Hydrogenation catalyst, preparation method and application thereof
阅读说明：本技术 加氢催化剂及其制备方法和应用 (Hydrogenation catalyst, preparation method and application thereof ) 是由 胡大为 聂红 杨清河 孙淑玲 王振 马云海 邓中活 于 2020-04-28 设计创作，主要内容包括：本发明涉及加氢催化剂技术领域,公开了一种加氢催化剂的制备方法,该方法包括如下步骤：(1)将拟薄水铝石与含磷化合物混合,然后进行成型、干燥,得到成型物；(2)将加氢活性金属组分负载到所述成型物上,然后进行任选地干燥；(3)将步骤(2)得到的固体产物进行活化,所述活化的条件包括：温度为600-800℃,时间为1-10小时；所述加氢活性金属组分含有至少一种VIB族金属组分以及至少一种VIII族金属组分。本发明的方法步骤简洁,制得的加氢催化剂具有更好的加氢活性、更好的稳定性。(The invention relates to the technical field of hydrogenation catalysts, and discloses a preparation method of a hydrogenation catalyst, which comprises the following steps: (1) mixing pseudo-boehmite with a phosphorus-containing compound, and then molding and drying to obtain a molded object; (2) loading a hydrogenation active metal component on the formed object, and then optionally drying; (3) activating the solid product obtained in the step (2), wherein the activating conditions comprise: the temperature is 600 ℃ and 800 ℃, and the time is 1-10 hours; the hydrogenation active metal component contains at least one VIB group metal component and at least one VIII group metal component. The method has simple steps, and the prepared hydrogenation catalyst has better hydrogenation activity and better stability.)
1. A method for preparing a hydrogenation catalyst, the method comprising the steps of:
(1) mixing pseudo-boehmite with a phosphorus-containing compound, and then molding and drying to obtain a molded object;
(2) loading a hydrogenation active metal component on the formed object, and then optionally drying;
(3) activating the solid product obtained in the step (2), wherein the activating conditions comprise: the temperature is 600 ℃ and 800 ℃, and the time is 1-10 hours;
the hydrogenation active metal component contains at least one VIB group metal component and at least one VIII group metal component.
2. The production method according to claim 1, wherein the amount of the phosphorus-containing compound is such that the phosphorus content in the resulting shaped article is 0.5 to 8% by weight, preferably 1 to 6% by weight, in terms of oxide, based on the dry weight of the shaped article;
preferably, the phosphorus-containing compound is selected from at least one of phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate, diammonium hydrogen phosphate, sodium phosphate, and potassium phosphate.
3. The production method according to claim 1, wherein the step (1) comprises mixing the pseudoboehmite, the phosphorus-containing compound and the hydroxyl group-rich compound, followed by the molding;
preferably, the hydroxyl-rich compound is used in an amount of 1 to 10 wt%, preferably 2 to 9.5 wt% of the amount of pseudoboehmite;
the hydroxyl-rich compound is at least one of organic carbohydrate compounds, acid compounds, alcohol compounds and cellulose compounds;
preferably, the organic sugar compound is selected from at least one of glucose, sucrose, ribose, fructose, and maltose;
preferably, the acid compound is selected from at least one of citric acid, glycolic acid, tartaric acid and amino acid;
preferably, the alcohol compound is selected from at least one of glycerol, ethylene glycol and isobutanol;
preferably, the cellulose-based compound is selected from at least one of hydroxymethyl cellulose, carboxymethyl cellulose, ethyl cellulose and hydroxypropyl methyl cellulose.
4. The production method according to claim 1, wherein the drying in step (1) is not followed by calcination;
preferably, the drying conditions of step (1) include: the drying temperature is 50-200 ℃, the drying time is 1-12 hours, the preferred drying temperature is 80-150 ℃, and the drying time is 2-8 hours.
5. The method according to any one of claims 1-4, wherein the activation temperature is 780 ℃, more preferably 630-750 ℃, and most preferably 650-730 ℃;
preferably, the temperature rise rate of the activation is 50-600 deg.C/hr, preferably 100-550 deg.C/hr.
6. The production method according to any one of claims 1 to 5, wherein the group VIB metal component is Mo and/or W, and the group VIII metal component is Co and/or Ni;
preferably, the forming matter and the hydrogenation active metal component are used in such amounts that the obtained hydrogenation catalyst contains 30-99 wt% of alumina and phosphorus in terms of oxides, 0.5-50 wt% of the group VIB metal component and 0.5-20 wt% of the group VIII metal component in terms of oxides, based on the total amount of the hydrogenation catalyst;
further preferably, the molding compound and the hydrogenation active metal component are used in amounts such that the content of alumina and phosphorus in terms of oxide in the prepared hydrogenation catalyst is 40-94 wt%, the content of the group VIB metal component is 5-45 wt%, and the content of the group VIII metal component is 1-15 wt%, based on the total amount of the hydrogenation catalyst;
more preferably, the method for loading the hydrogenation active metal component on the formed object comprises the steps of impregnating the formed object with an impregnating solution containing at least one group VIB metal compound and at least one group VIII metal compound, and then drying.
