WO2017185929A1

WO2017185929A1 - Selective hydrogenation catalyst used for producing aviation fuel, and method for preparation thereof and application thereof

Info

Publication number: WO2017185929A1
Application number: PCT/CN2017/078023
Authority: WO
Inventors: 王春锋; 石友良; 许莉; 杨伟光; 赖波; 赵焘
Original assignee: 武汉凯迪工程技术研究总院有限公司
Priority date: 2016-04-27
Filing date: 2017-03-24
Publication date: 2017-11-02
Also published as: CN105944752A

Abstract

Provided is a selective hydrogenation catalyst used for producing aviation biofuel, comprising a carrier and a main metal active ingredient, said main metal active ingredient being loaded on said carrier; the weight percentage of the main metal active ingredient with respect to the catalyst finished product is 0.05-1.15%; the main metal active ingredient is Pt or Pd; the weight percentages of the raw materials of the carrier are 2-10% molecular sieve, 25-65% amorphous silica-alumina, 30-65% aluminum oxide, and 2-10% graphene additive. The method for preparing the catalyst comprises: placing the carrier into a metal saline solution containing Pt or Pd and soaking for 4-20 h to obtain a carrier after soaking; after drying said carrier, processing in a reduction atmosphere to obtain a selective hydrogenation catalyst. At the same capacity, the active surface area of the catalyst is larger and has more active sites, reducing reaction temperature and improving hydrogenation performance.

Description

Selective hydrogenation catalyst for producing aviation coal, preparation method and application thereof

Technical field

The invention relates to the field of catalysts, in particular to a selective hydrogenation catalyst for the production of biodiesel and a preparation method and application thereof.

Background technique

The most notable characteristics of the low temperature Fischer-Tropsch synthesis reaction are wide product distribution, low product selectivity, low isomeric product content, and most of the products are linear hydrocarbons. The above characteristics result in a very low octane number of the Fischer-Tropsch gasoline fraction and a high freezing point of the kerosene fraction and the diesel fraction, which limits the use of Fischer-Tropsch synthetic oil as a fuel oil to some extent.

The low temperature Fischer-Tropsch paraffin wax can produce aviation kerosene by hydrocracking and isomerization, and the obtained jet coal quality can be improved by adjusting the ratio of high carbon number isoparaffin to normal paraffin. Since the degree of isomerization of cracked kerosene is low at low conversion rates, kerosene having a high branched chain alkane content needs to be obtained under conditions of high hydrocracking conversion. The high-chain paraffin has low condensing point and low-temperature fluidity, which can meet the requirements of oil flow in cold and low temperature areas and high-altitude flight; and has good thermal stability and oxidation stability, which can meet the needs of supersonic high-altitude flight. .

The Chinese invention disclosed in CN104525247A discloses a catalyst based on modified multistage pores of SAPO-11 as a carrier to produce bio-aviation kerosene in accordance with the conditions of use. Although the catalyst has a high jet coal selectivity of more than 80%, the modification process of SAPO-11 is complicated and costly, and the acidity of the SAPO-11 carrier is weak, which is not conducive to the cracking reaction.

Since the graphene material is substantially non-acidic, which is not conducive to the cracking reaction, and the single layer and the small layer of graphene are expensive to prepare, and do not have the conditions for large-scale industrial production, the graphite is completely used in the preparation of the hydrocracking catalyst carrier. The olefin not only does not have good cracking performance, but also has low economic efficiency. However, the use of graphene as an auxiliary agent can significantly improve the activity, thermal conductivity and stability of the catalyst, so it is urgent to develop a synthetic oil from Fischer-Tropsch. A large-scale production of bio-jet fuel catalysts.

Summary of the invention

It is an object of the present invention to provide a selective hydrogenation catalyst for the production of jet fuel and to a process and application thereof. The catalyst has high hydrocracking conversion rate, mild reaction condition, strong applicability and low cost, and overcomes the Fischer-Tropsch synthesis stone. The defects of low selectivity, low isomerization and high reaction temperature of the wax during hydrocracking.

In order to achieve the above object, the present invention provides a selective hydrogenation catalyst for producing jet fuel, comprising a carrier and a main metal active component, the main metal active component being supported on a carrier; characterized in that: The main metal active component accounts for 0.05 to 1.15% by weight of the finished catalyst, the main metal active component is Pt or / and Pd, and the carrier is composed of 2 to 10% by weight of the molecular sieve, 25 to 25% by weight of the raw material. 65% amorphous silicon aluminum, 30-65% alumina and 2-10% graphene auxiliary.

Further, the raw material of the graphene auxiliary agent is composed of a secondary metal active component and graphene, and the auxiliary metal active component is supported on graphene, and the auxiliary metal active component accounts for the weight percentage of the graphene auxiliary agent. It is 0.05 to 1.15%, wherein the auxiliary metal active component is Pt or/and Pd.

Still further, the method for preparing the graphene auxiliary comprises the following steps:

1) dissolving a metal salt containing Pt or/and Pd in a graphite oxide solution to obtain a mixed solution,

2) The mixed solution is placed in a water bath at a temperature of 70-80 ° C, and then KBH ₄ or NaBH ₄ solution is added. After the reaction solution is cooled, the solution is centrifuged, washed with ethanol to completely remove Cl ^- , and freeze-dried to obtain Graphene auxiliaries.

The reduction treatment of the auxiliary agent is carried out by dropwise adding a 0.2 mol/L KBH ₄ or NaBH ₄ solution to the graphene auxiliary precursor solution under a nitrogen atmosphere until no more gas is released in the system.

