminate solution and the carbon dioxide-containing gas are in countercurrent contact to perform a gelling reaction, and the slurry after the gelling reaction flows out from the overflow pipe of the gelling tank, and the liquid level in the gelling tank remains unchanged. When the deionized water added in advance is replaced by the slurry after the gelling reaction, the slurry is collected, and then filtered to obtain a filter cake (solid gelling product);

[0074] The concentration of sodium aluminate solution (calculated as alumina) is 10 g / L, the flow rate is 300 mL / min, and the residence time is 10 minutes. The pH value of the gelling reaction process is about 8.8 by adjusting the gas dosage. The temperature of the gelling reaction is 55°C.

[0075] (2) subjecting the filter cake to a first aging process at a temperature of 40° C. for 120 h to obtain a first aging product, adding the first aging product to deionized water for slurrying to obtain a slurry, wherein the concentration of the slurry is 100 g / L based on alumina, and then subjecting the filter cake to a second aging process at a temperature of 90° C. for 2 h to obtain an aged mixture;

[0076] (3) filtering and washing the aged mixture in sequence (the amount of washing water (deionized water) is 100 times the mass of the product obtained by filtration), and then drying at 120° C. for 8 h;

[0077] Pseudo-boehmite N4 was obtained; the obtained pseudo-boehmite was calcined at 550°C for 5h to obtain alumina A4, and the specific physicochemical properties are listed in Table 1.

[0078] Preparation Comparative Example 2

[0079] Pseudo-boehmite and alumina were prepared according to the method of Preparation Example 4, except that in step (2), the first aging was not performed, and the filter cake was directly mixed with deionized water and slurried to obtain a slurry with a concentration of 100 g / L in terms of alumina. The slurry was then aged at 90°C for 2 h to obtain pseudo-boehmite DN2; the obtained pseudo-boehmite was calcined at 550°C for 5 h to obtain alumina DA2. The specific physicochemical properties are listed in Table 1.

[0080] Preparation Example 5

[0081] According to the method provided by the present invention, pseudo-boehmite and alumina are prepared, and the specific steps are as follows:

[0082] (1) The same as step (1) of Preparation Example 4;

[0083] (2) subjecting the filter cake to a first aging process at a temperature of 30° C. for 48 h to obtain a first aging product, adding the first aging product to deionized water for slurrying to obtain a slurry, wherein the concentration of the slurry is 100 g / L based on alumina, and then subjecting the filter cake to a second aging process at a temperature of 90° C. for 2 h to obtain an aged mixture;

[0084] (3) Same as step (3) of Preparation Example 4;

[0085] Pseudo-boehmite N5 was obtained; the obtained pseudo-boehmite was calcined at 550°C for 5h to obtain alumina A5. The specific physicochemical properties are listed in Table 1.

[0086] Preparation Example 6

[0087] According to the method provided by the present invention, pseudo-boehmite and alumina are prepared, and the specific steps are as follows:

[0088] (1) The same as step (1) of Preparation Example 4;

[0089] (2) adding deionized water to the filter cake for slurrying to obtain a slurry, wherein the concentration of the slurry is 100 g / L in terms of alumina, and performing a first aging process at a temperature of 45° C. for 24 h to obtain a first aging product; and then performing a second aging process at a temperature of 90° C. for 2 h to obtain an aging mixture;

[0090] (3) Same as step (3) of Preparation Example 4;

[0091] Pseudo-boehmite N6 was obtained; the obtained pseudo-boehmite was calcined at 550°C for 5h to obtain alumina A6. The specific physicochemical properties are listed in Table 1.

[0092] Preparation Example 7

[0093] According to the method provided by the present invention, pseudo-boehmite and alumina are prepared, and the specific steps are as follows:

[0094] (1) 3 L of deionized water is added to the gelling tank in advance, and a carbon dioxide-containing gas (a mixture of carbon dioxide and air with a carbon dioxide content of 99% by volume) is introduced from the bottom of the gelling tank, and a sodium aluminate solution is introduced from the top of the gelling tank, so that the sodium aluminate solution and the carbon dioxide-containing gas are in countercurrent contact to perform a gelling reaction, and the slurry after the gelling reaction flows out from the overflow pipe of the gelling tank, and the liquid level in the gelling tank remains unchanged. When the deionized water added in advance is replaced by the slurry after the gelling reaction, the slurry is collected, and then filtered to obtain a filter cake (solid gelling product);

[0095] The concentration of sodium aluminate solution (calculated as alumina) is 15 g / L, the flow rate is 200 mL / min, and the residence time is 15 minutes. The pH value of the gelling reaction process is about 8.3 by adjusting the gas dosage. The temperature of the gelling reaction is 72°C.