7. A hydrogenation catalyst obtained by the production method according to any one of claims 1 to 6.
8. The hydrogenation catalyst of claim 7, wherein the hydrogenation catalyst exhibits an absorbance F at 630nm and 500nm, respectively, as measured by diffuse reflectance ultraviolet-visible spectrum (DRUVS)630And F500And the ratio Q ═ F of the two630/F500Is 1.3 to 3, preferably 1.4 to 2.5.
9. The hydrogenation catalyst according to claim 7 or 8, wherein the specific surface area of the support of the hydrogenation catalyst is 300 m2More than g, preferably more than 310 and 350 m2Per gram; the pore volume is more than 0.7 ml/g, preferably 0.75-1.15 ml/g;
preferably, the total amount of hydroxyl groups is 0.45mol/g or more, preferably 0.45 to 0.6mol/g, and the content ratio of acidic hydroxyl groups to basic hydroxyl groups is 10 or more, preferably 11 to 18.
10. Use of a hydrogenation catalyst as claimed in any one of claims 7 to 9 in the hydrogenation of heavy oils.
Technical Field
The invention relates to the technical field of hydrogenation catalysts, and particularly relates to a hydrogenation catalyst and a preparation method and application thereof.
Background
For heavy raw oil, after being pretreated by a hydrogenation process, secondary processing is carried out, so that the yield of light oil can be improved, and the content of pollutants such as sulfur, nitrogen and the like in the oil can be reduced, therefore, the demand of the market on the light oil is continuously increased, and environmental protection regulations tend to be strict today, and the heavy raw oil is generally favored by oil refining manufacturers. Compared with light oil products, heavy oil contains a large amount of impurities such as sulfur, nitrogen, metal and the like, and contains easily coking species such as asphaltene and the like, so that the heavy oil has higher requirements on the activity and the stability of the catalyst. Since the catalyst carrier plays a role in providing a diffusion path for reactants and products and providing attachment sites for the formation of a reactive active phase during the catalytic reaction, the adsorption of the carrier surface with the reactants and products and the interaction with the active component have an important influence on the performance of the catalyst. And the interaction forces are closely related to the number and the types of hydroxyl groups on the surface of the alumina carrier. Meanwhile, in the heavy distillate oil hydrotreating process, the raw materials contain a large number of reactant molecules with complex structures, large molecular diameters and rich heteroatom numbers, and the activity of the catalyst is continuously reduced due to the influence of metal deposition and carbon deposition in the reaction process, so that the catalyst is required to have good reaction activity, excellent diffusion performance and scale holding capacity, and the pore structure of the catalyst carrier has important influence on the performance of the catalyst. It is easy to see that the alumina carrier with high pore volume, large specific surface area and special surface hydroxyl distribution plays an important role in the preparation process of the heavy oil hydrogenation catalyst. In the prior art, the alumina carrier patent application technology is disclosed as follows:
CN1765509A discloses a macroporous alumina carrier, which takes alumina as a main component and contains boron oxide, and is characterized in that the weight content of the boron oxide in the carrier is 1-15%, the average pore diameter is 10-20 nm, the infrared acid of the carrier at a temperature of more than or equal to 350 ℃ is 0.05-0.3 mmol/g, and the pore volume of the carrier is 0.5-1.0 cm3A specific surface area of 150 to 270m2(ii) in terms of/g. This patent application controls the temperature at which boron is introduced into the alumina precursor, which is said to increase the amount of acid in the support while the macroporous alumina support is obtained using this method.
U.S. Pat. No. 5, 4,448,896 discloses a hydrodesulfurization and heavy metal catalyst using a support having a specific surface area of 100-350 m2Per gram, hole radiusThe pore volume of (A) is 0.5-1.5 ml/g, the ratio of the pore volume to the total pore volume is at least 90%, and the pores are distributed in pore radius smaller thanAndtwo places appear characteristic peak, hole radiusHas a pore volume of at least 0.2 ml/g and a pore radius ofThe pore volume of the carrier is at least 0.1 ml/g, and the carrier is prepared by mixing activated alumina or an activated alumina precursor with carbon black, molding and calcining. Carbon black based on the aluminaThe amount of (B) is 10-120 wt%.
Although the prior art improves the pore volume of the carrier to a certain extent and increases the specific surface area of the carrier, the hydrogenation activity and stability of the catalyst still need to be further improved.
Disclosure of Invention
The invention aims to overcome the problem of poor hydrogenation activity and stability of the catalyst in the prior art, and provides a hydrogenation catalyst, a preparation method and application thereof.
In order to achieve the above object, a first aspect of the present invention provides a method for preparing a hydrogenation catalyst, the method comprising the steps of:
(1) mixing pseudo-boehmite with a phosphorus-containing compound, and then molding and drying to obtain a molded object;
(2) loading a hydrogenation active metal component on the formed object, and then optionally drying;
(3) activating the solid product obtained in the step (2), wherein the activating conditions comprise: the temperature is 600 ℃ and 800 ℃, and the time is 1-10 hours;
the hydrogenation active metal component contains at least one VIB group metal component and at least one VIII group metal component.
Preferably, the step (1) includes mixing the pseudoboehmite, the phosphorus-containing compound and the hydroxyl-rich compound, and then performing the molding.
