CN103041820B - Preparation method of spherical hydrogenation catalyst - Google Patents

Abstract

The invention discloses a preparation method of a spherical hydrogenation catalyst. The method is prepared by adopting the spherical carrier prepared by the spherical sizing method, and then loading the active metal component by the impregnation method, wherein the carrier is improved by adding gemini surfactant to the alumina precursor Physical properties, adjust the adhesion and rheology of the material during the carrier molding process, reduce the plastic deformation of the carrier after molding, greatly increase the yield of the spherical carrier, improve the strength of the spherical carrier, and increase the particle size of the spherical carrier. Proportion. In addition, the use of gemini surfactants will not introduce Na ⁺ , Ca ²⁺ , K ⁺ , Cl ^- , Br ^- , F ^- , I ^- and other anions and cations, and the molecular weight of gemini surfactants is relatively large, so the pore expansion effect is good . The catalyst has large pore volume and specific surface area, and the spherical particles of the catalyst are uniform, which makes loading and unloading of the catalyst easy, and easily meets the requirement of dense phase packing.

Description

Preparation method of spherical hydrogenation catalyst

technical field

The invention relates to a preparation method of a spherical catalyst, especially a spherical hydrogenation catalyst. The method can be used for petroleum wax hydrorefining catalysts, and can also be used for heavy distillate oil hydrotreating catalysts, and is especially suitable for reactors with a large aspect ratio and a small reactor diameter.

Background technique

In recent years, with the increasing reduction and inferiority of high-waxy crude oil resources, the shortage and inferiority of paraffin resources have been caused; at the same time, the increase in domestic paraffin production and the increase in market demand have resulted in the processing of inferior paraffin and high-melting point waxes. The demand is increasing; while the requirements of environmental protection regulations are becoming increasingly stringent, the production and use of catalysts are required to be as pollution-free as possible and to achieve clean operation. Therefore, it is necessary to study high activity, low cost and environment-friendly catalysts for paraffin hydrotreating.

At present, the petroleum wax hydrorefining catalysts used in industry are basically cylindrical or three- and four-leaf clover strips. This type of catalyst has the advantages of high molding efficiency and large production volume. However, since the petroleum wax hydrogenation reactor is characterized by a large height-to-diameter ratio and a small reactor diameter (0.80-1.40m), it is not conducive to the loading and unloading of the catalyst. It is difficult to achieve uniform dense-phase packing of the catalyst, because the dense-phase packing cannot be installed in such a small-diameter reactor, so dense-phase packing cannot be realized. Therefore, the petroleum wax hydrorefining catalyst should be prepared in a spherical shape. The loading and unloading of the spherical catalyst is easy, and it is easy to meet the requirements of dense phase packing.

At present, industrial hydrotreating catalysts are usually supported by alumina or alumina containing a small amount of additives. The preparation methods of spherical particle catalysts mainly include: spray drying molding, rolling molding, molding in oil, spherical sizing method, etc.

Spray drying molding is a method of producing powdery and microspherical products using the principle of spray drying. That is, an atomizer is used to disperse the raw material slurry into droplets, and the droplets are dried with hot air. The key technology of spray molding lies in the micronization (atomization) of slurry solids, which requires finer atomized droplets. Therefore, spray molding is suitable for the preparation of microsphere (several microns or tens of microns) catalysts, fluid catalytic cracking catalysts It is mostly prepared by spray drying method.

Rotational molding is to send powder and appropriate amount of water (or other binders) into a low-speed rotating container. The powder particles are agglomerated under the action of liquid bridge and capillary force to form micronuclei. Under the action of rolling and rolling impact, it continuously turns and grows in the powder layer, and finally becomes spherical particles of a certain size and leaves the container. Rotational molding has a large processing capacity, less equipment investment, and high operating rate, but the particle density is not high, the strength is poor, it is difficult to prepare smaller particle balls, and the dust is relatively large during operation. Due to the above-mentioned shortcomings of this method, its application has gradually decreased.

Molding in oil is to use the characteristics of gelation of sol at an appropriate pH value and concentration. The sol is dropped into a medium such as kerosene in the form of small droplets. Due to the effect of surface tension, it shrinks into a ball and then gels to form small particles. . This kind of method exists the problem of environmental pollution, and its application is also gradually reduced.