[0096] (2) subjecting the filter cake to a first aging process at a temperature of 40° C. for 24 h to obtain a first aging product, adding the first aging product to deionized water for slurrying to obtain a slurry, wherein the concentration of the slurry is 100 g / L based on alumina, and then subjecting the filter cake to a second aging process at a temperature of 90° C. for 2 h to obtain an aged mixture;

[0097] (3) filtering and washing the aged mixture in sequence (the amount of washing water (deionized water) is 100 times the mass of the product obtained by filtration), and then drying at 120° C. for 8 h;

[0098] Pseudo-boehmite N7 was obtained; the obtained pseudo-boehmite was calcined at 550°C for 5h to obtain alumina A7. The specific physicochemical properties are listed in Table 1.

[0099] Preparation Comparative Example 3

[0100] The preparation of pseudo-boehmite and alumina is carried out according to the following method, and the specific steps are:

[0101] Pseudo-boehmite and alumina were prepared according to the method of Preparation Example 7, except that in step (2), the first aging was not performed, and the filter cake was directly mixed with deionized water and slurried to obtain a slurry with a concentration of 80 g / L based on alumina. The slurry was then aged at 90°C for 2 h to obtain pseudo-boehmite DN3 and alumina DA3. The specific physicochemical properties are listed in Table 1.

[0102] Preparation Comparative Example 4

[0103] Pseudo-boehmite and alumina were prepared according to the method of Comparative Example 3, except that the aging time at 90° C. was 26 h.

[0104] Pseudo-boehmite DN4 and alumina DA4 were obtained, and their specific physical and chemical properties are listed in Table 1.

[0105] Preparation Example 8

[0106] According to the method provided by the present invention, pseudo-boehmite and alumina are prepared, and the specific steps are as follows:

[0107] (1) The same as step (1) of Preparation Example 7;

[0108] (2) subjecting the filter cake to a first aging process at a temperature of 25° C. for 300 h to obtain a first aging product, adding the first aging product to deionized water for slurrying to obtain a slurry, wherein the concentration of the slurry is 80 g / L based on alumina, and then subjecting the filter cake to a second aging process at a temperature of 70° C. for 6 h to obtain an aged mixture;

[0109] (3) Same as step (3) of Preparation Example 7;

[0110] Pseudo-boehmite N8 was obtained; the obtained pseudo-boehmite was calcined at 650°C for 4h to obtain alumina A8. The specific physicochemical properties are listed in Table 1.

[0111] Preparation Example 9

[0112] According to the method provided by the present invention, pseudo-boehmite and alumina are prepared, and the specific steps are as follows:

[0113] (1) The same as step (1) of Preparation Example 7;

[0114] (2) adding deionized water to the filter cake to obtain a slurry, wherein the concentration of the slurry is 150 g / L in terms of alumina, and performing a first aging process at a temperature of 45° C. for 48 h to obtain a first aging product; and then performing a second aging process at a temperature of 80° C. for 4 h to obtain an aging mixture;

[0115] (3) Same as step (3) of Preparation Example 7;

[0116] Pseudo-boehmite N9 was obtained; the obtained pseudo-boehmite was calcined at 550°C for 5h to obtain alumina A9. The specific physicochemical properties are listed in Table 1.

[0117] Preparation Example 10

[0118] Pseudo-boehmite and alumina were prepared in the same manner as in Preparation Example 7, except that:

[0119] In step (1), the amount of gas is adjusted so that the pH value of the gelling reaction process is about 10.5;

[0120] Step (2) and step (3) are the same as those in Preparation Example 7;

[0121] Pseudoboehmite N 10 The obtained pseudo-boehmite was calcined at 550°C for 5h to obtain alumina A 10 The specific physical and chemical properties are listed in Table 1.

