CN107583659B - Catalyst for selective hydrodesulfurization and preparation method thereof - Google Patents
Catalyst for selective hydrodesulfurization and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a selective hydrodesulfurization catalyst, which comprises the following components in mass percentage by mass: active components CoO 3-5%, MoO310-13%, and the adjuvant B, P and K contents of modified carrier are respectively2O32‑3％，P2O51‑2％，K21 to 1.5 percent of O, 75.5 to 83 percent of composite oxide carrier, and the carrier of the catalyst is zinc oxide and aluminum oxide composite oxide of zinc-containing aluminum spinel prepared by non-constant pH alternative titration. The catalyst has good desulfurization selectivity and stability.
Description
Technical Field
The invention relates to a selective hydrodesulfurization catalyst and a preparation method thereof, in particular to a selective hydrodesulfurization catalyst taking a zinc oxide material containing zinc aluminate spinel as a carrier and a preparation method thereof.
Background
In recent years, with the rapid increase of the holding amount of motor vehicles in cities of various countries, the problem of air pollution caused by automobile exhaust emission is increasingly serious, and the control of the air quality in large and medium-sized cities is a problem which is urgently needed to be solved for improving the life quality of people of various countries and ensuring the sustainable development of national economy.
With the implementation of the national standard for clean gasoline in China IV of 1 month and 1 day in 2014, the sulfur content in gasoline is required to be reduced to 50 mug/g, and at the end of 2016, China will implement the more severe national standard for clean gasoline in China V, the sulfur content in gasoline is required to be reduced to 10 mug/g, and subsequently or more severe gasoline standards are provided, so the sulfur content in gasoline is reduced and the importance of the sulfur content in gasoline is reduced.
The sulfur content in gasoline comes mainly From Catalytic Cracking (FCC) gasoline, so reducing the sulfur content in FCC gasoline becomes the key point for producing clean gasoline. The adopted method is to hydrofining FCC gasoline. The key of the FCC gasoline hydrofining catalyst is to improve the selectivity of the catalyst and reduce the saturation of olefin while hydrodesulfurizing so as to avoid excessive octane number loss. The selection and preparation of hydrofining catalyst carrier is one of the important means for raising catalyst selectivity.
The composite material of zinc oxide and aluminum oxide is often used as a desulfurization catalytic material in the fields of adsorption desulfurization and hydrodesulfurization. Common methods for preparing the material at present include impregnation, mechanical mixing, coprecipitation, and peptization. The impregnation method and the mechanical mixing method use the aluminum oxide material as a precursor, and the specific surface area of the aluminum oxide material is adjusted, so that the composite material with higher specific surface area can be prepared by the two methods, but the aluminum oxide and the zinc oxide in the composite material have weaker interaction, so that the zinc oxide is easy to lose in the using process, and the zinc oxide is prevented from losing by promoting the two methods to form spinel by adopting a high-temperature roasting method; the coprecipitation method and the peptization method adopt compounds containing aluminum and zinc to prepare a zinc-aluminum precursor through precipitation or peptization, the aluminum and the zinc generate stronger interaction through reaction in the preparation process so as to avoid zinc oxide loss in the use process, but the specific surface area of the materials prepared by the peptization method is the lowest, so that the materials are restricted when being used as catalytic materials.
US4140626 discloses a class of catalysts supported on alumina and magnesia, wherein the catalysts described therein contain 3 wt.% CoO, 16 wt.% MoO370wtMgO and 11 wt% Al2O3The olefin saturation rate is 64 percent when the desulfurization rate is 96 percent, and the desulfurization selectivity is improved to a greater extent than that of the traditional hydrodesulfurization catalyst. However, the catalyst has poor mechanical strength and is difficult to meet industrial requirements.
US5525210 discloses a process for desulfurizing FCC gasoline, the main active component of which is L acid such as zinc oxide supported on alumina carrier, by impregnation and coprecipitation, wherein the impregnation produces a material with a specific surface area of 142m after calcination at 815 deg.C2(g), the specific surface area of the material prepared by the coprecipitation method is 74m after the material is roasted at 704 DEG C2(ii) in terms of/g. The two methods have higher roasting temperature and lower specific surface area of the prepared zinc-aluminum material.