Still further, the Pt-containing metal salt is chloroplatinic acid, and the Pd-containing metal salt is chloropalladium acid or palladium acetate.

Still further, the auxiliary metal active component accounts for 0.2 to 0.5% by weight of the graphene auxiliary.

Further, the method for preparing the graphite oxide comprises the following steps:

1) weighing natural graphite, anhydrous sodium nitrate and concentrated sulfuric acid by weight ratio: 1:0.5 to 2:50-100;

2) Slowly put natural graphite and anhydrous sodium nitrate into concentrated H ₂ SO ₄ placed in an ice bath, and slowly add potassium permanganate in a weight ratio of natural graphite: potassium permanganate = 1:5 to 10. Oxidation treatment, stirring for 0.5 to 2 hours to obtain a mixed solution;

3) The mixed solution is stirred in a water bath at a temperature of 25 to 45 ° C for 1 to 4 hours, while deionized water is slowly added to the mixed solution during the stirring;

4) further placing the mixed solution in a water bath at a temperature of 90-98 ° C and stirring for a high temperature reaction for 0.5 to 2 h; then diluting the mixed solution with deionized water to obtain a diluted solution;

5) according to the natural graphite: hydrogen peroxide weight ratio = 1: 20 ~ 50 hydrogen peroxide slowly added to the dilute solution, filtered hot to obtain a filtrate, wherein the mass fraction of hydrogen peroxide is 25 ~ 30%;

6) Wash thoroughly with hydrochloric acid until there is no SO ₄ ^{2- in the} filtrate, and then centrifuge several times with deionized water to remove Cl ^- until the filtrate becomes neutral, and a viscous yellow liquid is obtained;

7) The viscous yellow liquid is sonicated for 2 to 6 hours under the condition of 120-250 W, and the obtained graphite oxide solution is dried for 20 to 60 hours to obtain graphite oxide.

Further, the graphite oxide has a specific surface area of not less than 260 m ² /g and a layer spacing of not less than 0.80 nm.

Still further, the molecular sieve is any one or more of β, Y, ZSM-5, SAPO and MCM-41 molecular sieves.

Still further, the molecular sieve is a Y or beta molecular sieve.

Further, the alumina is composed of two grades, respectively, a small pore alumina and a large pore alumina; the weight percentage thereof is 1:1 to 2.3, respectively, wherein the specific surface area of the large pore alumina is 400 to 650 m. ² / g, the total pore volume is 0.8 ~ 1.3mL / g; the specific surface area of the small pore alumina is 200 ~ 380m ² / g, the total pore volume is 0.3 ~ 0.55mL / g.

Further, the main metal active component accounts for 0.2 to 0.5% by weight of the finished catalyst, and the carrier is composed of 3 to 6% molecular sieve, 30 to 50% of amorphous silica alumina, by weight of the raw material. 20 to 30% of macroporous alumina, 18 to 30% of small pore alumina, and 3 to 8% of graphene auxiliary.

Still further, the method for preparing the carrier comprises the following steps:

1) weighing molecular sieves, amorphous silica-alumina, alumina and graphene auxiliaries according to the above weight percentage;

2) Mixing molecular sieve, amorphous silica-alumina, alumina and graphene auxiliaries uniformly, and then adding tianjing powder (Tianjing powder dissipates in the subsequent roasting process, which acts to increase extrusion speed and improve the physical and chemical properties of the carrier) The mixture is kneaded and synthesized, dried and then calcined in an air atmosphere to obtain a carrier.

Further, in the step 2), the baking temperature is 350 to 500 ° C, and the time is 2 to 6 hours.

Still further, the carrier is in the form of a sheet, a strip, a ring, a wheel, a cylinder, a clover or a four-leaf clover.

The invention provides a preparation method of a selective hydrogenation catalyst for producing aviation coal, which comprises the following steps:

1) immersing the carrier in a solution containing Pt and/or Pd metal salt for 4-20 hours to obtain a carrier after impregnation;

2) The impregnated support is dried and then reduced in a reducing atmosphere to obtain a catalyst for selective hydrogenation.

Still further, the reduction treatment of the catalyst is carried out by passing hydrogen gas to the supported graphene catalyst precursor. For reduction, the catalyst reduction temperature of Pt and Pd is 110 to 180 ° C, and the treatment time is 3 to 5 hours. The obtained catalyst surface has a uniform atomic distribution and the same properties as a catalytically active center.

The invention also provides the application of the above selective hydrogenation catalyst in the maximum production of aviation coal in the Fischer-Tropsch synthesis oil, wherein the selective hydrogenation reaction temperature is 260-320 ° C, the reaction hydrogen The partial pressure is 1.0 to 6.0 MPa, the volumetric space velocity is 0.5 to 2 h ^-1 , and the hydrogen to oil volume ratio is 600 to 1000.

Principle of the invention

Carbon is one of the most common and wonderful materials on the planet. Since the discovery of graphene by British scientists in 2004, graphene has quickly become a hot topic in physics, chemistry and materials science due to its unique properties and two-dimensional nanostructures. Received widespread attention in the scientific community and was named one of the top ten scientific advances by Science Magazine in 2009. Graphene is a novel two-dimensional material with a single-layer two-dimensional honeycomb lattice structure, which is closely packed by carbon atoms and sp ² hybridized. The discovery of graphene forms a complete system from zero-dimensional fullerenes, one-dimensional carbon nanotubes, two-dimensional graphene to three-dimensional diamond and graphite, and graphene is considered to be fullerenes and carbon nanotubes. And the basic structural unit of graphite.