[0122] Preparation Example 11

[0123] Pseudo-boehmite and alumina were prepared in the same manner as in Preparation Example 7, except that:

[0124] In step (1), the temperature of the gelling reaction is 97°C;

[0125] Step (2) and step (3) are the same as those in Preparation Example 7;

[0126] Pseudoboehmite N 11 The obtained pseudo-boehmite was calcined at 550°C for 5h to obtain alumina A 11 The specific physical and chemical properties are listed in Table 1.

[0127] Preparation Example 12

[0128] Pseudo-boehmite and alumina were prepared in the same manner as in Preparation Example 7, except that:

[0129] In step (2), the first aging temperature is 60° C.

[0130] Step (1) and step (3) are the same as those in Preparation Example 7;

[0131] Pseudoboehmite N 12 The obtained pseudo-boehmite was calcined at 550°C for 5h to obtain alumina A 12 , the specific physical and chemical properties are listed in Table 1.

[0132] Preparation Example 13

[0133] The same as Preparation Example 1, the only difference is that the boric acid concentration in the sodium aluminate solution in the gelling reaction is 1.5 g boric acid / L. 13 The obtained pseudo-boehmite was calcined at 550°C for 5h to obtain alumina A 13 . With N 13 Based on dry basis, the boron content calculated as boron trioxide is 0.3%. The specific physical and chemical properties are shown in Table 1.

[0134] Preparation Example 14

[0135] The same as Preparation Example 1, the only difference is that the sodium aluminate solution in the gelling reaction contains 12 mL of concentrated phosphoric acid and 16 g of magnesium nitrate. 14The obtained pseudo-boehmite was calcined at 550°C for 5h to obtain alumina A 14 . With N 14 On a dry basis, the magnesium content is 1.0% as magnesium oxide, and the phosphorus content is 3.2% as phosphorus pentoxide. The specific physical and chemical properties are shown in Table 1.

[0136] Preparation Example 15

[0137] The same as Preparation Example 1, the only difference is that the sodium aluminate solution in the colloid reaction contains 10 mL of concentrated phosphoric acid and 1 gram of titanium dioxide. 15 The obtained pseudo-boehmite was calcined at 550°C for 5h to obtain alumina A 15 . With N 15 On a dry basis, the titanium content calculated as titanium dioxide is 0.4%, and the phosphorus content calculated as phosphorus pentoxide is 2.8%. The specific physical and chemical properties are shown in Table 1.

[0138] Table 1

[0139]

[0140] Table 1

[0141]

[0142] Table 1

[0143]

[0144] Note: “-” means the content was not detected.

[0145] It can be seen from the results in Table 1 that, compared with Comparative Examples 1-4 using the traditional aging method, the pseudo-boehmite prepared by the method of the present invention has a higher relative crystallinity, up to 90% by weight; a larger grain size, up to 3.9 nm; a lower sodium oxide content, and no dawsonite was detected; the average pore diameter of alumina prepared by the pseudo-boehmite is larger, up to 19.6 nm; and a larger pore volume, up to 1.18 mL / g.

[0146] Catalyst Preparation Examples 1-8 and Catalyst Preparation Comparative Examples 1-5 describe the preparation method of the hydrodesulfurization catalyst and the obtained hydrodesulfurization catalyst.

[0147] Catalyst Preparation Example 1

[0148] Take 300 grams of pseudo-boehmite N1 and 9 grams of sesbania powder and mix them evenly. At room temperature, mix the mixture with 260 ml of 1% nitric acid aqueous solution, continue to knead it into a plastic body on a twin-screw extruder, and extrude it into butterfly-shaped strips with a diameter of ф1.4 mm. After the wet strips are dried at 120°C for 4 hours, they are calcined at 600°C for 3 hours to obtain carrier Z1. The properties of carrier Z1 are shown in Table 2.