Preferably, step (1) is not fired after drying.
Preferably, the temperature of the activation is 610-780 ℃, more preferably 630-750 ℃, and most preferably 650-730 ℃.
Preferably, the temperature rise rate of the activation is 50-600 deg.C/hr, preferably 100-550 deg.C/hr.
In a second aspect, the present invention provides a hydrogenation catalyst prepared by the above process.
The hydrogenation catalyst prepared by the method has better activity and higher stability, and is particularly suitable for heavy oil hydrogenation reaction, so that the third aspect of the invention provides the application of the hydrogenation catalyst prepared by the first aspect or the preparation method of the second aspect in heavy oil hydrogenation reaction.
According to the technical scheme, the pseudo-boehmite and the phosphorus-containing compound are mixed, then are molded and dried, the molded matter which is not roasted is loaded with the hydrogenation active metal component, and is subjected to activation treatment at a specific temperature, so that the prepared hydrogenation catalyst has a specific spinel structure Ni (Co) Al2O4. The method has simple steps, and the prepared hydrogenation catalyst has better hydrogenation activity and better stability.
In a preferable case, the method provided by the invention also comprises the step of mixing the pseudo-boehmite, the phosphorus-containing compound and the compound rich in hydroxyl, so that the hydrogenation activity and the stability of the obtained hydrogenation catalyst are further improved.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In a first aspect, the present invention provides a method for preparing a hydrogenation catalyst, comprising the steps of:
(1) mixing pseudo-boehmite with a phosphorus-containing compound, and then molding and drying to obtain a molded object;
(2) loading a hydrogenation active metal component on the formed object, and then optionally drying;
(3) activating the solid product obtained in the step (2), wherein the activating conditions comprise: the temperature is 600 ℃ and 800 ℃, and the time is 1-10 hours;
the hydrogenation active metal component contains at least one VIB group metal component and at least one VIII group metal component.
The inventor of the invention finds that the hydrogenation catalyst with a specific spinel structure can be formed by mixing the pseudo-boehmite with the phosphorus-containing compound, then molding and drying to obtain a molded product, then loading the hydrogenation active metal component on the molded product, and then activating at the temperature of 600-800 ℃ for 1-10 hours. The activation temperature is too low or the activation time is too short, so that the content of spinel in the obtained catalyst is too low, and the hydrogenation activity and stability improvement effect of the hydrogenation active metal component is not obvious; if the activation temperature is too high or the activation time is too long, the spinel content in the obtained catalyst is too high, which affects the initial hydrogenation activity of the catalyst.
The inventor of the present invention further finds that although the formation of the spinel structure affects the initial activity of the catalyst, the formation of a proper amount of the spinel structure does not greatly affect the total activity of the catalyst, and the spinel structure gradually releases the reaction activity with the extension of the catalyst participating in the reaction process, so that the activity stability of the catalyst is better, the service life of the catalyst is greatly prolonged, and the production efficiency is improved on the premise of meeting the basic activity requirement.
According to the invention, the drying in step (1) is not followed by calcination. The formed object dried by the method provided by the invention is directly loaded with the hydrogenation active metal component without roasting, and compared with the prior art, the method saves one-time roasting, has simpler operation steps and is beneficial to reducing the energy consumption in the preparation process of the catalyst.
The range of the using amount of the phosphorus-containing compound is selected to be wide, and the using amount of the phosphorus-containing compound is preferably that the phosphorus content in the obtained molded product is 0.5-8 wt%, preferably 1-6 wt% calculated by oxide on the basis of the dry weight of the molded product.
In the present invention, the dry weight of a molded article means the weight of the molded article subjected to the subsequent activation treatment, unless otherwise specified.
In the present invention, the selection range of the phosphorus-containing compound is wide, and preferably, the phosphorus-containing compound is at least one selected from phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate, diammonium hydrogen phosphate, sodium phosphate, and potassium phosphate.
According to a preferred embodiment of the present invention, the step (1) comprises mixing the pseudoboehmite, the phosphorus-containing compound and the hydroxyl-rich compound, and then carrying out the molding. In the preferred embodiment, the total amount of the supported hydroxyl groups of the hydrogenation catalyst is higher, and the content ratio of the acidic hydroxyl groups to the basic hydroxyl groups is higher, so that the hydrogenation activity and stability of the hydrogenation catalyst are improved.
The present invention is not particularly limited to the mixing in step (1), and preferably, step (1) further includes: pseudo-boehmite, a phosphorus-containing compound and a hydroxyl-rich compound are mixed in the presence of a solvent (preferably water), and then subjected to molding.