CN200710177577.X discloses a selective hydrodesulfurization catalyst modified by multiple additives and a preparation method thereof, wherein a carrier uses a composite oxide of alumina and boron oxide, Mg, K and P are used as additives to modulate the carrier and carry active components of cobalt and molybdenum, and the prepared catalyst is applied to hydrodesulfurization of catalytic cracking gasoline. When the desulfurization degree is 86%, the olefin is saturated by 6-7 v%, and the octane number loss is 0.9 unit.
CN200710045746.4 discloses a catalytic cracking assistant capable of reducing the sulfur content of gasoline, which contains zinc-aluminum spinel, uniformly dispersed zinc oxide and at least one optional rare earth metal oxide composite oxide, and is prepared by roasting a mixture of zinc-aluminum layered substance with hydrotalcite-like structure and optional rare earth hydrated oxideTo obtain the chemical formula of ZnAl2O4·(1-9)ZnO·(0-0.5)RE2O3(ii) a The preparation method is that sodium hydroxide and soluble inorganic sodium salt are dripped into the mixed solution of zinc salt, aluminum salt and rare earth ions, the pH value of the solution is 8-11, and the solution is roasted for 1-4h at the temperature of 500-1000 ℃. The formed auxiliary agent is blended with a conventional FCC catalyst and/or an activity strengthening auxiliary agent and applied to a catalytic cracking process, has the function of reducing the sulfur content of gasoline and has excellent hydrothermal stability. In order to obtain a zinc-aluminium spinel structure, the material needs to be roasted at a higher temperature, and the specific surface area after roasting is 120m at most2/g。
CN201210178395.5 discloses a preparation method of nano zinc-aluminum spinel, which comprises the steps of adding zinc salt into water for dissolving, adding an aluminum source, stirring for 10-30 minutes, adding a pore-expanding agent, stirring, aging for 30-60 minutes at 20-100 ℃, drying, and roasting at 500-1200 ℃; the molar ratio of the raw materials is Zn, Al and water is 1: 2: 16-35; the addition amount of the pore-expanding agent is 0.5-30% calculated by taking the mass of the zinc oxide as 100%; the pore-enlarging agent is one or more of sucrose, glycerol, ammonium carbonate, ammonium bicarbonate, polystyrene emulsion and polyethylene glycol. The specific surface area of the synthesized zinc-aluminum spinel is from 60 to 300m2(ii) in terms of/g. The zinc-aluminum mixture ratio of the material fed by the method is low, and the pore-expanding agent is added in the preparation process, so that only the zinc-aluminum spinel is obtained, and the zinc-aluminum spinel does not contain uniformly dispersed zinc oxide.
CN201310625314.6 discloses a preparation method of a photocatalytic material with strong adsorption and high visible light degradation performance, and the invention relates to a zinc aluminum spinel with a high specific surface mesoporous structure, zinc oxide and nickel oxide nano composite photocatalytic material obtained by using ternary hydrotalcite as a precursor through high-temperature roasting, and a preparation method thereof. Zinc nitrate, nickel nitrate, aluminum nitrate, sodium carbonate, sodium hydroxide and the like are used as raw materials to be prepared into a salt solution and an alkali solution respectively, and the salt solution and the alkali solution are mixed by a constant flow pump under the magnetic stirring at the temperature of 80 ℃; transferring the reaction mixed solution into a hydrothermal reaction kettle, and carrying out hydrothermal treatment for 5-10h at the temperature of 130-; filtering, washing and drying to obtain a precursor, and roasting the precursor in a muffle furnace at 400-600 ℃ for 2-6 hoursObtaining the product, wherein the molar ratio of zinc ions to nickel ions to aluminum ions is 1-3:1-3:1-3, and the specific surface area is more than 150m2(ii) in terms of/g. The method needs hydrothermal treatment in the process of synthesizing the ternary hydrotalcite-like precursor, and the treatment time is long.