Graphene has excellent mechanical strength, large specific surface area, simple surface treatment and good electrical conductivity, thermal conductivity and chemical stability, making graphene an ideal composite carrier. Using graphene as a carrier, loading nanoparticles between graphene layers can not only improve the dispersibility of nanoparticles, but also promote the electron transfer during the catalytic reaction due to the electronic structure characteristics of graphene, and significantly improve the catalytic performance. Graphene has been used. Become a popular application material in many high-tech fields.

The beneficial effects of the invention are:

(1) Graphene is a carbonaceous new material in which a single layer of carbon atoms is closely packed into a two-dimensional honeycomb lattice structure. Compared with carbon nanotubes, it has a larger theoretical specific surface area. Because the active metal disperses well on graphene, it exhibits a larger active surface area and more active sites at the same loading. Lowering the reaction temperature and improving the performance of hydrogenation;

(2) The surface of the catalyst has low acidity, high hydrogenation activity and moderate cracking performance, less deposition of carbon and coke on the catalyst, and excellent stability and corrosion resistance of graphene, which are beneficial to prolong Catalyst regeneration cycle;

(3) The specific electronic properties of graphene can also interact with the active components, thereby improving the performance of the catalyst. Compared with traditional porous materials, this structure can avoid the blockage of the pores by the high-load active component, and can also Eliminating the internal diffusion of reactants and products in the pores, thereby increasing the reaction rate;

(4) Graphene has excellent thermal conductivity, which has obvious thermal conductivity advantage in the catalytic reaction of absorption and exothermic, and the temperature distribution of the catalyst bed is uniform;

(5) Since the production of graphene with a small layer and a high specific surface area is high, the present invention uses graphene supporting an active component as an auxiliary agent, and the content is only 2 to 10% by weight of the carrier, and the reduction process of the graphite oxide is At the same time, the metal is loaded, which greatly reduces the agglomeration of graphene, and achieves the high efficiency of graphene as an auxiliary agent while reducing the cost.

detailed description

In order to better explain the present invention, the main contents of the present invention will be further clarified below with reference to specific embodiments, but the content of the present invention is not limited to the following embodiments.

Preparation and purchase of raw materials

1. Preparation method of graphite oxide, the specific steps are as follows:

1) Weigh 1 g of natural graphite and 1 g of anhydrous NaNO _{3 and} slowly put them into 50 ml of concentrated H ₂ SO ₄ placed in an ice bath, and slowly add 6 g of KMnO ₄ as an oxidizing agent for oxidation treatment for 0.5 h (with continuous stirring). This is the pre-oxidation stage;

2) The flask was placed in a water bath at 35 ° C for 2 h, then 200 ml of deionized water was slowly added, during which the temperature was controlled not to exceed 50 ° C, then transferred to a 98 ° C water bath and stirred for a high temperature reaction for 30 min, using deionized water. Dilute to 400ml, slowly add 30ml of H ₂ O ₂ (30% by mass), filter it hot, wash it thoroughly with 5% HCl, until there is no SO ₄ ^{2- in the} filtrate, then wash it with deionized water. Once, remove Cl ^- until the solution becomes neutral;

3) Transfer the viscous yellow liquid to the beaker, then place it in the ultrasonic system for 4h to remove the graphite oxide at a power of 250W. (In order to prevent the agglomeration of the graphite oxide, the water is continuously changed during the ultrasonic process to ensure the water temperature in the ultrasonic system is not Above 40 ° C), the obtained graphite oxide solution was dried for 48 hours, that is, the obtained graphite oxide.

2. β molecular sieve: SiO ₂ /Al ₂ O ₃ is 50-80, specific surface is 500-650 m ² /g, pore volume is 0.35-0.6 ml/g; purchased at Nankai University Catalyst Factory;

Y molecular sieve: SiO ₂ /Al ₂ O ₃ is 2 to 3, specific surface 650 ~ 850 m ² / g, pore volume 0.35 ~ 0.5 ml / g;

ZSM-5 molecular sieve: SiO ₂ /Al ₂ O ₃ is 60-200, specific surface 450-600 m ² /g, pore volume 0.30-0.55 ml / g;

SAPO molecular sieve: specific surface 400 ~ 600m ² / g, pore volume 0.35 ~ 0.6ml / g;

MCM-41 molecular sieve: specific surface 800 ~ 1000m ² /g, pore volume 0.70 ~ 1ml / g;

Y, ZSM-5, SAPO and MCM-41 molecular sieves were purchased from Nankai University Catalyst Factory;

3, a specific surface area macroporous alumina 400 ~ 650m ² / g, a total mesopore volume 0.8 ~ 1.3mL / g; specific surface area alumina apertures 200 ~ 380m ² / g, a total pore pore volume 0.3 ~ 0.55mL / g; large pore alumina and small pore alumina were purchased from China Aluminum Corporation Shandong Branch.

4. Amorphous silica-alumina: SiO ₂ content is 35-60w%, specific surface 350-600m ² /g, pore volume 0.6-0.9ml/g; amorphous silicon-aluminum purchased from China Aluminum Shandong Branch;

5. Chloroplatinic acid, chloropalladic acid and palladium acetate were purchased from Hubei 798 Chemical Co., Ltd.

Tian Jing powder was purchased from the market, and other unspecified materials were purchased from the market.