The order of mixing in step (1) is not particularly limited in the present invention, and specifically, for example, the phosphorus-containing compound and the hydroxyl group-rich compound may be directly mixed with the pseudo-boehmite and then mixed with the solvent; or mixing the phosphorus-containing compound and the compound rich in hydroxyl with a solvent and then mixing with the pseudo-boehmite. The amount of the solvent used in the present invention is not particularly limited as long as it provides an environment for mixing the pseudo-boehmite, the phosphorus-containing compound and the hydroxyl-rich compound, and the molding requirement can be satisfied, and those skilled in the art can select the amount of the pseudo-boehmite, the phosphorus-containing compound and the hydroxyl-rich compound according to the actual requirement. In the present invention, the requirement for molding is defined as that the weight ratio of the solvent to the powder (in the present invention, the solid material before molding) in the mixed material is appropriate, and the selection of the weight ratio is well known to those skilled in the art, for example, when molding by the bar-extruding technique, the weight ratio of the solvent to the powder is 0.4 to 2, preferably 0.5 to 1.5.
According to the invention, the hydroxyl-rich compound is preferably used in an amount of 1 to 10% by weight, preferably 2 to 9.5% by weight, based on the amount of pseudoboehmite.
The hydroxyl-rich compound is selected from a wide range, and preferably, the hydroxyl-rich compound is at least one selected from the group consisting of organic sugar compounds, acid compounds, alcohol compounds and cellulose compounds.
According to the present invention, preferably, the organic saccharide compound is selected from at least one of glucose, sucrose, ribose, fructose and maltose.
According to the present invention, preferably, the acid compound is at least one selected from the group consisting of citric acid, glycolic acid, tartaric acid, and amino acids.
According to the present invention, preferably, the alcohol compound is at least one selected from the group consisting of glycerol, ethylene glycol and isobutanol.
According to the present invention, preferably, the cellulose-based compound is at least one selected from the group consisting of hydroxymethyl cellulose, carboxymethyl cellulose, ethyl cellulose and hydroxypropylmethyl cellulose.
In the present invention, there is no particular limitation on the molding in the step (1), and the molding may be performed in a molding manner conventional in the art, and the molding is preferably extrusion molding. In order to ensure that the molding is carried out smoothly, water, extrusion assistant and/or peptizing agent and optionally pore-expanding agent can be added in the step (1), and the selection range of the types and the dosage of the extrusion assistant, the peptizing agent and the pore-expanding agent is wide and can be the routine selection in the field. Specifically, for example, the extrusion aid may be selected from at least one of sesbania powder, methyl cellulose, starch, polyvinyl alcohol, and polyvinyl alcohol; the peptizing agent can be inorganic acid and/or organic acid; the pore-enlarging agent may be at least one of starch, synthetic cellulose, polymeric alcohol and surfactant. In the invention, the synthetic cellulose is preferably at least one of hydroxymethyl cellulose, carboxymethyl cellulose, ethyl cellulose and hydroxy fiber fatty alcohol polyvinyl ether; the polymeric alcohol is preferably at least one of polyethylene glycol, polypropylene glycol and polyvinyl alcohol; the surfactant is preferably at least one of fatty alcohol polyvinyl ether, fatty alcohol amide and derivatives thereof, an allyl alcohol copolymer with molecular weight of 200-10000 and a maleic acid copolymer. The shape after molding can be clover shape, butterfly shape, cylindrical shape, hollow cylindrical shape, four-leaf shape, five-leaf shape or spherical shape.
When the kind of the extrusion aid, the peptizer, or the pore-enlarging agent added in the molding process is the same as that of the above-mentioned hydroxyl-rich compound, it is counted as a hydroxyl-rich compound.
In the present invention, the drying conditions in step (1) are not particularly limited, and preferably, the drying conditions include: the drying temperature is 50-200 deg.C, and the drying time is 1-12 hr, preferably 80-150 deg.C, and the drying time is 2-8 hr. In the present invention, the drying method is not particularly limited, and for example, the drying may be at least one of drying, air-blast drying, spray drying, and flash drying. In the present invention, the drying atmosphere is not particularly limited, and may be performed in at least one of air, oxygen, and nitrogen, and air is preferable in order to reduce the production cost.
In the present invention, step (2) optionally means that the operation may be performed or may not be performed. Preferably, the hydrogenation-active metal component is supported on the molded article in the step (2), and then dried.
According to the present invention, the drying conditions after the hydrogenation-active metal component is supported on the shaped object in step (2) are not particularly limited, and specifically, for example, the drying conditions may include: the drying temperature is 50-350 deg.C, and the drying time is 1-12 hr, preferably 80-250 deg.C, and the drying time is 2-8 hr. The drying mode of the invention is as described above, and the invention is not described in detail herein.
According to a preferred embodiment of the present invention, the temperature of the activation is 780-. In the present invention, the activation refers to activation that is conventional in the art, and the activation may be raised from an ambient temperature to an activation temperature, or may be raised from a drying temperature directly after the impregnation of the metal component to the activation temperature, and is not particularly limited.
The temperature rise rate during the activation is selected in a wide range, preferably, the temperature rise rate of the activation is 50-600 ℃/h, preferably 100-550 ℃/h.
According to the present invention, the group VIB metal component may be selected from at least one of chromium, molybdenum and tungsten, and the group VIII metal component may be selected from at least one of iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum, so long as it is advantageous to improve the hydrogenation activity and stability of the hydrogenation catalyst. Preferably, the group VIB metal component is Mo and/or W and the group VIII metal component is Co and/or Ni.