CN200310121344.X discloses a preparation method of aluminum-doped nano-grade zinc oxide conductive powder. The method is characterized in that a mixed salt solution of soluble salts of zinc, doped elements of aluminum, gallium, indium, yttrium, scandium, tin, germanium and silicon and a precipitator are simultaneously dripped into water, coprecipitation is generated under the conditions of controlling the temperature of the whole reaction system to be 40-75 ℃ and the pH value to be 7.0-7.5 to generate doped zinc oxide precursor basic zinc carbonate, and the doped superfine zinc oxide conductive powder material is prepared by roasting in the mixed atmosphere of hydrogen and argon, but the material prepared by the method is applied to a conductive material, and the adding molar quantity of the doped elements is only 0.1-10% of the total molar quantity of zinc and the doped elements.
CN200510028233.3 discloses a method for preparing a catalytic cracking flue gas high-efficiency sulfur transfer agent, which comprises the steps of dropwise adding a mixed solution of zinc salt, magnesium salt, aluminum salt and cerium salt into a mixed solution of sodium hydroxide and sodium carbonate by taking zinc, magnesium and aluminum as active components and cerium and vanadium as auxiliaries at the temperature of 60-80 ℃ and the pH value of 8-10, roasting the obtained coprecipitation product at the temperature of 400-80 ℃ for 6-8h, and preparing zinc-magnesium-aluminum-cerium hydrotalcite by a coprecipitation method, wherein the molar ratio of the three metals of zinc, magnesium and aluminum is 1.0:1.0-4.5:1.0-2.0, and the sulfur transfer agent prepared by adopting the material has high-efficiency SOx adsorption and desorption performances and good mechanical strength.
CN200910087590.5 discloses a desulfurizing agent for reforming raw oil and a preparation method thereof, the preparation method of the catalyst relates to a blending method, a eutectic method and a coprecipitation method, and is characterized in that the desulfurizing agent comprises the following components by weight: ZnO: 10% -40%, NiO: 15% -22% of Al2O3：10％-17％、SiO2: 5% -22%, the balance being unavoidable impurities.
Research on auxiliary agent for reducing sulfur content of catalytically cracked gasoline-Synthesis of Zinc-aluminum spinel and its cracking desulfurization Performance (Author: Wangpo; China petrochemical Co., Ltd., [ Stone ]Oil journal (petroleum processing) 2003, vol 19, 2): discloses a preparation method of zinc aluminate spinel: mixing sodium metaaluminate solution and zinc nitrate solution according to m (Al)2O3) And m (ZnO) 9, adding dropwise into distilled water at 40 ℃ at the same rate, mixing uniformly, adding 16% sodium hydroxide solution, adjusting the pH value of the solution to 8.6, aging the generated precipitate for 15min, adding a small amount of sodium hydroxide solution, and adjusting the pH value to 9.0. Filtering and washing the precipitate for more than 3 times to remove Na+. Finally, the precipitate is dried at 120 ℃ for 4h and then calcined at 700 ℃ for 2 h. The specific surface area of the sample is basically 160m2And about/g.
Disclosure of Invention
The invention aims to prepare a hydrodesulfurization catalyst taking a zinc oxide material containing zinc-aluminum spinel as a carrier, and the hydrodesulfurization catalyst suitable for an FCC gasoline hydrogenation process is prepared by synthesizing a layered material carrier with a zinc-aluminum hydrotalcite-like structure, loading Co and Mo metal salts, and modifying elements such as boron, potassium, phosphorus and the like. The invention also aims to provide a preparation method of the catalyst, and a more ideal selective hydrodesulfurization catalyst is obtained by synthesizing a zinc oxide carrier containing zinc aluminate spinel and reasonably adjusting the proportion of the three auxiliaries; and the preparation process is simple and feasible, convenient to operate and easy to control.
In order to achieve the above object, the present invention provides a selective hydrodesulfurization catalyst, which comprises the following components by mass: active components CoO 3-5%, MoO310-13%, and the adjuvant B, P and K contents of modified carrier are respectively2O32-3％，P2O51-2％，K21 to 1.5 percent of O and 75.5 to 83 percent of composite oxide carrier. The carrier of the catalyst is a zinc oxide and alumina composite oxide of zinc-containing aluminum spinel prepared by non-constant pH alternative titration, the zinc oxide content of the zinc-containing aluminum spinel prepared by non-constant pH alternative titration in the carrier is 1-25 wt%, and the alumina content is 75-99 wt%.
