CN104056632A - Fuel oil deep-adsorption desulfurizationn catalyst, preparation method and application thereof - Google Patents

Abstract

The invention discloses a fuel oil deep-adsorption desulfurizationn catalyst. The desulfurizationn catalyst is characterized by consisting of an active component, a sulfur adsorbent and an adhesion agent, wherein the active component refers to one or more of Ni, Co, Cu, W and Mo oxides; the sulfur adsorbent refers to at least one of Mg, Ca, Zn, Ce, Fe, Mn and Ti oxides; the mass percent content of the active component is 2wt%-50wt%, the mass percent content of the sulfur adsorbent is 20wt%-90wt%, and the mass percent content of the rest components is the adhesion agent. The adhesion agent is one or a mixture of more than one of aluminium oxide, pseudo-boehmite, kaolin, imvite, bentonite, Yunmeng soil, kieselguhr, silica sol, silica gel and expanded perlite. The catalyst has the advantages of high specific surface area, moderate reaction, high intensity and low hydrogen consumption.

Description

A fuel oil deep adsorption desulfurization catalyst and its preparation method and application

technical field

The invention belongs to fuel oil desulfurization technology, in particular to a fuel oil deep adsorption desulfurization catalyst, a preparation method and application.

technical background

The organic sulfur in fuel oil will cause great harm to the environment after burning, so countries around the world have formulated strict laws and regulations to limit the sulfur content in fuel oil. In recent years, in response to the deteriorating environment, my country's gasoline quality standards will fully implement the National IV standard, and the sulfur content of oil products will be reduced from less than 150ppm in the National III standard to less than 50ppm, a reduction of 67%. In Beijing, Shanghai, Nanjing, Suzhou, Wuxi and other cities in Jiangsu, as well as Guangzhou and Shenzhen in Guangdong, the gasoline quality standard will meet the National V standard, and the sulfur content of oil products will be reduced from less than 50ppm in the National IV standard to less than 10ppm , another 80% reduction.

Gasoline in my country mainly comes from catalytic cracking, which has high sulfur content and must be desulfurized before it can be used. At present, there are two methods for desulfurization of fuel oil: hydrofinishing and adsorption desulfurization. However, hydrofinishing needs to consume a large amount of hydrogen, which is costly, and will saturate olefins and reduce the octane number of gasoline. For diesel oil, although hydrorefining can improve the cetane number, the cost of hydrogen consumption is too high. Therefore, a deep desulfurization method with relatively small hydrogen consumption is needed to reduce production costs.

The American ConocoPhillips Corporation has developed a S-Zorb adsorption desulfurization technology. This technology works at a temperature of 243-413°C, a pressure of 0.7-1.2MPa, a space velocity of 4-10h ^-1 , and under the conditions of hydrogenation and fluidization. Then, the adsorbent is regenerated by oxygen-enriched regeneration method, and the adsorbent is mainly composed of active component nickel oxide and adsorbent zinc oxide. The company improved this technology again in US7182918B2. In order to increase the strength of the catalyst and reduce the loss of aromatics, the catalyst has low activity and needs frequent regeneration.

CN1048418, CN1151333 disclose a kind of novel composition containing zinc oxide, silicon dioxide, colloidal oxide and promotor, improve pore volume and specific surface area by adding pore-forming agent in colloid, but the catalyst strength prepared by this method is relatively poor .

CN1130253C and US6150300 disclose a granular adsorbent composition comprising a mixture of zinc oxide, silicon oxide, aluminum oxide, reduced nickel or cobalt, which first prepares zinc oxide, aluminum oxide, and silicon oxide into a granular carrier, and then Nickel is supported, and a method of using the catalyst is provided. This process is relatively cumbersome, and the strength of the catalyst decreases seriously after the carrier is loaded with nickel, which is easy to cause pulverization.

At present, the catalysts using zinc oxide as the adsorbent have problems such as large catalyst particle size, low specific surface area, high reaction temperature, low strength, and high hydrogen consumption. Therefore, it is necessary to develop a new adsorption desulfurization catalyst to improve these properties to meet the production requirements.