Example 1

The preparation method of the graphene auxiliary 1 is as follows:

1) Weigh 1g of graphite oxide into 1L of deionized water, sonicate it, ultrasonic frequency is 180W, ultrasonic at 40 °C for 2h, after ultrasonication, add 2mL of 0.02mol/L PdCl ₂ solution to the solution, stir at room temperature for 10h , obtaining a mixed solution;

2) Under a water bath condition of 75 ° C, add 50 ml of 0.2 mol/L NaBH ₄ solution to the mixed solution for ₄ h. After the reaction solution is cooled, the solution is first washed twice with water, and then washed twice with ethanol. Then, it was washed several times with centrifugal water to completely remove Cl ^- (checked by AgNO ₃ ). The material obtained by centrifugation was freeze-dried in a freeze dryer for 20 hours, and the graphene auxiliary 1 was obtained after grinding.

The preparation method of the carrier 1 is as follows:

1) Weigh 2.0 g of graphene auxiliary 1, 0.5 g of β molecular sieve, 4.8 g of amorphous silica alumina, 2.5 g of macroporous alumina, 2 g of small pore alumina, and 0.1 g of phthalocyanine powder for kneading In the machine, dry mix for 15min, then add a 5% nitric acid solution, continue mixing for 30min;

2) The uniformly kneaded material was transferred to a squeezer to form an extruded strip, and the extruded carrier was freeze-dried for 20 hours, pelletized, and then reduced in a H ₂ atmosphere at 500 ° C for 4 hours, and then cooled to room temperature to obtain a carrier 1.

The preparation method of the selective hydrogenation catalyst 1 is as follows:

1) 5g of carrier 1 was immersed in 10mL of 0.02mol/L PdCl ₂ solution, soaked for 12h after supersaturation, and then filtered and allowed to stand for 2h.

2) Then, it was freeze-dried in a freeze dryer for 20 hours, finally cooled in a H ₂ atmosphere at 180 ° C for 4 hours, and then cooled to room temperature to obtain a selective hydrogenation catalyst 1.

Example 2

The preparation method of the graphene auxiliary 2, the specific steps are as follows:

1) Weigh 1g of graphite oxide into 1L of deionized water, sonicate it, ultrasonic frequency is 180W, ultrasonic at 40 °C for 2h, after ultrasonication, add 2mL of 0.01mol / L PtCl ₄ solution to the solution, stir at room temperature for 10h , obtaining a mixed solution;

2) Under a water bath condition of 75 ° C, add 50 ml of 0.2 mol/L NaBH ₄ solution to the mixed solution for ₄ h. After the reaction solution is cooled, the solution is first washed twice with water, and then washed twice with ethanol for 2 times. Centrifugal washing several times, completely remove Cl ^- (checked by AgNO ₃ ); the material obtained by centrifugation was freeze-dried in a freeze dryer for 20 h, and the graphene auxiliary 2 was obtained after grinding.

The preparation method of the carrier 2, the specific steps are as follows:

1) Weigh 2.0 g of graphene auxiliary 2, 0.5 g of β molecular sieve, 4.8 g of amorphous silica alumina, 2.5 g of macroporous alumina, 2 g of small pore alumina, and 0.1 g of phthalocyanine powder for kneading In the machine, dry mixing for 15 min; then add a 5% nitric acid solution, continue mixing for 30 min;

2) Transfer the uniformly mixed material to the extruder to form the extruded strip. The extruded carrier was freeze-dried for 20 hours, pelletized, and then reduced in an H ₂ atmosphere at 500 ° C for 4 hours and then cooled to room temperature to obtain a carrier 2.

The preparation method of the selective hydrogenation catalyst 2, the specific steps are as follows:

1) Weigh 5g of carrier 2 and immerse it in 10mL of 0.01mol/L PtCl ₄ solution, soak it for 12h after supersaturation, then filter and let it stand for 2h.

2) Then, it was freeze-dried in a freeze dryer for 20 hours, finally cooled in a H ₂ atmosphere at 180 ° C for 4 hours, and then cooled to room temperature to obtain a selective hydrogenation catalyst 2 .

Example 3

The preparation method in this embodiment is basically the same as that in Embodiment 1, except that:

The preparation method of the carrier 3, the specific steps are as follows:

1) Weigh 0.5 g of graphene auxiliary 1, 0.5 g of β molecular sieve, 4.5 g of amorphous silica alumina, 2.5 g of macroporous alumina, 2 g of small pore alumina, and 0.1 g of phthalocyanine powder for kneading In the machine, dry mix for 15min, then add a 5% nitric acid solution, continue mixing for 30min;

2) The uniformly kneaded material was transferred to a squeezer to form an extruded strip, and the extruded carrier was freeze-dried for 20 hours, pelletized, and then reduced in a H ₂ atmosphere at 500 ° C for 4 hours, and then cooled to room temperature to obtain a carrier 3.

The preparation method of the selective hydrogenation catalyst 3, the specific steps are as follows:

1) 5g of carrier 3 was immersed in 10mL of 0.02mol/L PdCl ₂ solution, soaked for 12h after supersaturation, and then filtered and allowed to stand for 2h.

2) Then, it was freeze-dried in a freeze dryer for 20 hours, finally cooled in a H ₂ atmosphere at 180 ° C for 4 hours, and then cooled to room temperature to obtain a selective hydrogenation catalyst 3.