The selective hydrodesulfurization catalyst provided by the invention adopts three promotersThe agent modified composite oxide consists of 1-25 wt% of zinc oxide and 75-99 wt% of alumina, wherein the specific surface area of the alumina is 350-450m2G, pore volume of 0.8-1.0 ml/g. The specific surface area of the adopted zinc oxide containing zinc aluminate spinel is 150-220m2G, pore volume of 0.5-0.7 ml/g.
The preferred catalyst composition according to the invention, the content of the promoter in the catalyst, calculated as oxides, based on the total weight of the catalyst, is respectively: b is2O32-3％，P2O51-2％，K21 to 1.5 percent of O; the preferred B/P/K atomic ratio of the auxiliary is (4-6): 1.5-2.2): 1.
The obtained selective hydrodesulfurization catalyst according to the invention has a specific surface area of 250-300m2G, pore volume of 0.4-0.6 ml/g.
The invention also provides a preparation method of the selective hydrodesulfurization catalyst, which comprises the following steps:
mixing zinc oxide and aluminum oxide, adding sesbania powder and nitric acid, kneading, molding, drying and roasting to prepare a composite oxide carrier;
the composite oxide carrier is dipped with boron, potassium and phosphorus, and is aged, dried and roasted to prepare the catalyst carrier modified by the auxiliary agent.
The catalyst carrier modified by the auxiliary agent is dipped with cobalt and molybdenum, and is aged, dried and roasted to prepare the selective hydrodesulfurization catalyst.
According to the preparation method, the zinc oxide material in the step (1) is prepared by adopting a non-constant pH alternative titration method of an aluminum-containing sodium carbonate solution and a zinc-containing solution, so that the zinc oxide material containing zinc-aluminum spinel is obtained. The dry weight ratio of the alumina to the alumina can be controlled to be 1 (3-99); the contents of the sesbania powder and the nitric acid are respectively 4-6% and 5-7% by the total weight of the catalyst. The alumina in the step (1) can adopt alumina dry glue powder.
In the step (2), the modification of the auxiliary agent may be carried out by using a corresponding salt solution thereof as an impregnation solution to impregnate the auxiliary agent component, for example, salts of boron may include boric acid, potassium tetraborate, potassium metaborate, etc., salts of potassium may include potassium carbonate, potassium tetraborate, potassium oxalate, etc., and salts of phosphorus may be one or a combination of more than one of phosphoric acid, ammonium phosphate and potassium phosphate.
In the step (3), when the active components cobalt and molybdenum are impregnated, the cobalt salt may include cobalt carbonate, cobalt oxalate, cobalt molybdate and the like, and the molybdenum salt may be ammonium molybdate, cobalt molybdate, potassium molybdate and the like.
The modification with the aid and the loading of the active ingredient can be carried out by conventional impregnation methods, i.e., by co-impregnation or by impregnation in steps.
In the steps of preparing the catalyst carrier and the catalyst modified by the auxiliary agent, the auxiliary agent and the active component are soaked and then are aged, dried and roasted, for example, the aging conditions are as follows: aging at room temperature for about 4-6 hours; the drying conditions were: drying at the temperature of 140 ℃ and 120 ℃; the roasting conditions are as follows: 600 ℃ and 700 ℃ for about 6-8 hours.
According to a specific embodiment of the present invention, the preparation method of the selective hydrodesulfurization catalyst provided by the present invention may include the following steps:
synthesis of zinc oxide materials
Dissolving soluble zinc salt in water to obtain a zinc-containing solution; dissolving sodium metaaluminate and sodium carbonate in water to obtain an aluminum-containing solution; dividing the zinc-containing solution into 2-4 parts, taking one part of the zinc-containing solution, dropwise adding an aluminum-containing solution at 40-80 ℃, and stopping dropwise adding the aluminum-containing solution when the pH value reaches 8.5-9.5; dripping one part of zinc-containing solution into the mixing system; continuously dripping the aluminum-containing solution after the part of the zinc-containing solution is completely dripped, and stopping dripping the aluminum-containing solution when the pH value reaches 8.5-9.5; and (3) titrating the aluminum-containing solution and the zinc-containing solution alternately according to the method until the zinc-containing solution with the feeding amount is completely dripped into the mixing system, dripping the aluminum-containing solution for the last time, and finishing the alternate titration process of the non-constant pH value when the pH value reaches 8.5-9.5. Controlling the titration speed to be 0.5-6 h; aging at 75-95 deg.C for 2-8h, cooling and washing to neutrality, drying at 80-140 deg.C in air atmosphere for 4-10h, and calcining at 550 deg.C for 4-10h to obtain zinc oxide material containing zinc aluminate spinel.