Contents of the invention

The object of the present invention is to provide a fuel oil deep adsorption desulfurization catalyst with high specific surface area, mild reaction, high strength and low hydrogen consumption, as well as its preparation method and application.

The catalyst of the present invention includes an active component, a sulfur adsorbent, and a binding agent, wherein the active component is one or more of Ni, Co, Cu, W, and Mo oxides, and the sulfur adsorbent is Mg, Ca, Zn, At least one of Ce, Fe, Mn, Ti oxides, the mass percentage of active components is 2wt%-50wt%, the mass percentage of sulfur adsorbent is 20wt%-90wt%, and the rest is binder .

The binder is one or a mixture of alumina, pseudo-boehmite, kaolin, montmorillonite, bentonite, montmorillonite, diatomite, silica sol, silica gel, and expanded perlite

Catalyst prepared by the present invention has the following characteristics:

The specific surface area of the catalyst is 20-200m ² /g;

The pore volume of the catalyst is 0.1-1.0cm ³ /g, and the average pore diameter is 5-50nm;

The catalyst strength is 30-120N/particle.

The particles of the sulfur adsorbent are nanoscale, and the particle diameter is 5-200nm.

The size and specific surface area of sulfur adsorbent have a great influence on the desulfurization performance. The smaller the particle size and the higher the specific surface area, the better the desulfurization performance. In order to improve the adsorption and desulfurization performance of the catalyst, the specific surface area of the invention is 20-200m ² /g, and the particle size of the sulfur adsorbent particles is 5-200nm.

The invention provides the preparation method of catalyst, and concrete steps are as follows:

(a) loading the active components on the sulfur adsorbent by kneading or impregnation;

(b) Mix the sample obtained in (a) with a binder and a pore-forming agent uniformly and form granules;

(c) drying the catalyst sample obtained in (b) at 80-150°C for 5-24h;

(d) Calcining the sample obtained in (c) at 180-250° C. for 1-10 hours, and then at 250-500° C. for 2-8 hours to obtain the desired catalyst.

In step (a), the active component is loaded on the sulfur adsorbent by a kneading method, and the active component oxide and the sulfur adsorbent oxide are kneaded in a kneader for 10-60 min.

In the step (a), the active component is loaded onto the sulfur adsorbent by impregnation, and the steps are as follows:

(1) The soluble salt of the active component is prepared into a mixed solution with deionized water, and the mixed solution is heated to keep the temperature between 20-80°C.

(2) Soak the oxide of the sulfur adsorbent in the prepared solution for 1-6 hours, and keep stirring during the dipping process.

(3) Dry the impregnated sample at 80-150°C for 5-24h, and roast the dried catalyst at 180-250°C for 1-10h, then at 250-500°C for 2-8h.

The pore-forming agent in step (b) is starch, cellulose, polyethylene glycol, polypropylene alcohol, and its consumption is 1wt%-10wt% of the total amount of catalyst; one.

The soluble salt of the active component described in step (1) is nitrate, acetate or chloride.

The application method of catalyst of the present invention is as follows:

The reduction conditions are hydrogen pressure 0.1-5.0MPa, temperature 350°C-550°C, reduction time 2-20h; reaction conditions: temperature 200-500°C, pressure 0.1-5.0MPa, fuel oil mass space velocity 0.2-5.0 h ^-1 , H ₂ /oil volume ratio is 50-1000.

The catalyst of the invention is suitable for deep adsorption desulfurization of fuel oils such as catalytic cracking gasoline, diesel oil and kerosene.

The advantages of the present invention are as follows:

The invention provides a method for preparing a catalyst for deep adsorption desulfurization of fuel oil. The catalyst prepared by the method has the advantages of high specific surface area, low hydrogen consumption, high desulfurization depth, large sulfur capacity, long service life and the like. The catalyst prepared by the invention also has the advantage of being easy to regenerate. After the catalyst reaches adsorption saturation, it can be easily regenerated in an oxidizing atmosphere.

Detailed ways

The present invention is further illustrated by the following examples, but the invention is not limited thereto.