Example 4

The preparation method of the carrier 4, the specific steps are as follows:

1) Weigh 0.7 g of graphene auxiliary 1, 0.5 g of β molecular sieve, 4.3 g of amorphous silica alumina, 2.5 g of macroporous alumina, 2 g of small pore alumina, and 0.1 g of phthalocyanine powder for kneading In the machine, dry mix for 15min, then add a 5% nitric acid solution, continue mixing for 30min;

2) The uniformly kneaded material was transferred to a squeezer to form an extruded strip, and the extruded carrier was freeze-dried for 20 hours, pelletized, and then reduced in a H ₂ atmosphere at 500 ° C for 4 hours, and then cooled to room temperature to obtain a carrier 4.

The preparation method of the selective hydrogenation catalyst 4 is as follows:

1) 5g of carrier 4 was immersed in 10mL of 0.02mol/L PdCl ₂ solution, soaked for 12h after supersaturation, and then filtered and allowed to stand for 2h.

2) Then, it was freeze-dried in a freeze dryer for 20 hours, finally cooled in a H ₂ atmosphere at 180 ° C for 4 hours, and then cooled to room temperature to obtain a selective hydrogenation catalyst 4.

Example 5

The preparation method of the carrier 5, the specific steps are as follows:

1) Weigh 1 g of graphene auxiliary 1, 0.5 g of β molecular sieve, 4 g of amorphous silica alumina, 2.5 g of macroporous alumina, 2 g of small pore alumina, 0.1 g of celery powder in a kneader , dry mixed for 15min, then add a 5% nitric acid solution, continue mixing for 30min;

2) The uniformly kneaded material was transferred to a squeezer to form an extruded strip, and the extruded carrier was freeze-dried for 20 hours, pelletized, and then reduced in a H ₂ atmosphere at 500 ° C for 4 hours, and then cooled to room temperature to obtain a carrier 5.

The preparation method of the selective hydrogenation catalyst 5 is as follows:

1) 5 g of the carrier 5 was immersed in 10 mL of a 0.02 mol/L PdCl ₂ solution, soaked for 12 hours under supersaturation, and then left to stand for 2 hours.

2) Then, it was freeze-dried in a freeze dryer for 20 hours, finally cooled in a H ₂ atmosphere at 180 ° C for 4 hours, and then cooled to room temperature to obtain a selective hydrogenation catalyst 5.

Example 6

The preparation method in this embodiment is basically the same as that in Embodiment 2, except that:

The preparation method of the carrier 6 is as follows:

1) Weigh 0.5 g of graphene auxiliary 2, 0.5 g of β molecular sieve, 4.5 g of amorphous silica alumina, 2.5 g of macroporous alumina, 2 g of small pore alumina, and 0.1 g of phthalocyanine powder for kneading In the machine, dry mixing for 15 min; then add a 5% nitric acid solution, continue mixing for 30 min;

2) Transfer the uniformly mixed material to the extruder to form the extruded strip. The extruded carrier was freeze-dried for 20 hours, pelletized, and then reduced in an H ₂ atmosphere at 500 ° C for 4 hours and then cooled to room temperature to obtain a carrier 6.

The preparation method of the selective hydrogenation catalyst 6 is as follows:

1) Weigh 5g of carrier 6 and immerse it in 10mL of 0.01mol/L PtCl ₄ solution, soak it for 12h after supersaturation, and then filter and let it stand for 2h.

2) Then, it was freeze-dried in a freeze dryer for 20 hours, finally cooled in a H ₂ atmosphere at 180 ° C for 4 hours, and then cooled to room temperature to obtain a selective hydrogenation catalyst 6.

Example 7

The preparation method of the carrier 7 is as follows:

1) Weigh 0.7 g of graphene auxiliary 2, 0.5 g of β molecular sieve, 4.3 g of amorphous silica alumina, 2.5 g of macroporous alumina, 2 g of small pore alumina, and 0.1 g of phthalocyanine powder for kneading In the machine, dry mixing for 15 min; then add a 5% nitric acid solution, continue mixing for 30 min;

2) Transfer the uniformly mixed material to the extruder to form the extruded strip. The extruded carrier was freeze-dried for 20 hours, pelletized, and then reduced in an H ₂ atmosphere at 500 ° C for 4 hours and then cooled to room temperature to obtain a carrier 7.

The preparation method of the selective hydrogenation catalyst 7 is as follows:

1) Weigh 5 g of carrier 7 and immerse it in 10 mL of 0.01 mol/L PtCl ₄ solution, soak it for 12 h after supersaturation, and then filter and let stand for 2 h.

2) Then, it was freeze-dried in a freeze dryer for 20 hours, finally cooled in a H ₂ atmosphere at 180 ° C for 4 hours, and then cooled to room temperature to obtain a selective hydrogenation catalyst 7.

Example 8

The preparation method of the carrier 8 is as follows:

1) Weigh 1 g of graphene additive 2, 0.5 g of β molecular sieve, 4 g of amorphous silica alumina, 2.5 g of macroporous alumina, 2 g of small pore alumina, 0.1 g of celery powder in a kneader , dry mixed for 15min; then add a 5% nitric acid solution, continue mixing for 30min;

2) Transfer the uniformly mixed material to the extruder to form the extruded strip. The extruded carrier was freeze-dried for 20 hours, pelletized, and then reduced in a H ₂ atmosphere at 500 ° C for 4 hours and then cooled to room temperature to obtain a carrier 8.

The preparation method of the selective hydrogenation catalyst 8 is as follows:

1) Weigh 5g of carrier 8 and immerse it in 10mL of 0.01mol/L PtCl ₄ solution, soak it for 12h after supersaturation, and then filter and let it stand for 2h.