Spherical granulation method is to add water, peptizer and forming aids to the material, knead it into a soft block plastic body, then add it to the extruder, extrude the cylindrical strip through the cylindrical orifice plate, pelletize, roll the ball , dried and calcined to obtain a spherical catalyst carrier. Then the active metal is impregnated to obtain a spherical catalyst. This method has no pollution to the environment, and the preparation of spherical catalysts is developing in this direction.

CN1085594A discloses a kind of wax material hydrogenation refining catalyst, with Mo, Ni as active components, the preparation process of this catalyst: neutralize the silica-alumina mixed sol after low-temperature aging with ammonia water, after filtering, washing, with phosphoric acid and nitric acid Peptization, and then forming through the oily ammonia column, and the carrier is formed through the oily ammonia column. This ball forming process is complicated, and there is ammonia nitrogen pollution problem, which does not meet the environmental protection requirements. Manual operation is adopted in the forming process of drop ball and oil ammonia column, and workers are exposed to the environment full of ammonia gas for a long time, which will cause great harm to their health.

CN01114183.2 discloses a wax hydrorefining catalyst and its preparation method. This method adopts SiO ₂ -P ₂ O ₅ -Al ₂ O ₃ with large pore volume, large specific surface area, highly concentrated pore distribution and weak acidity as the carrier, and W and Ni as the active metal components. Ni/W( Mole) ratio is 0.30～0.80. The pore volume of the catalyst is 0.40-0.55 cm ³ /g, and the pore volume fraction within the pore diameter range of 4-15 nm accounts for 95%-99% of the pore volume fraction within the pore diameter range of 0-100 nm. The catalyst has higher activity and selectivity when it is used for hydrofinishing of wax. However, this method also adopts the process of forming into balls through the oily ammonia column at room temperature, the process is complicated, and there is ammonia nitrogen pollution in the production process, and the ball size is not uniform, the strength is low, the yield is low, and the molding efficiency is low.

CN200910079772.8 discloses a toothed spherical heavy oil hydrotreating catalyst and a preparation method thereof. Preparation of alumina carrier precursor: add peptizer, pore expander and forming aid to aluminum hydroxide, after mixing evenly, add deionized water and nitric acid, mix evenly, and obtain soft block plastic body; said peptizer It is nitric acid, citric acid, acetic acid or tartaric acid or a mixture of any two or more of the foregoing. In this way, the strong acid and alumina will inevitably have a strong interaction, which will cause serious loss of pore volume and specific surface area, and reduce the pore volume and specific surface area of the final catalyst.

CN03134003.2 discloses a petroleum wax hydrorefining catalyst and its preparation method. The catalyst uses tungsten, molybdenum and nickel (or cobalt) as active metals, and alumina containing two additives of silicon and phosphorus as a carrier , and its preparation method is prepared by respectively impregnating an aqueous solution containing tungsten-nickel or cobalt and an aqueous solution containing molybdenum-boron on an alumina carrier containing silicon and phosphorus. The alumina support containing silicon and phosphorus is prepared by adding silicon-containing aluminum hydroxide prepared by _CO2 neutralization method as a raw material, and adding a phosphorus-containing compound during the forming process of the support. The method can effectively adjust the physical and chemical properties of the catalyst through the synergistic adjustment effect of the two composite additives, so that the catalyst has a reasonable pore structure and suitable surface acid properties. The catalyst can process petroleum wax materials including high melting point wax materials, and can produce food-grade petroleum wax products. CN03133997.2 discloses a petroleum wax hydrogenation catalyst and its preparation method. The method is to use the silicon-containing and phosphorus-containing aluminum hydroxide prepared by the _CO2 neutralization method as the carrier material of the catalyst, wherein the two additives of silicon and phosphorus in the silicon-containing and phosphorus-containing aluminum hydroxide are added step by step, and part of the silicon-containing It is mixed with phosphorus-containing compounds and sodium metaaluminate solution to form a gel. Part of the silicon-containing compound is added after the gel is formed or during the aging process. Most of the phosphorus-containing compounds are formed in the aluminum hydroxide and washed in the gel. Added in the process of dissolving or slurrying, so that most of the silicon and phosphorus are distributed on the surface of aluminum hydroxide, and effectively play the role of silicon and phosphorus in synergistically adjusting the physical and chemical properties and pore structure of the catalyst surface. The catalyst has good activity and selectivity when processing petroleum wax materials, including high melting point petroleum wax. The petroleum wax hydrorefining catalysts in the above two patents are formed by extrusion, which has high molding efficiency, can prepare catalysts with relatively small particle equivalent diameters, and solves the problem of diffusion and mass transfer of heavy components. If it is made into a spherical catalyst, the molding efficiency will not be too high and needs to be improved.