[0149] 200 g of carrier Z1 was impregnated with 180 ml of a mixed solution of ammonium molybdate and cobalt nitrate with a MoO3 content of 195 g / L and a CoO content of 60 g / L for 1 hour, dried at 120°C for 2 hours, and calcined at 580°C for 3 hours to obtain catalyst C1. The contents of molybdenum oxide and cobalt oxide in catalyst C1 were determined by X-ray fluorescence method based on the total weight of the catalyst (for specific methods, see petrochemical analysis method RIPP133-90), and the results are shown in Table 3.

[0150] Catalyst Preparation Example 2

[0151] Take 300g of pseudo-boehmite N4 and 9g of sesbania powder and mix them evenly. At room temperature, mix the mixture with 270ml of 1% nitric acid aqueous solution, continue to knead it into a plastic body on a twin-screw extruder, and extrude it into butterfly-shaped strips with a diameter of ф1.4 mm. After the wet strips are dried at 120°C for 4 hours, they are calcined at 600°C for 3 hours to obtain carrier Z2. The properties of carrier Z2 are shown in Table 2.

[0152] Take 200g of carrier Z2, impregnate it with 190ml of ammonium molybdate solution with MoO3 content of 176g / L for 1 hour, dry it at 120℃ for 2 hours, and calcine it at 420℃ for 3 hours to obtain semi-finished catalyst Z2-C2; impregnate Z2-C2 with 190ml of nickel nitrate solution with NiO content of 51g / L for 1 hour, dry it at 120℃ for 2 hours, and calcine it at 580℃ for 3 hours to obtain catalyst C2. The results of active metal content are shown in Table 3.

[0153] Catalyst Preparation Example 3

[0154] Take 300 grams of pseudo-boehmite N5 and 9 grams of sesbania powder and mix them evenly. At room temperature, mix the mixture with 330 ml of 1% nitric acid aqueous solution, continue to knead it into a plastic body on a twin-screw extruder, and extrude it into butterfly-shaped strips with a diameter of ф1.4 mm. After the wet strips are dried at 120°C for 4 hours, they are calcined at 930°C for 3 hours to obtain carrier Z3. The properties of carrier Z3 are shown in Table 2.

[0155] Take 200g of carrier Z3, impregnate it with 170ml of ammonium molybdate solution with MoO3 content of 118g / L for 1 hour, dry it at 120℃ for 2 hours, and calcine it at 420℃ for 3 hours to obtain semi-finished catalyst Z3-C3; impregnate Z3-C3 with 170ml of nickel nitrate solution with NiO content of 35g / L for 1 hour, dry it at 120℃ for 2 hours, and calcine it at 580℃ for 3 hours to obtain catalyst C3. The results of active metal content are shown in Table 3.

[0156] Catalyst Preparation Example 4

[0157] Take 300 grams of pseudo-boehmite N7 and 9 grams of sesbania powder and mix them evenly. At room temperature, mix the mixture with 280 ml of 1% nitric acid aqueous solution, continue to knead it into a plastic body on a twin-screw extruder, and extrude it into butterfly-shaped strips with a diameter of ф1.4 mm. After the wet strips are dried at 120°C for 4 hours, they are calcined at 600°C for 3 hours to obtain carrier Z4. The properties of carrier Z4 are shown in Table 2.

[0158] 200 g of carrier Z3 was impregnated with 200 ml of a mixed solution of ammonium molybdate and basic cobalt carbonate with a MoO3 content of 135 g / L and a CoO content of 36 g / L for 1 hour to obtain a semi-finished catalyst Z4-C4; Z4-C4 was impregnated with 200 ml of a solution containing 30 g of citric acid for 1 hour, and dried at 150°C for 3 hours to obtain a catalyst C4. The results of the active metal content are shown in Table 3.

[0159] Catalyst Preparation Example 5

[0160] The catalyst was prepared according to the method of Catalyst Preparation Example 4, wherein the pseudo-boehmite was N8, the carrier was Z5, the catalyst was C5, and the active metal content results were shown in Table 3.

[0161] Catalyst Preparation Example 6

[0162] The carrier was prepared according to the method of Catalyst Preparation Example 1, except that the pseudo-boehmite was N 13 The catalyst was prepared according to the method of Catalyst Preparation Example 4, except that the carrier was Z6 and the catalyst was C6. The results of active metal content are shown in Table 3.