Example 1:

Adopt kneading method to load active component nickel oxide on the mixture of zinc oxide and iron oxide, weigh 22g nickel oxide, 80g zinc oxide (particle diameter is 5nm), 20g iron oxide (particle diameter is 200nm), add 10ml water and Grind for 10 minutes to make it evenly mixed. Add 100g of pseudo-boehmite to the mixed solution to fully knead the active component oxide, sulfur adsorbent oxide, and binder together. The resulting mixture was pressed into tablets, and the formed catalyst was baked at 80°C for 24h, then calcined at 180°C for 10h, and then calcined at 250°C for 8h to obtain an active component content of 11.5wt%, and a sulfur adsorbent content of 52wt% (including 41.6wt% zinc oxide, 10.4wt% iron oxide), and a catalyst with 36.5wt% alumina content.

Weigh 100g of catalyst and perform temperature-programmed reduction activation in a fixed-bed reactor. The activation conditions are: hydrogen pressure of 0.1MPa, volume space velocity of 1000h ^-1 , reduction at 350°C for 2h. After the reduction, lower the temperature to 200°C, pump catalytically cracked gasoline with a sulfur content of 800ppm and an octane number of 91 (RON) into the fixed-bed reactor for reaction, the mass space velocity is 0.2h ^-1 , H ₂ /oil The volume ratio is 50, and the results are shown in Table 1.

Example 2

Active components are loaded on the sulfur adsorbent by impregnation method, 250g nickel nitrate hexahydrate, 100g copper nitrate are weighed, dissolved in deionized water, the total volume of the solution is 300ml and stirred evenly, adding 100g calcium oxide (particle diameter is 50nm ), 50g manganese oxide (particle size is 100nm), 30g zinc oxide (particle size is 50nm) equal volume impregnation, stirring constantly in the process of impregnation, after 1h, place the impregnated sample in a desiccator with blast to dry , The dryer was slowly raised from room temperature to 150°C for 5 hours. The dried samples were roasted under the following conditions: roasting at 250°C for 2 hours, and rising to 500°C for 2 hours. Add 100g of alumina, 20g of diatomaceous earth, and 40g of cellulose to the roasted sample, and mix well. The obtained mixture was pressed into tablets, and the formed sample was baked at 150°C for 1 hour, and the obtained sample was fired at 230°C for 9 hours, and then fired at 400°C for 5 hours, to obtain an active component content of 24.5wt% (wherein NiO was 9.2%, CuO is 15.3%), sulfur adsorbent content is 45.3wt% (among them calcium oxide is 25.2wt%, manganese oxide is 12.6wt%, zinc oxide is 7.6wt%), binder content is 30.2wt% (of which Alumina is 25.2wt%, diatomaceous earth is 5.0wt%) catalyst.

Weigh 100g of catalyst and perform temperature-programmed reduction activation in a fixed-bed reactor. The activation conditions are: hydrogen pressure of 5MPa, volume space velocity of 10000h ^-1 , reduction at 550°C for 2h, and heating rate of 20°C/h. After the reduction, lower the temperature to 500°C, pump FCC gasoline with a sulfur content of 800ppm and an octane number of 91 into the fixed-bed reactor for reaction, the mass space velocity is 5h ^-1 , and the H ₂ /oil volume ratio is 1000 , and the results are shown in Table 1.

Example 3

The active component is loaded on the sulfur adsorbent by the impregnation method, and 300g of nickel nitrate hexahydrate is weighed, dissolved and stirred evenly with deionized water, so that the total volume of the solution is 300ml, 100g of titanium oxide (particle size is 20nm) is added, and 50g of Cerium (particle size: 60nm), 30g zinc oxide (particle size: 55nm) equal volume impregnation, stirring continuously during the impregnation process, after 6h, place the impregnated sample in a desiccator with blower to dry, and the desiccator starts from room temperature Slowly increase to 120 ° C for 8 hours. The dried samples were roasted under the following conditions: roasting at 200°C for 5 hours, rising to 450°C for 4 hours. Add 20g of kaolin, 50g of diatomite, and 40g of polypropylene alcohol to the roasted sample, and mix well. Roll the obtained mixture into pellets, bake the formed sample at 120°C for 5 hours, then bake at 280°C for 6 hours, and then bake at 350°C for 5 hours to obtain an active component content of 23.56 wt%, and a sulfur adsorbent content of 55.04wt% (of which titanium oxide is 30.57wt%, cerium oxide is 15.29wt%, zinc oxide is 9.17wt%), binder content is 21.4wt% (of which diatomite is 15.29wt%, kaolin is 6.12wt% ) catalyst.