2) Then, it was freeze-dried in a freeze dryer for 20 hours, finally cooled in a H ₂ atmosphere at 180 ° C for 4 hours, and then cooled to room temperature to obtain a selective hydrogenation catalyst 8 .

Example 9

The preparation method in this embodiment is basically the same as that in the third embodiment, and the difference is that:

The preparation method of the selective hydrogenation catalyst 9 is as follows:

1) 5 g of carrier 3 was immersed in 10 mL of 0.01 mol/L PdCl ₂ solution, soaked for 12 h after supersaturation, filtered and allowed to stand for 2 h, then freeze-dried in a freeze dryer for 20 h, and finally reduced at 180 ° C in H ₂ atmosphere. After 4 h, it was cooled to room temperature; the obtained catalyst was immersed in 10 mL of 0.005 mol/L PtCl ₄ solution, soaked for 12 h after supersaturation, and then filtered and allowed to stand for 2 h.

2) Then, it was freeze-dried in a freeze dryer for 20 hours, finally cooled in a H ₂ atmosphere at 180 ° C for 4 hours, and then cooled to room temperature to obtain a selective hydrogenation catalyst 9 .

Example 10

The preparation method of the carrier 10 is as follows:

1) Weigh 0.9 g of graphene auxiliary 1, 0.3 g of Y molecular sieve, 5 g of amorphous silica alumina, 2.0 g of macroporous alumina, 1.8 g of small pore alumina, and 0.1 g of phthalocyanine powder for kneading In the machine, dry mix for 15min; then add the quality score For 5% nitric acid solution, continue to knead for 30 min;

2) Transfer the uniformly mixed material to the extruder to form the extruded strip. The extruded carrier was freeze-dried for 20 hours, pelletized, and then reduced in an H ₂ atmosphere at 500 ° C for 4 hours and then cooled to room temperature to obtain a carrier 10.

Example 11

The preparation method of the carrier 11 is as follows:

1) Weigh 0.4 g of graphene auxiliary 2, 0.3 g of β molecular sieve, 0.3 g of Y molecular sieve, 3 g of amorphous silica alumina, 3.0 g of macroporous alumina, 3.0 g of small pore alumina, 0.1 g The rice phthalocyanine powder is mixed in a kneader for 15 min; then a nitric acid solution having a mass fraction of 5% is added, and the kneading is continued for 30 min;

2) Transfer the uniformly mixed material to the extruder to form the extruded strip. The extruded carrier was freeze-dried for 20 hours, pelletized, and then reduced in an H ₂ atmosphere at 500 ° C for 4 hours and then cooled to room temperature to obtain a carrier 11.

Example 12

The preparation method of the carrier 12 is as follows:

1) Weigh 0.8 g of graphene auxiliary 1, 1 g of β molecular sieve, 2.5 g of amorphous silica alumina, 3.5 g of macroporous alumina, 2.2 g of small pore alumina, and 0.1 g of phthalocyanine powder for kneading In the machine, dry mixing for 15 min; then add a 5% nitric acid solution, continue mixing for 30 min;

2) Transfer the uniformly mixed material to the extruder to form the extruded strip. The extruded carrier was freeze-dried for 20 hours, pelletized, and then reduced in an H ₂ atmosphere at 500 ° C for 4 hours and then cooled to room temperature to obtain a carrier 12.

Example 13

The preparation method of the carrier 13 is as follows:

1) Weigh 0.3g of graphene additive 2, 0.2g of SAPO molecular sieve, 4.5g of amorphous silica alumina, 2.5g of macroporous alumina, 2.5g of small pore alumina, 0.1g of phthalocyanine powder In the kneading machine, dry mixing for 15 min; then adding a nitric acid solution with a mass fraction of 5%, and continuing to knead for 30 min;

2) Transfer the uniformly mixed material to the extruder to form the extruded strip. The extruded carrier was freeze-dried for 20 hours, pelletized, and then reduced in an H ₂ atmosphere at 500 ° C for 4 hours and then cooled to room temperature to obtain a carrier 13.

Example 14

The preparation method in this embodiment is basically the same as that in the embodiment 9, except that:

The preparation method of the carrier 14 is as follows:

1) Weigh 0.2 g of graphene auxiliary 3, 0.1 g of SAPO molecular sieve, 0.2 g of MCM-41 molecular sieve, 6.5 g of amorphous silica alumina, 2.0 g of macroporous alumina, 1.0 g of small pore alumina 0.1 g of tianjing powder in a kneader, dry-mixed for 15 min; then add a nitric acid solution with a mass fraction of 5%, and continue to knead for 30 min;

2) Transfer the uniformly mixed material to the extruder to form the extruded strip. The extruded carrier was freeze-dried for 20 hours, pelletized, and then reduced in an H ₂ atmosphere at 500 ° C for 4 hours and then cooled to room temperature to obtain a carrier 14.

Comparative example 1

The preparation method of the carrier 15 is as follows:

1) Weigh 0.5g of β molecular sieve, 5g of amorphous silica alumina, 2.5g of macroporous alumina, 2g of small pore alumina, 0.1g of phthalocyanine powder in a kneader, dry mix for 15min, then add quality a 5% nitric acid solution, continue to knead for 30 min;

2) Transfer the uniformly mixed material to the extruder to form the extruded strip. The extruded carrier was freeze-dried for 20 hours, pelletized, and then calcined at 500 ° C for 4 hours in an air atmosphere, and then cooled to room temperature to obtain a carrier 15.