In the prior art, the method of preparing spherical catalysts by extruding and pelletizing generally involves adding peptizers and forming aids to the materials. Peptizers are generally nitric acid, citric acid, acetic acid or tartaric acid. Forming aids are generally safflower powder or polyethylene glycol, etc. The adhesion and rheological properties of the cylindrical strips extruded through the cylindrical orifice plate are not good, resulting in low molding efficiency.

Contents of the invention

Aiming at the deficiencies of the prior art, the invention provides a method for preparing a spherical hydrogenation catalyst with large pore volume, large specific surface area and weak acidity. The spherical hydrogenation catalyst obtained by the method has uniform spherical particle size, high strength, high yield and small loss. When the catalyst is used for hydrogenation of petroleum wax, it has good hydrofinishing and aromatic hydrocarbon saturation capabilities.

The preparation method of spherical hydrogenation catalyst of the present invention comprises:

(1) Mix the alumina precursor, gemini surfactant, and adhesive evenly. The amount of adhesive added is 2.0% to 10.0% of the weight of alumina, and the amount of gemini surfactant added is 0.5% to 8.0% of the weight of alumina. %;

(2) After the mixture obtained in step (1) is kneaded, extruded and pre-dried, it is pelletized and pelletized with a spherical granulator, and then dried and roasted to obtain a spherical catalyst carrier;

(3) The spherical catalyst carrier obtained in step (2) is loaded with active metal components by an impregnation method, and then dried and calcined to obtain a spherical hydrogenation catalyst.

The spherical catalyst carrier of the present invention may also contain auxiliary components, and the auxiliary agent is one or more of silicon, zirconium, titanium, iron, phosphorus, boron and the like. The way in which the auxiliary agent is introduced into the carrier can be introduced in any way in the prior art, such as the method of introducing silicon and phosphorus in CN01114183.2, CN03133997.2, CN03134003.2, the introduction of boron, phosphorus, silicon, zirconium and titanium in CN 200410050777.5 method.

In step (1), the order of adding the alumina precursor, gemini surfactant and adhesive is not limited. The adhesive is prepared by mixing one or more of small-pore alumina, aluminum nitrate and aluminum sulfate with inorganic acid and/or organic acid, wherein the amount of inorganic acid and/or organic acid accounts for 30% of the weight of the adhesive. %~60%. Among them, the properties of small-pore alumina are generally as follows: the specific surface area is 200m ² /g~400m ² /g, and the pore volume is 0.3ml/g~0.6ml/g. The inorganic acid can be selected from one or more of nitric acid, phosphoric acid, sulfuric acid and hydrochloric acid, preferably nitric acid, and the organic acid can be selected from one or more of acetic acid, citric acid and oxalic acid.

The Gemini surfactant can be selected from one or more of the quaternary ammonium salt gemini surfactant series and the acetylenic diol gemini surfactant 400 series. Quaternary ammonium salt gemini surfactant series are commonly used dibromide-N,N'-bis(dimethyldodecyl)propylene diammonium, N,N'-dimethylcarboxybetaine, 1,3-bis One of dodecyl-N,N-dimethyl bromide-2-propanol, 1,3-ditetradecyl-N,N-dimethyl bromide-2-propanol, etc. One or more, acetylenic diol gemini surfactant 400 series commonly used one or more of Cido-420, Cido-440, Cido-465, Cido-485 surfactants. In the process of mixing and kneading, in order to further facilitate extrusion molding, extrusion aids, such as one or more of safflower powder, polyethylene glycol, etc., can also be added. In order to ensure that the catalyst carrier has the required macropore ratio, a pore-enlarging agent can be added during the preparation process, and the amount of the pore-enlarging agent added is 0.1% to 5.0% of the weight of the alumina precursor. The pore-enlarging agent can be selected from conventional types, such as one or more of conventional combustible solid powders such as methylcellulose, starch derivatives, sodium polyacrylate, and carbon black, preferably sodium polyacrylate.

The pre-drying temperature in step (2) is 20-70°C, the time is 0.2-1.0 hours, the drying is at a temperature of 90-130°C for 2-4 hours, and the roasting is at a temperature of 600-900°C Roast for 3 to 6 hours.