Weigh 100g of catalyst and perform temperature-programmed reduction activation in a fixed-bed reactor. The activation conditions are: hydrogen pressure of 2MPa, volume space velocity of 10000h ^-1 , reduction at 350°C for 5h, and heating rate of 20°C/h. After the reduction, lower the temperature to 300°C, pump FCC gasoline with a sulfur content of 800ppm and an octane number of 91 into the fixed-bed reactor for reaction, the mass space velocity is 3h ^-1 , and the H ₂ /oil volume ratio is 300 , and the results are shown in Table 1.

Example 4

The active components nickel oxide and tungsten oxide are supported on the mixture of cerium oxide, titanium oxide, magnesium oxide and zinc oxide by kneading method. Take by weighing 2g nickel oxide, 3g tungsten oxide, 80g cerium oxide (particle size is 10nm), 20g titanium oxide (particle size is 80nm), 10g magnesium oxide (particle size is 20nm) and 60g zinc oxide (particle size is 20nm), Add 50ml of water and keep grinding for 60min to make it evenly mixed. Add 30g silica gel, 10g expanded perlite, 40g starch to the mixed solution, add 100ml of 5wt% dilute nitric acid solution, and fully knead the active component, sulfur adsorbent and binder together. The resulting mixture is extruded into a strip, the shaped catalyst is baked at 140°C for 20h, then fired at 200°C for 5h, and then fired at 450°C for 4h to obtain an active component content of 2.5wt% (wherein nickel oxide 1.0wt% %, cobalt oxide 1.5wt%), sulfur adsorbent content is 87.6wt% (cerium oxide 41.2wt%, titanium oxide 10.3wt%, magnesium oxide 5.2wt%, zinc oxide 30.9wt%), binder content 9.8% (wherein silicon oxide is 4.6wt%, expanded perlite 5.2wt%) catalyst.

Weigh 100g of catalyst and perform temperature-programmed reduction activation in a fixed-bed reactor. The activation conditions are: hydrogen pressure of 2MPa, volume space velocity of 1000h ^-1 , reduction at 480°C for 7h, and heating rate of 20°C/h. After the reduction, lower the temperature to 280°C, pump catalytically cracked gasoline with a sulfur content of 800ppm and an octane number of 91 into the fixed-bed reactor for reaction, with a mass space velocity of 3h ^-1 and a volume ratio of H ₂ /oil of 100 , and the results are shown in Table 1.

Example 5

The active components of nickel oxide, molybdenum oxide and cobalt oxide are supported on the mixture of manganese oxide and zinc oxide by kneading method. Weigh 50g of nickel oxide, 30g of molybdenum oxide, 20g of cobalt oxide, 20g of manganese oxide (with a particle size of 60nm), 60g of zinc oxide (with a particle size of 100nm), add 50ml of water and keep grinding for 20min to make it evenly mixed. Add 20g of aluminum oxide, 20g of starch, and 50ml of 5wt% dilute nitric acid solution to the mixed solution to fully knead the active component, sulfur adsorbent and binder together. The resulting mixture is extruded, and the formed catalyst is baked at 120°C for 10 hours, and then fired at 500°C for 5 hours at 180°C for 2 hours to obtain an active component content of 50 wt% (25 wt% of nickel oxide, oxidized Molybdenum 15wt%, cobalt oxide 10wt%), sulfur adsorbent content 40wt% (manganese oxide 10wt%, zinc oxide 30wt%), binder alumina content 10% catalyst.