The selectable ranges of the usage amounts of the VIB group metal component and the VIII group metal component are wide, and preferably, the usage amounts of the formed product and the hydrogenation active metal component are such that the content of alumina and phosphorus calculated by oxides in the prepared hydrogenation catalyst is 30-99 wt% based on the total amount of the hydrogenation catalyst, the content of the VIB group metal component is 0.5-50 wt% calculated by oxides, and the content of the VIII group metal component is 0.5-20 wt%.
Further preferably, the molding and the hydrogenation active metal component are used in such amounts that the content of alumina and phosphorus in terms of oxide in the prepared hydrogenation catalyst is 40-94 wt%, the content of the group VIB metal component in terms of oxide is 5-45 wt%, and the content of the group VIII metal component in terms of oxide is 1-15 wt%, based on the total amount of the hydrogenation catalyst.
According to the present invention, the manner in which the hydrogenation-active metal component is supported on the shaped article is not particularly limited, and may be any conventional method in the art, and may be, for example, a kneading method, a dry blending method, or an impregnation method.
According to a preferred embodiment of the present invention, the method for loading the hydrogenation active metal component on the formed object comprises impregnating the formed object with an impregnation solution containing at least one group VIB metal compound and at least one group VIII metal compound, and then drying the impregnated object.
Further according to the invention, the group VIB metal compound and the group VIII metal compound are each independently selected from at least one of their soluble compounds (including the corresponding metal compounds soluble in water in the presence of a co-solvent). Specifically, the group VIB metal compound, for example, molybdenum, may be selected from salts and/or oxides of molybdenum-containing metals, for example, at least one selected from molybdenum oxide, molybdate, paramolybdate and phosphomolybdate, and preferably at least one selected from molybdenum oxide, ammonium molybdate, ammonium paramolybdate and phosphomolybdic acid; the group VIII metal compound may be selected from at least one of cobalt nitrate, cobalt acetate, cobalt hydroxycarbonate, and cobalt chloride, preferably cobalt nitrate and/or cobalt hydroxycarbonate, for example, cobalt, at least one of salts, oxides, and hydroxides containing nickel, for example, at least one of nitrates, chlorides, formates, acetates, phosphates, citrates, oxalates, carbonates, hydroxycarbonates, hydroxides, phosphides, sulfides, and oxides containing nickel, for example, at least one of oxalates, carbonates, hydroxycarbonates, hydroxides, phosphates, and oxides containing nickel, for example, and more preferably at least one of nickel nitrate, nickel acetate, nickel hydroxycarbonate, nickel chloride, and nickel carbonate.
According to the invention, the invention may also contain organic additives during the catalyst preparation, such as during the preparation of the soluble compounds of the group VIB metal compounds and the group VIII metal compounds. The method for introducing the organic additive is not particularly limited, and the organic additive may be introduced in any manner, for example, may be introduced together with the group VIII metal, may be introduced together with the group VIB metal element, may be introduced after introducing the group VIII and/or group VIB metal element, or may be introduced before introducing the group VIII and/or group VIB element. The present invention is not particularly limited in the kind of the organic additive, and the organic additive is at least one selected from oxygen-containing and/or nitrogen-containing organic substances, the oxygen-containing organic substances are selected from organic alcohols and/or organic acids, and the nitrogen-containing organic substances are selected from at least one selected from organic amines and organic amine salts. Specifically, the oxygen-containing organic matter is at least one selected from ethylene glycol, glycerol, polyethylene glycol (molecular weight 200-. The nitrogen-containing organic substance is at least one selected from ethylenediamine, diethylenetriamine, cyclohexanediaminetetraacetic acid, glycine, nitrilotriacetic acid, EDTA and amine salts thereof, and preferably EDTA and/or nitrilotriacetic acid.
In the present invention, the impregnation method and the impregnation time are not particularly limited, and the impregnation method may be excess liquid impregnation, pore saturation impregnation, multiple impregnation, or the like depending on the amount of the impregnation liquid, and may be immersion method, spray impregnation, or the like depending on the impregnation operation. In the present invention, the impregnation time is preferably 0.5 to 3 hours. Further, by adjusting and controlling the concentration, amount or carrier amount of the impregnation solution, a hydrogenation catalyst with a specific component content can be prepared, which is well known to those skilled in the art.
The hydrogenation catalyst provided by the invention can also contain any auxiliary agent which does not affect the performance of the hydrogenation catalyst or can improve the performance of the hydrogenation catalyst, such as at least one of elements in groups IA, IIA, IIIA, IVA, VA, VIIA, IIB and IIIB and rare earth metal elements, preferably at least one of boron, fluorine, silicon, sodium, magnesium, lithium, zinc, calcium, potassium, titanium, lanthanum and cerium, and the content of the auxiliary agent calculated by simple substance elements is not more than 10 wt%, preferably 0.5-6 wt% based on the catalyst. The method for loading the hydrogenation catalyst with the aid is not particularly limited, and the method can be carried out according to the method for loading the hydrogenation active metal component, and the method is not repeated herein.
The hydrogenation catalyst prepared by the method has better hydrogenation activity and stability, so the second aspect of the invention provides the hydrogenation catalyst prepared by the preparation method.