The spherical granulator described in step (2) adopts the existing spherical granulator.

In step (3), before drying, it is best to store the impregnated material in air or inert gas for 0.5-2.0 hours to prevent the spherical catalyst from bursting during the roasting process. The drying temperature in step (3) is 100-120° C., the drying time is 2.0-5.0 hours, the roasting temperature is 350-550° C., and the roasting time is 3.0-6.0 hours. Described impregnation method can adopt conventional method to carry out, wherein active metal can be the VIII group and the VIB group metal, wherein the VIII group metal is Ni or Co, the VIB group metal is W or Mo, the weight of catalyst is As a benchmark, the content of Group VIII metals (calculated as oxides) is 0.5wt%~9.0wt%, and the content of Group VIB metals (calculated as metal oxides) is 5.0wt%~30.0wt%.

The spherical catalyst carrier used in the present invention is prepared by a spherical sizing method, and the physical properties of the surface of the alumina carrier are improved by adding gemini surfactants to the alumina precursor, and the adhesion of materials during the carrier molding process is adjusted. It reduces the plasticity of the carrier after molding, greatly increases the yield of the spherical carrier, improves the strength of the spherical carrier, and increases the proportion of complete particles of the spherical carrier, which not only reflects the advantages of anionic and cationic surfactants, At the same time, it does not introduce anion and cation heteroions such as Na ⁺ , Ca ²⁺ , K ⁺ , Cl ^- , Br ^- , F ^- , I ^-, etc. In addition, the gemini surfactant has a large molecular weight and has a good pore expansion effect. The catalyst has large pore volume and specific surface area, and the spherical particles of the catalyst are uniform, which makes loading and unloading of the catalyst easy, and easily meets the requirement of dense phase packing.

The spherical catalyst prepared by the invention can be used in the hydrofinishing process of paraffin wax raw materials with a large metal content. Wherein the metal content in the paraffin wax raw material can be above 5 μg/g, or above 10 μg/g, or above 20 μg/g. The hydrofining conditions can adopt common conditions in this field, such as reaction pressure (hydrogen partial pressure) 3~16MPa, reaction temperature 230~310℃, liquid volume space velocity 0.5~2.0h ^-1 , hydrogen/wax volume ratio 200~800 .

Detailed ways

The spherical hydrogenation catalyst prepared by the method of the present invention is preferably used as a silicon and boron auxiliary agent in the process of paraffin hydrogenation refining. The catalyst is mainly composed of alumina and contains boria and silica. The weight content of boron oxide in the carrier is generally 0.5% to 10.0%, preferably 2.0% to 8.0%. The weight content of silica in the carrier is The content is generally 0.5% to 20.0%, preferably 2.0% to 15.0%. In the preparation process of the spherical catalyst carrier, the silicon source and the boron source are added in step (1), wherein the silicon source is water glass or silica sol, and the boron source is boric acid. The boric acid is preferably added in the form of boric acid aqueous solution or boric acid acidic solution, wherein the temperature of the solution is 30-100°C, preferably 40-80°C.

During the preparation process of the spherical catalyst carrier, the silicon source can be added in any step of mixing the alumina precursor, anionic surfactant, cationic surfactant, and adhesive, and the boron source can be added after the above materials are evenly mixed.

The properties of the above-mentioned spherical hydrogenation catalyst are as follows: based on the weight of the catalyst, the content of _MoO3 or _WO3 is 5.0wt%~30.0wt%, preferably 12.0wt%~23.0wt%, and the content of NiO or CoO is 0.5wt% %~9.0wt%, preferably 1.0wt%~8.0wt%, specific surface area is 150~300m ² /g, preferably 180~250m ² /g, pore volume is 0.30~0.70cm ³ /g, preferably 0.35~ 0.45 cm ³ /g, the amount of infrared acid is 0.20-0.80 mmol/g, preferably 0.30-0.70 mmol/g, and the mechanical strength is ≥35.0 N/grain.

To further illustrate the method of the present invention, the following examples are cited. wt% is mass fraction.