[0163] Catalyst Preparation Example 7

[0164] The carrier was prepared according to the method of Catalyst Preparation Example 1, except that the pseudo-boehmite was N 14 The catalyst was prepared according to the method of Catalyst Preparation Example 4, except that the carrier was Z7 and the catalyst was C7. The results of active metal content are shown in Table 3.

[0165] Catalyst Preparation Example 8

[0166] The carrier was prepared according to the method of Catalyst Preparation Example 1, except that the pseudo-boehmite was N 15 The catalyst was prepared according to the method of Catalyst Preparation Example 4, except that the carrier was Z8 and the catalyst was C8. The results of active metal content are shown in Table 3.

[0167] Catalyst Preparation Comparative Example 1

[0168] The carrier and catalyst were prepared according to the method of Catalyst Preparation Example 1, except that the pseudo-boehmite was DN1, the carrier obtained was DZ-1, and the catalyst was DC1. The results of active metal content are shown in Table 3.

[0169] Catalyst Preparation Comparative Example 2

[0170] The carrier and catalyst were prepared according to the method of Catalyst Preparation Example 4, except that the pseudo-boehmite was DN3, the carrier was DZ2, and the catalyst was DC2. The results of active metal content are shown in Table 3.

[0171] Catalyst Preparation Comparative Example 3

[0172] The carrier and catalyst were prepared according to the method of Catalyst Preparation Example 4, except that the pseudo-boehmite was DN4, the carrier was DZ3, and the catalyst was DC3. The results of active metal content are shown in Table 3.

[0173] Catalyst Preparation Comparative Example 4

[0174] 300 g of pseudo-boehmite P1 and 9 g of sesbania powder were mixed evenly, and the mixture was mixed evenly with 280 ml of 1% nitric acid aqueous solution at room temperature, and then further kneaded into a plastic body on a twin-screw extruder, and then extruded into butterfly-shaped strips of ф1.4 mm. The wet strips were dried at 120°C for 4 hours and then calcined at 600°C for 3 hours to obtain carrier DZ4. The properties of carrier DZ4 are shown in Table 2. P1: dry rubber powder produced by Changling Catalyst Branch (pore volume of 0.9 ml / g, specific surface area of ​​280 m 2 / gram).

[0175] Take 200g of carrier DZ4, impregnate it with 190ml of ammonium molybdate solution with MoO3 content of 176g / L for 1 hour, dry it at 120℃ for 2 hours, and calcine it at 420℃ for 3 hours to obtain semi-finished catalyst DZ4-DC4; impregnate DZ4-DC4 with 190ml of nickel nitrate solution with CoO content of 51g / L for 1 hour, dry it at 120℃ for 2 hours, and calcine it at 580℃ for 3 hours to obtain catalyst DC4. The results of active metal content are shown in Table 3.

[0176] Catalyst Preparation Comparative Example 5

[0177] 300 g of pseudo-boehmite P2 and 9 g of sesbania powder were mixed evenly, and the mixture was mixed evenly with 270 ml of 1% nitric acid aqueous solution at room temperature, and then further kneaded into a plastic body on a twin-screw extruder, and then extruded into butterfly-shaped strips of ф1.4 mm. The wet strips were dried at 120°C for 4 hours and then calcined at 600°C for 3 hours to obtain carrier DZ5. The properties of carrier DZ5 are shown in Table 2. P2: dry rubber powder produced by Zibo Qimao Catalyst Co., Ltd. (pore volume of 0.9 ml / g, specific surface area of ​​290 m 2 / gram).

[0178] Take 200g of carrier DZ5, impregnate it with 170ml of ammonium molybdate solution with MoO3 content of 118g / L for 1 hour, dry it at 120℃ for 2 hours, and calcine it at 420℃ for 3 hours to obtain semi-finished catalyst DZ5-DC5; impregnate DZ5-DC5 with 170ml of nickel nitrate solution with NiO content of 35g / L for 1 hour, dry it at 120℃ for 2 hours, and calcine it at 580℃ for 3 hours to obtain catalyst DC5. The results of active metal content are shown in Table 3.