The inventor of the invention finds that although the initial activity of the catalyst is influenced by the formation of the spinel structure, the formation of a proper amount of the spinel structure does not bring too much influence on the total activity of the catalyst, and the formed spinel structure gradually releases the reaction activity along with the extension of the catalyst participating in the reaction process, so that the activity stability of the catalyst is better, the service life of the catalyst is greatly prolonged on the premise of meeting the basic activity requirement, and the production efficiency is improved.
According to the invention, preferably, the absorbance of the hydrogenation catalyst at 630nm and 500nm is F when measured by diffuse reflectance ultraviolet-visible spectroscopy (DRUVS)630And F500And the ratio Q ═ F of the two630/F500Is 1.3-3. In this preferred embodiment, it is more advantageous to improve the hydrogenation activity and stability of the hydrogenation catalyst.
The inventors of the present invention have further found that by supporting a specific hydrogenation-active metal component on a shaped product containing a phosphorus element and making the above-mentioned ratio Q representing the content of the spinel structure in the catalyst further preferably 1.4 to 2.5, it is further advantageous that the catalyst can obtain a better initial activity and a better subsequent hydrogenation activity and stability. When the Q value is less than 1, the improvement of the activity stability is not obvious; when the Q value is more than 3, the initial activity is too low, which affects the normal use of the catalyst.
According to the invention, the support of the hydrogenation catalyst preferably has a specific surface area of 300 m2More than g, preferably more than 310 and 350 m2Per gram; the pore volume is 0.7 ml/g or more, preferably 0.75 to 1.15 ml/g.
According to the present invention, it is preferred that the total amount of hydroxyl groups in the hydrogenation catalyst is 0.45mol/g or more, preferably 0.45 to 0.6 mol/g.
The content ratio of the acidic hydroxyl group to the basic hydroxyl group is selected from a wide range, and preferably, the content ratio of the acidic hydroxyl group to the basic hydroxyl group is 10 or more, preferably 11 to 18. In this preferred case, it is advantageous to increase the activity and stability of the hydrogenation catalyst.
The hydrogenation catalyst prepared by the invention has better activity and higher stability, and is particularly suitable for heavy oil hydrogenation reaction, so the third aspect of the invention provides the application of the hydrogenation catalyst in the heavy oil hydrogenation reaction. The hydrogenation catalyst provided by the invention can be used alone or combined with other catalysts when used for heavy oil hydrogenation reaction.
In the present invention, the hydrogenation catalyst may be presulfided according to a conventional method in the art before use to convert the active metal component supported thereon into a metal sulfide component; the prevulcanization method can be as follows: the hydrogenation catalyst is presulfided with sulfur, hydrogen sulfide or sulfur-containing raw materials in the presence of hydrogen at the temperature of 140 ℃ and 400 ℃. The prevulcanisation can be carried out either ex situ or in situ.
In the present invention, the hydrogenation conditions for the application of the hydrogenation catalyst are not particularly limited, and the reaction conditions generally used in the art may be employed; preferably, the reaction temperature is 200-420 ℃, and more preferably 220-400 ℃; the pressure is 2-18MPa, and the preferable pressure is 2-16 MPa; liquid hourly volume space velocity of 0.1-10h-1More preferably 0.15 to 6 hours-1(ii) a The hydrogen-oil volume ratio is 50 to 5000, and more preferably 50 to 4000.
The heavy oil of the present invention has a general meaning in the art, and the present invention is not particularly limited thereto, and for example, the heavy oil includes, but is not limited to, at least one of wax oil, residual oil, fischer-tropsch synthesis oil, coal liquefaction oil, light deasphalted oil, and heavy deasphalted oil.
The hydrotreating reaction apparatus in the application of the hydrogenation catalyst in the present invention is not particularly limited, and may be any reactor sufficient for the contact reaction of the feedstock oil with the hydrogenation catalyst under the hydrotreating reaction conditions, such as a fixed bed reactor, a slurry bed reactor, a moving bed reactor, or a fluidized bed reactor.
The present invention will be described in detail below by way of examples.
In the following examples, room temperature means 25 ℃ unless otherwise specified; except where specifically stated, are chemically pure reagents;
the dried gum powder was purchased from Changling catalyst Inc. under the designation RPB 90;
sesbania powder is produced by Shunhun commerce, Inc., Jiangsu Feng county;
in the following examples, the composition of the catalyst was determined by X-ray fluorescence spectroscopy (i.e., XRF) as described in petrochemical analysis method RIPP 133-90;
the specific surface area and the pore volume of the catalyst are measured by a mercury intrusion method;
the total amount of hydroxyl on the surface of the catalyst and the content ratio of acidic hydroxyl to basic hydroxyl are measured by an infrared method, and an experimental instrument is a Nicolet 870 type Fourier infrared spectrometer of Nicolet company in America. Pressing a sample into a self-supporting sheet, placing the self-supporting sheet in an infrared cell, treating the sample for 3 hours at 450 ℃ under a vacuum condition, and measuring the infrared spectrum of the sample;
the formation of spinel structure of the metal component with aluminum in the catalyst was determined by ultraviolet visible spectroscopy (DRUVS). The instrument adopts a Cary300 ultraviolet visible light analyzer of Agilent company, and the wavelength ranges are as follows: 190nm-1100nm, wavelength precision: ± 0.1nm, wavelength reproducibility: ± 0.1nm, baseline stability: 0.0003/h, stray light: 0.02% or less, photometric accuracy: + -0.003.