Example 1

Weigh 200g of pseudo-boehmite powder prepared by carbonization (containing Al(OH) ₃ <3wt%), add 20.0 grams of water glass, 8.0 grams of sodium polyacrylate and 15.0 grams of polyethylene glycol, mix, then add 14 grams of adhesive (wherein the small-pore alumina is 35.0wt% , concentrated nitric acid is 34.4wt%, water is 30.6wt%) and a mixture of gemini surfactants (4 grams of N, N'-dimethylcarboxybetaine), and then add Dissolve 6.5 grams of boric acid in 100ml of 50°C water, mix well, knead it into a plastic shape, and extrude it into a strip (the diameter of the strip orifice is 1.9mm). Then it was pre-dried in a drying oven at 30°C for 0.35 hours, cut into balls by a spherical granulator, dried at 110°C for 3 hours, and roasted at a constant temperature of 600°C for 3.0 hours to obtain a spherical hydrogenation catalyst carrier.

Weigh 100 grams of spherical carrier and impregnate with 100 ml of impregnation solution. (the content of MoO ₃ is 25.2 g/100ml, the content of NiO is 6.6g/100ml, and the content of phosphorus is 2.1 g/100ml), the wet bulb catalyst is placed in the air for 1.0 hours, and then dried at 110°C for 2 hours, 450 The catalyst A was obtained by calcining at ℃ for 4 hours.

Example 2

Take 200g of pseudo-boehmite powder prepared by carbonization (containing Al(OH) ₃ < 3wt%), mix 25.0g of silica sol, 10.0g of methylcellulose and 3.0g of scallop powder, mix well, add 18g of adhesive (30.0wt% small-pore alumina, 39.1wt% concentrated phosphoric acid, 30.9wt% water) and a mixture of surfactants 1,3-didodecyl-N,N-dimethylammonium bromide -2-propanol is 6 grams ) , then add 6.5 grams of boric acid dissolved in 100ml of 70°C water, mix thoroughly, knead into a plastic shape and extrude into strips (the diameter of the strip orifice is 2.1mm). It was then pre-dried in a drying oven at 40° C. for 0.3 hours. After being cut and pelletized by a spherical granulator, it was dried at 110°C for 4 hours, and then calcined at a constant temperature of 600°C for 4.0 hours to make a spherical hydrogenation catalyst carrier.

Weigh 100 grams of spherical carrier and impregnate with 100 ml of impregnation solution. (the content of MoO ₃ is 27.3 g/100ml, the content of NiO is 3.8g/100ml, the content of CoO is 0.8g/100ml, and the content of phosphorus is 1.6g/100ml), the wet bulb catalyst is placed in the air for 1.5 hours, Then, it was dried at 120° C. for 2 hours, and calcined at 500° C. for 4 hours to obtain catalyst B.

Example 3

Take 200g of pseudo-boehmite powder (containing Al(OH) ₃ < 3 wt %) prepared by the aluminum nitrate method, mix 20.0g of silica sol, 6.0g of carbon black and 3.0g of scallop powder, and then add 20g of adhesive ( in which small A mixture of 40.0 wt % porous alumina , 38.6 wt % citric acid, and 21.4 wt % water) and a surfactant (4 grams of acetylenic diol gemini surfactant Cido-420) is mixed evenly, and then added with 100 ml Boric acid 6.0 dissolved in water at 60°C, fully mixed, kneaded into a plastic shape, extruded into strips (the diameter of the strip-shaped orifice plate is 2.3mm), and then pre-dried in a drying oven at 20°C for 0.7 hours. After being cut and pelletized by a spherical granulator, it was dried at 110°C for 3 hours, and then calcined at a constant temperature of 600°C for 4.0 hours to make a spherical catalyst carrier.

Weigh 100 grams of spherical carrier, 100ml impregnation solution for impregnation (the content of MoO ₃ is 19.1g/100ml, the content of WO ₃ is 7.9 g/100ml, the content of NiO is 3.8g/100ml, the content of CoO is 1.3g/100ml , the phosphorus content is 3.5 g/100ml), the wet bulb catalyst was placed in the air for 2.5 hours, then dried at 130°C for 2 hours, and calcined at 550°C for 3 hours to obtain catalyst C.

Example 4

Take 200g of pseudo-boehmite powder (containing Al(OH) ₃ < 3 wt %) prepared by the aluminum nitrate method, mix 22.0 grams of silica sol, 6.1 grams of carbon black and 2.8 grams of scallop powder, and then add 22 grams of adhesive ( in which small 40.0 wt % porous alumina , 38.6 wt % citric acid, 21.4 wt % water) and a mixture of gemini surfactants (1,3-Ditetradecyl-N,N-dimethylammonium bromide- 2-propanol is 4 grams) after mixing evenly, add boric acid 6.0 dissolved in 100ml 60 ℃ water, mix well, knead into a plastic shape and extrude into strips (the diameter of the strip-shaped orifice plate is 2.3mm) and then in 20 ℃ Pre-dried in a drying oven for 0.7 hours. After being cut and pelletized by a spherical sizing machine, it was then dried at 110°C for 3 hours, and then calcined at a constant temperature of 600°C for 4.0 hours to make a spherical catalyst carrier.