The preparation method of the hydrogenation catalyst 15 is as follows:

1) Weigh 5g of carrier 15 and immerse it in 10mL of 0.01mol/L PdCl ₂ solution, soak it for 12h after supersaturation, filter and let stand for 2h, then freeze-dry in the freeze dryer for 20h, and finally 180°C in H ₂ atmosphere. After reduction for 4 h, it was cooled to room temperature; the obtained catalyst was immersed in 10 mL of 0.005 mol/L PtCl ₄ solution, soaked for 12 h after supersaturation, and then left to stand for 2 h after filtration.

2) Then freeze-drying in a freeze dryer for 20 h, finally cooling in a H ₂ atmosphere at 180 ° C for 4 h, and then cooling to room temperature to obtain a selective hydrogenation catalyst 15

Comparative example 2

The preparation method of the carrier 16 is as follows:

1) Weigh 0.5g of β molecular sieve, 4.5g of amorphous silica alumina, 3g of macroporous alumina, 2g of small pore alumina, 0.1g of phthalocyanine powder in a kneader, dry mix for 15min, then add quality a 5% nitric acid solution, continue to knead for 30 min;

2) Transfer the uniformly mixed material to the extruder to form the extruded strip. The extruded carrier was freeze-dried for 20 hours, pelletized, and then calcined at 500 ° C for 4 hours in an air atmosphere, and then cooled to room temperature to obtain a carrier 16.

The preparation method of the hydrogenation catalyst 16 is as follows:

1) Weigh 5g of carrier 16 and immerse it in 10mL of 0.01mol/L PdCl ₂ solution, soak it for 12h after supersaturation, filter and let stand for 2h, then freeze-dry in the freeze dryer for 20h, and finally in 180°C in H ₂ atmosphere After cooling for 4 h, it was cooled to room temperature; the obtained catalyst was immersed in 10 mL of 0.005 mol/L PtCl ₄ solution, soaked for 12 h after supersaturation, and then filtered and allowed to stand for 2 h.

2) Then, it was freeze-dried in a freeze dryer for 20 hours, finally cooled in a H ₂ atmosphere at 180 ° C for 4 hours, and then cooled to room temperature to obtain a selective hydrogenation catalyst 16 .

Comparative example 3

The preparation method of the carrier 17, the specific steps are as follows:

1) Weigh 0.5g of β molecular sieve, 4.5g of amorphous silica alumina, 2g of macroporous alumina, 3g of small pore alumina, 0.1g of phthalocyanine powder in a kneader, dry mix for 15min, then add quality a 5% nitric acid solution, continue to knead for 30 min;

2) Transfer the uniformly mixed material to the extruder to form the extruded strip. The extruded carrier was freeze-dried for 20 hours, pelletized, and then calcined at 500 ° C for 4 hours in an air atmosphere, and then cooled to room temperature to obtain a carrier 17.

The preparation method of the hydrogenation catalyst 17 is as follows:

1) Weigh 5g of carrier 17 and immerse it in 10mL of 0.01mol/L PdCl ₂ solution, soak it for 12h after supersaturation, then filter and let it stand for 2h, then freeze-dry in the freeze dryer for 20h, and finally at 180°C in H ₂ atmosphere. After cooling for 4 h, it was cooled to room temperature; the obtained catalyst was immersed in 10 mL of 0.005 mol/L PtCl ₄ solution, soaked for 12 h after supersaturation, and then filtered and allowed to stand for 2 h.

2) Then, it was freeze-dried in a freeze dryer for 20 hours, finally cooled in a H ₂ atmosphere at 180 ° C for 4 hours, and then cooled to room temperature to obtain a selective hydrogenation catalyst 17 .

Table 2 main properties of raw oil

Table 3 Hydrogenation evaluation results of the catalyst of the present invention

It can be seen from Examples 1-8 that, under other conditions, the addition of graphene auxiliaries within a certain range can increase the yield of jet fuel; from Examples 10 to 14, the process parameters can be seen. It has a great influence on the yield and properties of the product, and the increase of reaction temperature and pressure can significantly improve the conversion rate of the raw materials; High catalyst conversion and jet fuel yield.

Other parts not described in detail are prior art. While the above-described embodiments have been described in detail, the present invention is only a part of the embodiments of the present invention, but not all of the embodiments, and other embodiments may be obtained without inventiveness according to the embodiments. All belong to the scope of protection of the present invention.

Claims

A selective hydrogenation catalyst for producing aviation coal, comprising a carrier and a main metal active component, the main metal active component being supported on a carrier; wherein the main metal active component occupies the finished catalyst product The weight percentage is 0.05 to 1.15%, the main metal active component is Pt or / and Pd, and the carrier is composed of 2 to 10% molecular sieve, 25 to 65% amorphous silicon aluminum, 30% by weight of the raw material. ~65% alumina and 2-10% graphene additive.
The selective hydrogenation catalyst for producing jet fuel according to claim 1, wherein the raw material of the graphene auxiliary agent is composed of a secondary metal active component and graphene, and the auxiliary metal active component is supported on On the graphene, the auxiliary metal active component accounts for 0.05 to 1.15% by weight of the graphene auxiliary agent, wherein the auxiliary metal active component is Pt or/and Pd.
The selective hydrogenation catalyst for producing jet fuel according to claim 2, characterized in that the method for preparing the graphene auxiliary comprises the following steps:

1) dissolving a metal salt containing Pt or/and Pd in a graphite oxide solution to obtain a mixed solution,