Example 1
The preparation of the hydrogenation catalyst according to the method of the invention comprises the following steps:
(1) taking 300 g of dry rubber powder, uniformly mixing with 5 g of sesbania powder and 5 g of hydroxymethyl cellulose to obtain a mixture, mixing the mixture with 360 ml of aqueous solution containing 11 g of ammonium dihydrogen phosphate and 15 g of citric acid at room temperature, kneading the mixture into a plastic body on a double-screw extruder, extruding the plastic body into a trilobal wet strip with the outer diameter of 1.5 mm, and drying the wet strip at 120 ℃ for 4 hours to obtain a formed product;
(2) 100g of the molded product obtained in step (1) was taken and immersed in 110 ml of an immersion liquid (containing MoO in terms of oxides)3160 g/L and NiO 50 g/L ammonium molybdate and nickel nitrate) for 1 hour, and drying for 4 hours at 110 ℃;
(3) activating the solid product of the step (2), wherein the activating conditions comprise: the temperature is 700 ℃, the time is 4 hours, the temperature rise rate of activation is 120 ℃/hour, and a hydrogenation catalyst C1 is obtained;
the composition and physicochemical properties of C1 are listed in table 1.
Comparative example 1
The preparation of the hydrogenation catalyst was carried out in the same manner as in example 1, except that the conditions for activation in step (3) included: the temperature is 500 ℃, the time is 4 hours, the temperature rise rate of activation is 120 ℃/hour, and a hydrogenation catalyst D1 is obtained;
the composition and physicochemical properties of D1 are shown in table 1.
Comparative example 2
The preparation of a hydrogenation catalyst was carried out in the same manner as in example 1, except that no ammonium dihydrogen phosphate-containing was added in step (1), and the conditions for activation in step (3) included: the temperature is 500 ℃, the time is 4 hours, the temperature rise rate of activation is 120 ℃/hour, and a hydrogenation catalyst D2 is obtained;
the composition and physicochemical properties of D2 are shown in table 1.
Example 2
The preparation of the hydrogenation catalyst according to the method of the invention comprises the following steps:
(1) taking 300 g of dry glue powder, uniformly mixing with 6 g of sesbania powder and 8 g of hydroxypropyl methyl cellulose to obtain a mixture, mixing the mixture with 360 ml of aqueous solution containing 13 g of phosphoric acid and 20 g of glucose at room temperature, kneading the mixture into a plastic body on a double-screw extruder, extruding the plastic body into butterfly-shaped wet strips with the outer diameter of 1.6 mm, and drying the wet strips at 120 ℃ for 4 hours to obtain a formed product;
(2) 100g of the shaped product from step (1) was taken and 110 ml of an impregnating solution (containing WO in terms of oxides) was used3220 g/L and NiO 50 g/L ammonium metatungstate and nickel nitrate) for 1 hour, and drying for 4 hours at 110 ℃;
(3) activating the solid product of the step (2), wherein the activating conditions comprise: the temperature is 650 ℃, the time is 6 hours, the temperature rise rate of activation is 100 ℃/hour, and a hydrogenation catalyst C2 is obtained;
the composition and physicochemical properties of C2 are listed in table 1.
Example 3
The preparation of the hydrogenation catalyst according to the method of the invention comprises the following steps:
(1) taking 300 g of dry glue powder, uniformly mixing with 5 g of sesbania powder and 10 g of starch to obtain a mixture, mixing the mixture with 360 ml of aqueous solution containing 7 g of phosphoric acid and 10 g of glycerol at room temperature, kneading the mixture into a plastic body on a double-screw extruder, extruding the plastic body into a four-leaf wet strip with the outer diameter of 1.2 mm, and drying the wet strip at 120 ℃ for 4 hours to obtain a formed product;
(2) 100g of the molded product obtained in step (1) was taken and immersed in 110 ml of an immersion liquid (containing MoO in terms of oxides)3160 g/L and NiO 50 g/L ammonium molybdate and nickel nitrate) for 1 hour, and drying for 4 hours at 110 ℃;
(3) activating the solid product of the step (2), wherein the activating conditions comprise: the temperature is 730 ℃, the time is 3 hours, the temperature rise rate of activation is 120 ℃/hour, and a hydrogenation catalyst C3 is obtained;
the composition and physicochemical properties of C3 are listed in table 1.