Weigh 100 grams of spherical carrier, 100ml impregnation solution for impregnation (the content of MoO ₃ is 19.1g/100ml, the content of WO ₃ is 7.9 g/100ml, the content of NiO is 3.8g/100ml, the content of CoO is 1.3g/100ml , the phosphorus content is 3.5 g/100ml), the wet bulb catalyst was placed in the air for 2.5 hours, then dried at 130°C for 2 hours, and calcined at 550°C for 3 hours to obtain catalyst D.

Comparative example 1

Weigh 200g of pseudo-boehmite powder prepared by carbonization (containing Al(OH) ₃ < 3wt%), add 20.0 grams of water glass, 8.0 grams of sodium polyacrylate and 15.0 grams of polyethylene glycol, mix, and then add 14 grams of adhesive (35.0wt% of small-pore alumina , 34.4wt% of concentrated nitric acid, and 30.6wt% of water), then add 6.5g of boric acid dissolved in 100ml of 50°C water, mix well, knead into a plastic shape and extrude into strips. (The diameter of the strip orifice is 1.9mm). It was then pre-dried in a drying oven at 40° C. for 0.3 hours. After being cut and pelletized by a spherical granulator, it was dried at 110°C for 3 hours, and then calcined at a constant temperature of 600°C for 3.0 hours to obtain a spherical hydrogenation catalyst carrier.

Weigh 100 grams of spherical carrier, 100ml of impregnation solution for impregnation (the content of _MoO3 is 18.7g/100ml, the content of _WO3 is 8.0g/100ml, the content of NiO is 4.0g/100ml, the content of phosphorus is 3.5g/100ml ), the wet bulb catalyst was placed in air for 2.5 hours, then dried at 130°C for 2 hours, and calcined at 550°C for 3 hours to obtain catalyst E.

Comparative example 2

Take 200g of pseudo-boehmite powder (containing Al(OH) ₃ < 3wt %) prepared by carbonization, mix 25.0 grams of silica sol, 10.0 grams of methylcellulose and 3.0 grams of turmeric powder, and then add 4.2 grams of hexadecyl Trimethyl ammonium chloride, after mixing evenly, add 12 grams of adhesive (30.0wt% of small-pore alumina, 39.1wt% of concentrated phosphoric acid, 30.9wt% of water), and then add 6.5% of boric acid dissolved in 100ml of 70°C water gram, fully mixed, kneaded into a plastic shape and then extruded into strips (the diameter of the strip orifice is 2.1mm). It was then pre-dried in a drying oven at 30° C. for 0.35 hours. After being cut and pelletized by a spherical granulator, it was dried at 110°C for 4 hours, and then calcined at a constant temperature of 600°C for 4.0 hours to make a spherical hydrogenation catalyst carrier.

Weigh 100 grams of spherical carrier and impregnate with 100 ml of impregnation solution. (the content of MoO ₃ is 25.2g/100ml, the content of NiO is 6.6g/100ml, and the content of phosphorus is 2.1g/100ml), the wet bulb catalyst is placed in the air for 1.5 hours, and then dried at 120°C for 2 hours, 500 The catalyst F was obtained by calcining at ℃ for 4 hours.

Comparative example 3

Take 200g of pseudo-boehmite powder prepared by the aluminum nitrate method (containing Al(OH) ₃ < 3 wt %), mix 20.0 grams of silica sol, 6.0 grams of carbon black and 3.5 grams of scallop powder, and then add 20 grams of adhesive (in which small holes Aluminum oxide is 40.0 wt % , citric acid is 38.6 wt %, water is 21.4 wt %) and a mixture of surfactant (sodium octadecylbenzene sulfonate content is 4 grams), mix well and then add 100ml 60 ℃ 6.0 grams of boric acid dissolved in water, fully mixed, kneaded into a plastic shape and then extruded into strips (the diameter of the strip orifice is 2.3mm). It was then pre-dried in a drying oven at 50° C. for 0.2 hours. After being cut and pelletized by a spherical granulator, it was dried at 110°C for 3 hours, and then calcined at a constant temperature of 600°C for 4.0 hours to make a spherical catalyst carrier.