Preparation of composite oxide support
Mixing the alumina dry glue powder or the conventional pseudo-boehmite with the zinc oxide prepared in the step 1 according to a dry basis (3-99):1, uniformly grinding, adding 4-6 wt% of sesbania powder and 5-7 wt% of nitric acid into the formed mixture, performing extrusion forming after kneading, performing drying treatment at 120-140 ℃ for about 6-8 hours, and performing roasting treatment at 600 ℃ for 8 hours.
Preparation of adjuvant-modified catalyst supports
Preparing mixed impregnation liquid of boric acid, phosphoric acid and potassium phosphate with proper concentration according to the saturated water absorption of the composite oxide carrier and the weight content of the required additive, spraying the mixed impregnation liquid on the composite oxide carrier with proper concentration, aging at room temperature for about 4 hours, drying at 140 ℃ for 6-8 hours, and roasting at 600-700 ℃ for 8 hours to prepare the additive modified catalyst carrier.
Preparation of selective hydrodesulfurization catalyst
According to the saturated water absorption of the catalyst carrier, preparing a mixed solution of cobalt molybdate and ammonium molybdate with proper concentration at normal temperature, adding ammonia water to adjust the pH value to completely dissolve solid salt into an impregnation solution of an active component, spraying the impregnation solution on the catalyst carrier modified by a proper amount of an auxiliary agent, aging at room temperature for 4-6 hours, drying at the temperature of 140-.
The gasoline selective hydrodesulfurization catalyst provided by the invention has the following advantages:
1. compared with the prior art, the zinc oxide of the zinc-containing aluminum spinel is prepared by non-constant pH alternative titration, so that aluminum zinc precursors can be orderly stacked into a layered structure, and the specific surface area can be 150-220m2The specific surface area can be 180-200m2/g，160-210m2/g，155-175m2/g，200-220m2The concentration is in the same range as the concentration of the zinc oxide, the problem that a precursor obtained by titrating the zinc-aluminum mixed solution by adopting an alkaline solution in one step needs to be roasted at high temperature to fix the zinc oxide is solved, and the hydrothermal treatment process is also reduced. Oxygen containing zinc-aluminum spinelThe zinc oxide is used as a carrier, so that the desulfurization activity of the catalyst is effectively improved without increasing the olefin saturation activity, and the catalyst has excellent hydrodesulfurization selectivity; under the condition of 90 percent of desulfurization rate, the olefin saturation rate is only about 10 percent, and the desulfurization selectivity is good.
2. The zinc-aluminum spinel structure formed in the carrier not only has the cracking desulfurization performance, but also can inhibit the loss of active component ZnO, thereby enhancing the stability of the catalyst and being beneficial to the long-period operation of the catalyst.
3. The catalyst is added with various additives such as boron, potassium, phosphorus and the like, so that the surface acidity of the catalyst is changed, olefin polymerization can be reduced, carbon deposition can be inhibited, and good desulfurization activity can be maintained.
4. The catalyst has certain isomerization generating capacity, and the RON loss of the treated oil product is small and is about 0.7 unit.
5. The catalyst of the invention can be suitable for the modification of full-fraction FCC gasoline, and the single-stage single agent is adopted in the treatment process, so the process is simple; the reaction process has the advantages of mild conditions, low reaction temperature, low pressure, low requirements on device materials and less equipment investment.
Drawings
Fig. 1 is an XRD characterization pattern of a sample of zinc oxide material containing zinc aluminum spinel prepared in example 1. The XRD spectrogram of the sample contains XRD characteristic peaks of two phases of zinc aluminate spinel and zinc oxide, which indicates that the material is a zinc oxide material containing zinc aluminate spinel.