Weigh 100g of catalyst and perform temperature-programmed reduction activation in a fixed-bed reactor. The activation conditions are: hydrogen pressure of 2.5MPa, volume space velocity of 1000h ^-1 , reduction at 400°C for 5h, and heating rate of 10°C/h. After the reduction, lower the temperature to 320°C, pump FCC gasoline with a sulfur content of 800ppm and an octane value of 91 into the fixed-bed reactor for reaction, the mass space velocity is 4h ^-1 , and the H ₂ /oil volume ratio is 300 , and the results are shown in Table 1.

Table 1 Catalyst technical characteristics and reaction results

Claims (8)

1. A deep adsorption desulfurization catalyst for fuel oil, characterized in that the catalyst includes an active component, a sulfur adsorbent, and a binding agent, wherein the active component is one or more of Ni, Co, Cu, W, Mo oxides species, the sulfur adsorbent is at least one of Mg, Ca, Zn, Ce, Fe, Mn, Ti oxides, the mass percentage of the active component is 2wt%-50wt%, the mass percentage of the sulfur adsorbent It is 20 wt%-90wt%, and the rest is binder, and the binder is alumina, pseudoboehmite, kaolin, montmorillonite, bentonite, montmorillonite, diatomaceous earth, silica sol, silica gel One or more mixtures of glue and expanded perlite. 2. A fuel oil deep adsorption desulfurization catalyst as claimed in claim 1, characterized in that said catalyst has the following characteristics: The specific surface area of the catalyst is 20-200m ² /g; The pore volume of the catalyst is 0.1-1.0cm ³ /g, and the average pore diameter is 5-50nm; The catalyst strength is 30-120N/particle; The particles of the sulfur adsorbent are nanoscale, and the particle diameter is 5-200nm. 3. The preparation method of a kind of fuel oil deep adsorption desulfurization catalyst as claimed in claim 1 or 2, is characterized in that comprising the steps: (a) loading the active component on the sulfur adsorbent by kneading or impregnation; (b) Mix the sample obtained in (a) with a binder and a pore-forming agent uniformly and form granules; (c) drying the catalyst sample obtained in (b) at 80-150 ^o C for 5-24h; (d) Calcining the sample obtained in (c) at 180-250 ^o C for 1-10 hours, and then at 250-500 ^o C for 2-8 hours to obtain the desired catalyst. 4. The preparation method of a fuel oil deep adsorption desulfurization catalyst as claimed in claim 3, characterized in that in step (a), the active component is loaded on the sulfur adsorbent by kneading method by mixing the active component oxide and sulfur The adsorbent oxide is kneaded in a kneader for 10-60min. 5. The preparation method of a fuel oil deep adsorption desulfurization catalyst according to claim 3, characterized in that in step (a), the active component is loaded onto the sulfur adsorbent by impregnation, and the steps are as follows: (1) Make a mixed solution of the soluble salt of the active component with deionized water, and heat the mixed solution to keep the temperature between 20-80 ^o C; (2) Soak the oxide of the sulfur adsorbent in the prepared solution for 1-6 hours, and keep stirring during the dipping process; (3) Dry the impregnated sample at 80-150 ^o C for 5-24 hours, and roast the dried catalyst at 180-250 ^o C for 1-10 hours, then at 250-500 ^o C for 2-8 hours. Can. 6. The preparation method of a fuel oil deep adsorption desulfurization catalyst as claimed in claim 5, characterized in that the soluble salt of the active component in step (1) is nitrate, acetate or chloride. 7. The preparation method of a fuel oil deep adsorption desulfurization catalyst as claimed in claim 3, characterized in that the pore-forming agent in step (b) is starch, cellulose, polyethylene glycol, polypropylene alcohol, and its dosage It is 1wt%-10wt% of the total amount of catalyst. 8. the application of a kind of fuel oil deep adsorption desulfurization catalyst as claimed in claim 1 or 2, is characterized in that comprising the steps: The reduction conditions are hydrogen pressure 0.1-5.0MPa, temperature 350 ^o C-550 ^oC , reduction time 2-20h; reaction conditions: temperature 200-500 ^o C, pressure 0.1-5.0MPa, fuel oil mass space velocity 0.2 -5.0h ^-1 , the H ₂ /oil volume ratio is 50-1000.