[0179] Table 2

[0180]

[0181] Table 3

[0182]

[0183] Examples 1-8, Comparative Examples 1-5

[0184] This series of examples and comparative examples illustrate the effects of the method provided by the present invention.

[0185] The catalyst and contrast agent were crushed into particles with a diameter of 2-3 mm and loaded into the reactor. The reaction conditions were: reaction temperature 300°C, hydrogen partial pressure 1.6 MPa, volume space velocity 4 h -1 , hydrogen-to-oil volume ratio of 60, the sulfur content of the oil product is determined by the method Determination of sulfur content in gasoline and diesel (see ASTM D7039 for specific methods), and the mercaptan sulfur content is determined by the method Determination of mercaptan sulfur in gasoline, kerosene, jet fuel and distillate fuel (see GBT 1792-2015 for specific methods).

[0186] The properties of the raw oils used in the examples and comparative examples are shown in Table 4.

[0187] Table 4

[0188] Crude oil 1 Crude oil 2 <![CDATA[Density (20 °C) / (g / cm -3 )]]> 0.7982 0.7878 Total sulfur content / (μg / g) 3410 2243 Thiol sulfur content / (μg / g) 133 108

[0189] The desulfurization and desulfurization performance of C1, C4, C5, C6, C7, C8, DC1, DC2, and DC3 catalysts were evaluated, and the raw material oil was 1. The desulfurization and desulfurization performance of C2, C3, DC4, and DC5 catalysts were evaluated, and the raw material oil was 2; the activity data of each catalyst are shown in Table 5.

[0190] Table 5

[0191]

[0192] From the results in Table 5, it can be seen that the desulfurization and desulfurization performance of the aviation kerosene hydroprocessing method of the present invention is better than that of the existing method, indicating that the catalyst provided by the present invention can be used for aviation kerosene hydroprocessing, and the introduction of the additive further improves the catalyst hydrodesulfurization performance. In addition, the improvement of the catalyst preparation process of the present invention can reduce the production cost of the catalyst and improve the market competitiveness.

Claims

1. A hydroprocessing method for producing jet fuel, comprising contacting a jet fuel feedstock with a hydrodesulfurization catalyst under jet fuel hydroprocessing conditions, wherein the jet fuel hydroprocessing conditions are: a reaction temperature of 200-400°C, a hydrogen partial pressure of 0.5-6 MPa, and a volume space velocity of 1-10 h -1 , hydrogen to oil volume ratio 30-300; the hydrodesulfurization catalyst comprises an alumina carrier and at least one metal component selected from Group VIII and at least one metal component selected from Group VIB supported on the carrier, wherein, The alumina carrier is prepared from a pseudo-boehmite with high crystallinity and large grains, wherein the relative crystallinity of the pseudo-boehmite is higher than 65%, the grain size is 2-5 nm, and the sodium content calculated as oxide is not higher than 0.08wt% based on the dry weight of the pseudo-boehmite; the preparation method of the pseudo-boehmite comprises the following steps: (1) Gelation: a solution of sodium metaaluminate and / or sodium aluminate is contacted with a gas containing carbon dioxide to carry out a gelation reaction to obtain a solid gelation product; (2) Aging: subjecting the solid gelled product to a first aging and a second aging in sequence to obtain an aged mixture; the temperature of the second aging is higher than the temperature of the first aging; wherein the conditions of the first aging include: a temperature of 0-45°C and a time of 2-240 hours; the conditions of the second aging include: a temperature of 50-100°C and a time of 1-24 hours; (3) Separation and drying: performing solid-liquid separation on the aged mixture to obtain a solid aged product, and drying the solid aged product to obtain the pseudo-boehmite.

2. The method according to claim 1, wherein: The aviation kerosene raw material has a sulfur content of 200-5000µg / g, a mercaptan sulfur content of 20-200µg / g, an initial distillation point of 120-180°C, and a final distillation point of 220-280°C.

3. The method according to claim 1, wherein: The Group VIII metal component is cobalt and / or nickel, and the Group VIB metal component is molybdenum and / or tungsten. The content of the Group VIII metal component is 1-10% by weight and the content of the Group VIB metal component is 4-50% by weight, calculated as oxide and based on the catalyst.