Detailed Description
The following examples are intended to further illustrate the process of the present invention but should not be construed as limiting thereof.
The reagents of the invention are all commercial products. The FCC gasoline is FCC gasoline of Lanzhou petrochemical refinery.
Example 1
The preparation of this example comprises: 5% CoO, 10% MoO based on the total weight of the catalyst3，2％B2O3，1％P2O5，1％K2O，5％ZnO-76％Al2O3The catalyst A of (1).
800g of zinc nitrateDissolving the mixture in 4L water to prepare a zinc-containing solution, dissolving 120g of sodium metaaluminate and 120g of sodium carbonate in 1.7L water to prepare an aluminum-containing solution, taking 2L zinc-containing solution, controlling the temperature of the system to be 60 ℃, dropwise adding the aluminum-containing solution into the zinc-containing solution until the pH value reaches 9, stopping dropwise adding the aluminum-containing solution, dropwise adding the rest 2L zinc-containing solution into a mixing system, continuously dropwise adding the aluminum-containing solution until the pH value reaches 9, titrating for 4 hours in total, aging the obtained mixture at 85 ℃ for 4 hours, cooling and washing to be neutral, drying the mixture at 120 ℃ in an air atmosphere for 5 hours, roasting the mixture at 500 ℃ for 6 hours to obtain a zinc oxide sample containing zinc aluminum spinel, wherein the content of the zinc oxide is 60%, and2/g。
10g of the zinc oxide sample was weighed, and alumina dry glue powder (30 wt% moisture, manufactured by Shandong Tai photo chemical Co., Ltd.) was used, and the specific surface area after baking was 400m2G, the pore volume is 1.0ml/g)124.6g and sesbania powder 6g, 10g of nitric acid with the mass concentration of 65 percent and 70g of distilled water are added after grinding and mixing evenly. Mixing, kneading, extruding into 1.5mm clover shape in a extruder, drying at 140 deg.C for 6 hr, calcining at 650 deg.C for 8 hr, cooling, and sieving to obtain 1-2 cm-long composite oxide carrier.
Then 3.54g of boric acid, 1.5g of potassium phosphate and 0.7g of phosphoric acid are weighed and completely dissolved in 56g of distilled water to prepare an auxiliary agent impregnation solution, the auxiliary agent impregnation solution is sprayed on 81g of composite oxide carrier in a rotary drum at room temperature, the carrier is placed and aged for 6h at room temperature, the carrier is dried at 140 ℃ for 6h, and the carrier is roasted at 650 ℃ for 8h to obtain the modified composite oxide carrier.
Weighing 19.42g of cobalt nitrate and 12.27g of ammonium heptamolybdate, dissolving the cobalt nitrate and the ammonium heptamolybdate in a mixed solution of 40g of concentrated ammonia water with the mass fraction of 25% and 30g of distilled water, completely dissolving to prepare an active substance impregnation solution, spraying the active substance impregnation solution on 85g of composite oxide carrier in a rotary drum at room temperature, standing and aging for 6h at room temperature, drying at 140 ℃ for 6h, and roasting at 650 ℃ for 8h to prepare the selective hydrodesulfurization catalyst A.
Example 2
The preparation of this example comprises: 4% CoO, 12% MoO based on the total weight of the catalyst3，2.5％B2O3，1.6％P2O5，1.3％K2O，15.6％ZnO-63％Al2O3The catalyst B of (1).
The preparation method of the composite oxide carrier was the same as in example 1, except that the amount of the zinc oxide sample was 26g and the amount of the alumina dry gel powder was 90g when the composite oxide carrier was prepared.
Then weighing 4.44g of boric acid, 1.95g of potassium phosphate and 1.31g of phosphoric acid, completely dissolving in 56g of distilled water to prepare an auxiliary agent impregnation solution, spraying the auxiliary agent impregnation solution on 78.6g of composite oxide carrier in a rotary drum at room temperature, standing and aging for 6h at room temperature, drying at 140 ℃ for 6h, and roasting at 650 ℃ for 8h to obtain the modified composite oxide carrier.