Weigh 100 grams of spherical carrier, 100ml of impregnation solution for impregnation (the content of _MoO3 is 27.3g/100ml, the content of NiO is 3.8g/100ml, the content of CoO is 0.8g/100ml, and the content of phosphorus is 1.6g/100ml ), the wet bulb catalyst was placed in air for 1.5 hours, then dried at 120°C for 2 hours, and calcined at 500°C for 4 hours to obtain catalyst G.

The physical and chemical properties of the catalyst supports of the above examples are shown in Table 1, and the properties of the catalysts are shown in Table 2. See Table 3 for the properties of the feed oil used in the evaluation of the above-mentioned catalysts, see Table 4 for the process conditions, and see Table 5 for the evaluation results.

Table 1 The physical and chemical properties of the carrier of each embodiment Example 1 Example 2 Example 3 Example 4 Comparative example 1 Comparative example 2 Comparative example 3 Specific surface area, ^m2 /g 290 284 278 275 243 280 300 Pore volume, cm ³ /g 0.775 0.752 0.764 0.758 0.490 0.660 0.685 Average pore diameter, nm 10.7 10.6 11.0 11.0 8.1 9.4 9.1 Strength, N/grain 55 60 65 53 30 32 35 Particle size, mm 1.84 2.02 2.23 2.22 1.84 2.01 2.24 Qualified product, wt% 90 95 98 95 75 80 78 Plasticity, wt% 2.6 2.4 2.1 2.0 4.5 3.5 4.0 acid distribution Weak acid center, mmol/g 0.30 0.31 0.31 0.30 0.35 0.34 0.38 Medium strong acid center, mmol/g 0.25 0.27 0.30 0.29 0.30 0.32 0.35 Strong acid center, mmol/g 0.03 0.05 0.03 0.02 0.08 0.10 0.07

[Note]: It is determined by ammonia adsorption-TPD method, where 150~250℃, 250~400℃, 400~500℃ correspond to the desorption temperature of ammonia in weak acid center, medium strong acid center and strong acid center respectively.

Table 2 Comparison of physical and chemical properties of catalysts in each case A B C D. E. f G chemical components WO ₃ , wt% - - 5.8 5.7 5.7 - - MoO ₃ , wt % 19.2 21.2 14.0 14.1 14.2 19.2 21.2 NiO, wt % 5.0 2.9 2.8 2.9 3.0 5.1 2.9 CoO, wt % - 0.6 1.0 0.9 0.9 - 0.6 Specific surface, m ² /g 242 245 238 235 230 249 248 Pore volume, cm ³ /g 0.60 0.54 0.53 0.55 0.46 0.52 0.50 Average pore diameter, nm 9.9 8.8 8.9 9.4 8.0 7.9 8.1

Table 3 Properties of raw oil Melting point, °C 60.3 Oil content, wt % 0.48 Saybolt Color, No. +1 Photostability, No. 7 Simple FDA (Aromatic Hydrocarbon UV Absorption Value) 280 ~ 289 0.387 290 ~ 299 0.250

Table 4 process conditions Reaction temperature/℃ 270 Liquid hourly volumetric space velocity/h ^-1 1.5 Reaction pressure/MPa 6 Hydrogen Wax Volume Ratio 300

Table 5 Activity evaluation results of each catalyst A B C D. E. f G Melting point, °C 60.3 60.3 60.3 60.3 60.4 60.5 60.5 Oil content, wt % 0.48 0.48 0.48 0.48 0.51 0.50 0.50 Saybolt Color, No. +30 +30 +30 +30 +30 +30 +30 Photostability, No. 3 3 3 3 4 3~4 3~4 Easy carbide qualified qualified qualified qualified qualified qualified qualified Simple FDA (Aromatic Hydrocarbon UV Absorption Value) 280 ~ 289 0.032 0.041 0.042 0.040 0.065 0.055 0.057 290 ~ 299 0.010 0.011 0.013 0.012 0.024 0.027 0.031

Claims (13)

1. a preparation method for spherical hydrogenation catalyst, comprising:

(1) aluminium oxide precursor, Gemini surface active agent, adhesive are mixed, wherein the addition of adhesive is 2.0% ~ 10.0% of alumina weight, and the addition of Gemini surface active agent is 0.5% ~ 8.0% of alumina weight; Described Gemini surface active agent be Bis-quaternary Ammonium Surfactants series and acetylenic glycols Gemini surface active agent 400 series in one or more; Described adhesive adopt in little porous aluminum oxide, aluminum nitrate and aluminum sulfate one or more mix obtained with inorganic acid and/or organic acid, wherein inorganic acid and/or organic acid addition account for the 30wt% ~ 70wt% of adhesive weight; Wherein said inorganic acid selects one or more in nitric acid, phosphoric acid, sulfuric acid, hydrochloric acid, and one or more in acetic acid, citric acid, oxalic acid selected by described organic acid;

(2) step (1) gained mixture through kneading, extrusion and predrying after, with Spheroidgranulatemachine pelletizing and balling-up, then dry and roasting, obtains spherical carrier of catalyst; Described predrying temperature is 20 ~ 70 DEG C, and the time is 0.2 ~ 1.0 hour;

(3) spherical carrier of catalyst of step (2) gained adopts infusion process supported active metals component, then carries out drying and roasting, obtains spherical hydrogenation catalyst.

2. in accordance with the method for claim 1, it is characterized in that described Bis-quaternary Ammonium Surfactants series is dibrominated-N, N '-two (dimethyl dodecyl base) propane-diammonium, N, N '-dimethyl carboxybetaine, 1, two dodecyl-the N of 3-, N-dimethyl amine bromide-2-propyl alcohol, 1, two myristyl-the N of 3-, one or more in N-dimethyl amine bromide-2-propyl alcohol, acetylenic glycols Gemini surface active agent 400 series is one or more in Cido-420, Cido-440, Cido-465, Cido-485 surfactant.

3. in accordance with the method for claim 1, it is characterized in that described spherical carrier of catalyst contains adjuvant component, described auxiliary agent is one or more in silicon, zirconium, titanium, iron, phosphorus, boron.

4. in accordance with the method for claim 1, it is characterized in that, in mixing, kneading process, adding extrusion aid and/or expanding agent.

5. in accordance with the method for claim 1, it is characterized in that the predrying temperature described in step (2) is 20 ~ 70 DEG C, the time is 0.2 ~ 1.0 hour; Described drying is be 90 ~ 130 DEG C of drying times in temperature is 2 ~ 4 hours, and roasting is be 600 ~ 900 DEG C of roastings in temperature is 3 ~ 6 hours.

6. in accordance with the method for claim 1, it is characterized in that described spherical carrier of catalyst take aluminium oxide as main component, containing boron oxide and silica, boron oxide weight content is in the carrier 0.5% ~ 10.0%, and silica weight content is in the carrier 0.5% ~ 20.0%.

7. in accordance with the method for claim 6, it is characterized in that in described spherical carrier of catalyst, the weight content of boron oxide is 2.0% ~ 8.0%, and the weight content of silica is 2.0% ~ 15.0%.

8. according to the method described in claim 6 or 7, it is characterized in that in the preparation process of described spherical carrier of catalyst, silicon source and boron source add in step (1), and wherein silicon source is waterglass or Ludox, and boron source adopts boric acid.

9. in accordance with the method for claim 8, it is characterized in that described boric acid adopts the mode of boric acid aqueous solution or boric acid acid solution to add, the temperature of solution is 30 ~ 100 DEG C.

10. in accordance with the method for claim 8, it is characterized in that in the preparation process of described spherical carrier of catalyst, silicon source adds in arbitrary step of aluminium oxide precursor, Gemini surface active agent, adhesive mixing, and boron source adds after above-mentioned mixing of materials is even again.

11. in accordance with the method for claim 1, it is characterized in that in step (3), before the drying, is that material after dipping is deposited 0.5 ~ 2.0 hour in air or inert gas.

12. in accordance with the method for claim 1, and it is characterized in that the baking temperature described in step (3) is 100 ~ 120 DEG C, drying time is 2.0 ~ 5.0 hours, and roasting is 350 ~ 550 DEG C in temperature, and roasting time is 3.0 ~ 6.0 hours.

13. in accordance with the method for claim 1, it is characterized in that described active metal is group VIII and group vib metal, wherein group VIII metal is Ni or Co, group vib metal is W or Mo, with the weight of catalyst for benchmark, group VIII metal with the content of oxide basis for 0.5wt% ~ 9.0wt%, group vib metal with the content of oxide basis for 5.0wt% ~ 30.0 wt%.