4. The method according to claim 3, wherein: The content of the Group VIII metal component is 1.5-5% by weight, and the content of the Group VIB metal component is 6-35% by weight, calculated as oxide and based on the catalyst.

5. The method according to claim 1, wherein: The relative crystallinity of the pseudo-boehmite is greater than 65% and less than or equal to 95%, the grain size is 3-4.5 nm, and the sodium content calculated as oxide based on the dry weight of the pseudo-boehmite is not higher than 0.06wt%.

6. The method according to claim 5, wherein: The pseudo-boehmite has a relative crystallinity of 70-90%, a grain size of 3.3-4 nm, and a sodium content of 0.01-0.05% by weight based on the dry weight of the pseudo-boehmite and calculated as oxide; The pseudo-boehmite contains an additive, which is one or more of phosphorus, boron, titanium and magnesium. The additive content is 0.3-8wt% based on the dry basis of the pseudo-boehmite and calculated as oxide.

7. The method according to claim 6, wherein: The additive content is 0.4-6wt% based on the dry basis of pseudo-boehmite and calculated as oxide.

8. The method according to claim 1, wherein: In step (1) and / or (2), the step of adding an auxiliary agent is also included. The auxiliary agent includes one or more of phosphorus, boron, titanium and magnesium. The amount of the auxiliary agent is such that the final auxiliary agent content is 0.3-8wt% based on the pseudo-boehmite calculated on a dry basis and calculated on the basis of oxide.

9. The method according to claim 8, wherein: The amount of the additive is such that the additive content calculated on a dry basis based on pseudo-boehmite and calculated as oxide is 0.4-6 wt %.

10. The method according to claim 1, wherein: The contacting in step (1) comprises: continuously contacting a solution of sodium metaaluminate and / or sodium aluminate with a gas containing carbon dioxide in countercurrent; The conditions of the gelling reaction include: pH value of 7-10; residence time of 2-60 minutes; temperature of 30-95°C.

11. The method according to claim 10, wherein: The conditions of the gelling reaction include: pH value of 7.5-9.5; residence time of 7-50 minutes; temperature of 35-85°C.

12. The method according to claim 1, wherein: The concentration of the sodium metaaluminate and / or sodium aluminate solution is 5-40 g / L based on alumina; The volume content of carbon dioxide in the carbon dioxide-containing gas is greater than 20 volume %.

13. The method according to claim 12, wherein: The concentration of the sodium metaaluminate and / or sodium aluminate solution is 8-35 g / L based on alumina; The volume content of carbon dioxide in the carbon dioxide-containing gas is greater than 30 volume %.

14. The method according to claim 1, wherein: The temperature of the second aging is 10-100°C higher than the temperature of the first aging.

15. The method according to claim 14, wherein: The temperature of the second aging is 25-85°C higher than the temperature of the first aging.

16. The method according to claim 1, wherein: The first aging conditions include: temperature of 10-40°C; time of 4-120h; The second aging conditions include: temperature of 65-95° C. and time of 2-12 h.

17. The method according to claim 1, wherein: Step (2) comprises: subjecting the solid gelled product to a first aging to obtain a first aged product, and subjecting the first aged product to a second aging by slurrying with water to obtain an aged mixture; or Step (2) comprises: adding water to the solid gelled product for slurrying, performing a first aging to obtain a first aged product, and performing a second aging on the first aged product to obtain an aged mixture.

18. The method according to claim 1, wherein: The alumina obtained after calcination of the pseudo-boehmite has a pore volume of 0.8-1.3 mL / g, an average pore diameter greater than 14 nm, and a specific surface area of ​​200-260 m 2 / g.

19. The method according to claim 18, wherein: The alumina obtained after calcination of the pseudo-boehmite has a pore volume of 0.9-1.2 mL / g, an average pore diameter greater than 15 nm, and a specific surface area of ​​210-255 m 2 / g; The calcination conditions include: a temperature of 500-1200° C. and a time of 2-8 hours.

20. The method according to claim 19, wherein: The calcination conditions include: a temperature of 550-850° C. and a calcination time of 3-6 hours.

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