Example 4
The preparation of the hydrogenation catalyst according to the method of the invention comprises the following steps:
(1) taking 300 g of dry rubber powder, uniformly mixing with 6 g of sesbania powder and 7 g of ethyl cellulose to obtain a mixture, mixing the mixture with 360 ml of aqueous solution containing 23 g of diammonium hydrogen phosphate and 15 g of glycolic acid at room temperature, kneading the mixture into a plastic body on a double-screw extruder, extruding the plastic body into a trilobal wet strip with the outer diameter of 1.5 mm, and drying the wet strip at 120 ℃ for 4 hours to obtain a formed product;
(2) 100g of the shaped product from step (1) was taken and 110 ml of an impregnating solution (containing WO in terms of oxides) was used3220 g/l of ammonium metatungstate and 50 g/l of CoO and cobalt nitrate) for 1 hour, and drying for 4 hours at 110 ℃;
(3) activating the solid product of the step (2), wherein the activating conditions comprise: the temperature is 700 ℃, the time is 4 hours, the temperature rise rate of activation is 120 ℃/hour, and a hydrogenation catalyst C4 is obtained;
the composition and physicochemical properties of C4 are listed in table 1.
Example 5
The preparation of a hydrogenation catalyst was carried out in the same manner as in example 1, except that hydroxymethylcellulose and citric acid were not added in the step (1), to obtain a hydrogenation catalyst C5;
the composition and physicochemical properties of C5 are listed in table 1.
Example 6
The preparation of the hydrogenation catalyst was carried out in the same manner as in example 1, except that the conditions for activation in step (3) included: the temperature is 610 ℃, the time is 4 hours, the temperature rise rate of activation is 120 ℃/hour, the hydrogenation catalyst C6 is obtained, and the composition and the physicochemical properties of the C6 are shown in Table 1.
Example 7
A hydrogenation catalyst was prepared in the same manner as in example 1, except that ammonium dihydrogen phosphate was used in an amount of 17 g, to obtain a hydrogenation catalyst C7, wherein the composition and physical and chemical properties of C7 are shown in Table 1.
TABLE 1
Note: the hydroxyl group ratio represents the content ratio of acidic hydroxyl groups to basic hydroxyl groups.
Test example 1
This test example was used to test the hydrogenation activity and reaction stability of the hydrogenation catalysts in the above examples.
The hydrogenation catalysts prepared in 100 ml of examples 1-7, comparative example 1 and comparative example 2 are respectively presulfided after being crushed into particles with the diameter of 2-3 mm, and the presulfiding conditions comprise: the vulcanized oil adopts 5 weight percent of dimethyl disulfide/Jingmen diesel oil, and the liquid hourly volume space velocity of the vulcanized oil is 1.2h-1The hydrogen partial pressure is 14MPa, the volume ratio of hydrogen to oil is 400, and the vulcanization is carried out for 3 hours at the constant temperature of 360 ℃; evaluation was then carried out in a 100 ml small fixed-bed reactor (catalyst loading 100 ml).
The specific properties of the heavy oil are shown in Table 2. At the reaction temperature of 380 ℃, the hydrogen partial pressure of 54MPa and the liquid hourly space velocity of 0.6h-1And carrying out a hydrogenation activity performance test under the condition that the volume ratio of hydrogen to oil is 600.
In particular, the amount of the solvent to be used,
the Ni removal rate, V removal rate, desulfurization rate and carbon residue removal rate of the product after 600h reaction are tested, and the results are shown in Table 3;
the calculation methods of the Ni removal rate, the V removal rate, the desulfurization rate and the carbon residue removal rate are the same, and the calculation method is exemplarily illustrated by taking the Ni removal rate as an example:
the Ni removal rate is (Ni content in the raw material-Ni content in the hydrogenated product)/Ni content in the raw material;
the content of nickel (Ni) and vanadium (V) in the oil sample is measured by an inductively coupled plasma emission spectrometer (ICP-AES) (the used instrument is a PE-5300 type plasma photometer of PE company in America, and the specific method is shown in petrochemical engineering analysis method RIPP 124-90);
measuring the sulfur content in the oil sample by using an electric quantity method (the specific method is shown in petrochemical analysis method RIPP 62-90);
the content of carbon residue in the oil sample is determined by a micro-method (the specific method is shown in petrochemical analysis method RIPP 149-90).
TABLE 2
Raw oil
Inferior heavy oil
Density (20 ℃), kg/m3
0.975
Ni，μg/g
31
V，μg/g
70
S，％
3.5
Residual carbon content%
12.1
TABLE 3
Example numbering
Ni removal rate/%)
Degree of V removal/%)
Desulfurization rate/%)
Percent carbon removal /)
Example 1
82
84
81
53
Comparative example 1
68
70
67
44
Comparative example 2
69
69
70
45
Example 2
81
82
79
50
Example 3
83
83
82
52
Example 4
81
80
81
51
Example 5
78
80
77
48
Example 6
80
81
79
50
Example 7
83
84
82
52
As can be seen from the data in Table 1, the hydrogenation catalyst carrier provided by the invention has larger pore volume, larger specific surface area and larger total amount of hydroxyl and content ratio of acidic hydroxyl to basic hydroxyl. The hydrogenation catalyst provided by the invention has a spinel structure, and the Q value is within the range of 1.3-3.
As can be seen from the data in Table 3, the hydrogenation catalyst prepared by the preparation method provided by the invention has better hydrogenation activity and higher stability, so that the operation period of the catalyst is prolonged, and the economic benefit of a refinery is improved. In addition, the preparation method of the catalyst provided by the invention is simple, only needs one-step activation, and is more beneficial to energy conservation and consumption reduction.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
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