2) The mixed solution is placed in a water bath at a temperature of 70-80 ° C, and then KBH 4 or NaBH 4 solution is added. After the reaction solution is cooled, the solution is centrifuged, washed with ethanol to completely remove Cl - , and freeze-dried to obtain Graphene auxiliaries.
The selective hydrogenation catalyst for producing jet fuel according to claim 3, wherein the Pt-containing metal salt is chloroplatinic acid, and the Pd-containing metal salt is chloropalladium acid or palladium acetate.
The selective hydrogenation catalyst for producing jet fuel according to claim 2 or 3, characterized in that the auxiliary metal active component accounts for 0.2 to 0.5% by weight of the graphene auxiliary.
The selective hydrogenation catalyst for producing jet fuel according to claim 3, characterized in that the method for preparing the graphite oxide comprises the following steps:

1) weighing natural graphite, anhydrous sodium nitrate and concentrated sulfuric acid by weight ratio: 1:0.5 to 2:50-100;

2) Slowly put natural graphite and anhydrous sodium nitrate into concentrated H 2 SO 4 placed in an ice bath, and slowly add potassium permanganate in a weight ratio of natural graphite: potassium permanganate = 1:5 to 10. Oxidation treatment, stirring for 0.5 to 2 hours to obtain a mixed solution;

3) The mixed solution is stirred in a water bath at a temperature of 25 to 45 ° C for 1 to 4 hours, while deionized water is slowly added to the mixed solution during the stirring;

4) further placing the mixed solution in a water bath at a temperature of 90-98 ° C and stirring for a high temperature reaction for 0.5 to 2 h; then diluting the mixed solution with deionized water to obtain a diluted solution;

5) according to the natural graphite: hydrogen peroxide weight ratio = 1: 20 ~ 50 hydrogen peroxide slowly added to the dilute solution, filtered hot to obtain a filtrate, wherein the mass fraction of hydrogen peroxide is 25 ~ 30%;

6) Wash thoroughly with hydrochloric acid until there is no SO 4 2- in the filtrate, and then centrifuge several times with deionized water to remove Cl - until the filtrate becomes neutral, and a viscous yellow liquid is obtained;

7) The viscous yellow liquid is sonicated for 2 to 6 hours under the condition of 120-250 W, and the obtained graphite oxide solution is dried for 20 to 60 hours to obtain graphite oxide.
The selective hydrogenation catalyst for producing jet fuel according to claim 6, wherein the graphite oxide has a specific surface area of not less than 260 m 2 /g and a layer spacing of not less than 0.80 nm.
The selective hydrogenation catalyst for producing jet fuel according to claim 1 or 2, wherein the molecular sieve is any one or more of β, Y, ZSM-5, SAPO and MCM-41 molecular sieves.
The selective hydrogenation catalyst for producing jet fuel according to claim 8, wherein the molecular sieve is a Y or β molecular sieve.
The selective hydrogenation catalyst for producing jet fuel according to claim 1 or 2, wherein the alumina is composed of two grades, respectively, a small pore alumina and a large pore alumina; are from 1/1 to 2.3; wherein the large pore surface area alumina 400 ~ 650m 2 / g, a total mesopore volume 0.8 ~ 1.3mL / g; specific surface area alumina apertures 200 ~ 380m 2 / g, total The pore volume is 0.3 to 0.55 mL/g.
The selective hydrogenation catalyst for producing biodiesel according to claim 10, wherein the main metal active component accounts for 0.2 to 0.5% by weight of the finished catalyst, and the carrier is based on the weight percentage of the raw material. It is composed of 3 to 6% molecular sieve, 30 to 50% amorphous silica alumina, 20 to 30% macroporous alumina, 18 to 30% small pore alumina, and 3 to 8% graphene auxiliary.
The selective hydrogenation catalyst for producing jet fuel according to claim 1, wherein the preparation method of the carrier comprises the following steps:

1) weighing molecular sieves, amorphous silica-alumina, alumina and graphene auxiliaries according to the above weight percentage;

2) The molecular sieve, the amorphous silicon aluminum, the aluminum oxide and the graphene auxiliary are uniformly mixed, and then added to the Tianjing powder to be kneaded and kneaded, dried, and then calcined in an air atmosphere to obtain a carrier.
The selective hydrogenation catalyst for producing jet fuel according to claim 12, wherein in the step 2), the calcination temperature is 350 to 500 ° C and the time is 2 to 6 h.
The selective hydrogenation catalyst for producing jet fuel according to claim 12 or 13, wherein the carrier is in the form of a sheet, a strip, a ring, a wheel, a cylinder, a clover or a four-leaf clover .
A method for preparing a selective hydrogenation catalyst for producing jet fuel according to claim 1, comprising the steps of:

1) immersing the carrier in a solution containing Pt and/or Pd metal salt for 4-20 hours to obtain an impregnated carrier;

2) The impregnated support is dried and then treated under a reducing atmosphere to obtain a catalyst for selective hydrogenation.
The method for preparing a selective hydrogenation catalyst for producing jet fuel according to claim 15, wherein the metal salt containing Pt is chloroplatinic acid, and the metal salt containing Pd is chloropalladium acid or palladium acetate.
The invention relates to the application of the selective hydrogenation catalyst of claim 1 in the maximum production of jet fuel of Fischer-Tropsch synthetic oil, characterized in that: in the production of aviation coal, the selective hydrogenation reaction temperature is 260-320 ° C The partial pressure of hydrogen reacted is 1.0 to 6.0 MPa, the volumetric space velocity at a liquid time is 0.5 to 2 h -1 , and the volume ratio of hydrogen to oil is 600 to 1000.