Weighing 15.5g of cobalt nitrate and 14.7g of ammonium heptamolybdate, dissolving the cobalt nitrate and the ammonium heptamolybdate in a mixed solution of 40g of concentrated ammonia water with the mass fraction of 25% and 30g of distilled water, completely dissolving to prepare an active substance impregnation solution, spraying the active substance impregnation solution on 85g of composite oxide carrier in a rotary drum at room temperature, standing and aging for 6h at room temperature, drying at 140 ℃ for 6h, and roasting at 650 ℃ for 8h to prepare the selective hydrodesulfurization catalyst B.
Example 3
The preparation of this example comprises: 5% CoO, 10% MoO based on the total weight of the catalyst3，2％B2O3，1％P2O5，1％K2O，20％ZnO-61％Al2O3Catalyst C of (1).
The preparation method was the same as in example 1, except that the amount of the zinc oxide sample was 40g and the amount of the alumina dry gel powder was 96g in the preparation of the composite oxide carrier.
Comparative example 1
The preparation of this example comprises: 5% CoO, 10% MoO based on the total weight of the catalyst3，2％B2O3，1％P2O5，1％K2O，81％Al2O3Catalyst D according to (1).
The procedure was as in example 1, except that the oxide support was 138.9g of dry alumina gel powder.
Application example
This example is the application of the above catalyst in selective hydrodesulfurization of FCC gasoline.
The catalysts A-D are respectively loaded into a small fixed bed reactor, the loading amount is 10ml, and after the air tightness is qualified, the catalyst is presulfurized. The vulcanized oil is straight-run gasoline, the vulcanizing agent is CS2, and the concentration of the vulcanized oil is 1.0 wt%; the vulcanization pressure is 2.8MPa, the hydrogen-oil volume ratio is 300, the volume space velocity of the vulcanized oil is 2.0h < -1 >, and the vulcanization procedure is that the vulcanization treatment is carried out for 8h at 230 ℃ and 280 ℃ respectively. After the vulcanization treatment is finished, the whole fraction FCC gasoline is switched to be subjected to displacement treatment for 10 hours, then the reaction pressure is reduced to 1.6MPa, the reaction temperature is reduced to about 200 ℃, the hydrogen-oil volume ratio is adjusted to 200, the feeding volume airspeed is adjusted to 3.0h < -1 >, and the sampling analysis is carried out after the reaction is about 50 hours. The results are shown in Table 1, and desulfurization degree (HDS), olefin saturation degree (HYD) and selectivity factor (S) were used as evaluation indexes. The selectivity factor is the ratio of the desulfurization rate activity of the catalyst to the olefin saturation activity, and the calculation formula is as follows:
S＝ln(1-HDS)/ln(1-HYD)
tables 1 and 2 show the desulfurization rate activity, olefin saturation activity and octane number loss of the catalysts in examples and comparative examples. As is clear from tables 1 and 2, catalyst B had good selective hydrodesulfurization activity, and the RON loss of the product treated with this catalyst was 0.7 unit.
TABLE 1 FCC gasoline selective hydrodesulfurization reaction results for catalysts A-D
| Catalyst and process for preparing same | HDS，％ | HYD，％ | S |
| A | 80 | 10 | 15.3 |
| B | 88 | 11 | 18.2 |
| C | 85 | 11 | 16.3 |
| D | 78 | 11 | 13.0 |
TABLE 2 Properties of feed oil and product Properties of catalyst B
| Item | Raw oil | Product(s) |
| Sulfur (μ g/g) | 300 | 45 |
| Olefin (v%) | 43.1 | 32.1 |
| Aromatic hydrocarbons (v%) | 14.1 | 14.2 |
| Saturated hydrocarbon (v%) | 42.8 | 52.7 |
| RON | 93.0 | 92.3 |
The stability of catalyst B to selective hydrodesulfurization of full-distillate FCC gasoline was investigated with the catalyst B as the subject, and the results are shown in table 3. As can be seen from Table 3, during the operation period of 300h, each reaction performance index of the catalyst is stable and consistent with the previous result, which shows that the hydrodesulfurization stability is good and the catalyst has industrial application value.
TABLE 3 stability test results for catalyst B
The present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof, and it is therefore intended that all such changes and modifications as fall within the true spirit and scope of the invention be considered as within the following claims.
Claims (8)
1. A selective hydrodesulfurization catalyst characterized by the composition, by mass of oxides: active components CoO 3-5%, MoO310-13%, and the adjuvant B, P and K contents of modified carrier are respectively2O32-3％，P2O51-2％，K21 to 1.5 percent of O, 75.5 to 83 percent of composite oxide carrier, wherein the carrier of the catalyst is zinc oxide and aluminum oxide composite oxide of zinc-containing aluminum spinel prepared by non-constant pH alternative titration,the zinc oxide content of the zinc-containing aluminum spinel prepared by non-constant pH alternative titration in the carrier is 1-25 wt%, and the alumina content is 75-99 wt%;
the preparation method of the zinc oxide containing the zinc-aluminum spinel comprises the following steps: dissolving soluble zinc salt in water to obtain a zinc-containing solution; dissolving sodium metaaluminate and sodium carbonate in water to obtain an aluminum-containing solution; dividing the zinc-containing solution into 2-4 parts, taking one part of the zinc-containing solution, dropwise adding an aluminum-containing solution at 40-80 ℃, and stopping dropwise adding the aluminum-containing solution when the pH value reaches 8.5-9.5; dripping one part of zinc-containing solution into the mixing system; continuously dripping the aluminum-containing solution after the part of the zinc-containing solution is completely dripped, and stopping dripping the aluminum-containing solution when the pH value reaches 8.5-9.5; alternately titrating the aluminum-containing solution and the zinc-containing solution according to the method until the zinc-containing solution with the feeding amount is completely dripped into the mixing system, dripping the aluminum-containing solution for the last time, and finishing the alternate titration process of the non-constant pH value when the pH value reaches 8.5-9.5; controlling the titration speed to be 0.5-6 h; aging at 75-95 deg.C for 2-8h, cooling and washing to neutrality, drying at 80-140 deg.C in air atmosphere for 4-10h, and calcining at 550 deg.C for 4-10h to obtain zinc oxide material containing zinc aluminate spinel.
2. The selective hydrodesulfurization catalyst of claim 1 wherein the alumina has a specific surface area of 350-450m2The specific surface area of the zinc oxide containing the zinc aluminate spinel is 150-2G, pore volume of 0.5-0.7 ml/g.
3. The selective hydrodesulfurization catalyst of claim 1 wherein the promoter B/P/K atomic ratio is (4-6): 1.5-2.2): 1.
4. The selective hydrodesulfurization catalyst of claim 1 wherein the zinc oxide specific surface area of the zinc-containing aluminum spinel is 180-200m2/g or 155-2/g。
5. The selective hydrodesulfurization catalyst of claim 1A catalyst, which is characterized in that the zinc oxide specific surface area of the zinc-containing aluminum spinel is 200-220m2/g。
6. The selective hydrodesulfurization catalyst of claim 1 wherein the zinc oxide specific surface area of the zinc-containing aluminum spinel is 160-210m2/g。
7. A method for preparing a selective hydrodesulfurization catalyst as defined in claim 1 comprising the steps of: 1) mixing zinc oxide and aluminum oxide, adding sesbania powder and nitric acid, wherein the content of the sesbania powder and the content of the nitric acid are respectively 4-6% and 5-7% based on the total weight of the catalyst, kneading, molding, drying at 120-140 ℃ for about 6-8 hours, and roasting at 600 ℃ for 8 hours to prepare a composite oxide carrier; 2) soaking the composite oxide carrier in boron, potassium and phosphorus, aging at room temperature for about 4 hours, drying at 140 ℃ for 6-8 hours, and roasting at 600-700 ℃ for 8 hours to prepare an assistant modified catalyst carrier; 3) the catalyst carrier modified by the auxiliary agent is impregnated with cobalt and molybdenum, then is aged for 4-6 hours at room temperature, and is dried for 4 hours at the temperature of 140 ℃ and 160 ℃ and is roasted for 8 hours at the temperature of 600 ℃ and 700 ℃ to prepare the selective hydrodesulfurization catalyst.
8. The selective hydrodesulfurization catalyst of claim 1 wherein the catalyst has a specific surface area of 250-300m2G, pore volume of 0.4-0.6 ml/g.
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