CN103566944B - A kind of hydrogenation catalyst and preparation and application - Google Patents
A kind of hydrogenation catalyst and preparation and application Download PDFInfo
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- CN103566944B CN103566944B CN201210266852.6A CN201210266852A CN103566944B CN 103566944 B CN103566944 B CN 103566944B CN 201210266852 A CN201210266852 A CN 201210266852A CN 103566944 B CN103566944 B CN 103566944B
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Abstract
A kind of hydrogenation catalyst and preparation and application, be included on a kind of shaping carrier of moisture and aluminium oxide and introduce at least one group VIII metal component and at least one group vib metal component, wherein, the method of introducing at least one group VIII metal component and at least one group vib metal component on the shaping carrier of moisture and aluminium oxide comprises the following steps: (1) with contain at least one containing compound of group vib metallic element and at least one containing the compound of group VIII metallic element and containing or not containing the shaping carrier of the described moisture and aluminium oxide of the aqueous solution dipping of cosolvent, obtain a kind of dip compound, (2) dip compound step (1) being obtained carries out hydrothermal treatment consists in closed reactor, and described hydrothermal treatment consists is P at pressure0Under the condition of+Δ P, carry out, wherein, Δ P is 0.05-15MPa; And the mixture that (3) obtain hydrothermal treatment consists carries out Separation of Solid and Liquid, and the solid phase obtaining is dried. The catalyst of preparation is when refining for hydrocarbon oil hydrogenation thus, and its performance improves.
Description
Technical field
The present invention relates to a kind of method of hydrogenation catalyst and this catalyst of preparation; The invention still further relates to a kind of hydrocarbon oil hydrogenation process for purification that uses this catalyst.
Background technology
Along with environmental requirement increasingly stringent in world wide, various countries are day by day harsh to the quality requirement of vehicle fuel. In addition, because petroleum resources reduce, oil property becomes and heavily becomes bad, and refinery has to process crude oil more inferior. Therefore, significantly reduce bavin well cuts and polycyclic aromatic hydrocarbon content, significantly improve diesel quality, become oil refining enterprise's problem in the urgent need to address. Hydrogen addition technology is impurity content in reduction oil product, improves one of major technique of oil quality, and its core is hydrogenation catalyst.
Therefore the catalyst that, exploitation has a higher hydrogenation activity becomes study hotspot.
CN101298043B discloses a kind of hydro-thermal deposition preparation of support type monometallic Hydrobon catalyst, and the method comprises:
(1) add a kind of metal salt solution that is selected from group vib active metal to being added with in the autoclave of aluminium oxide, taking inorganic acid as precipitating reagent, taking organic acid as dispersant, the temperature of controlling hydro-thermal reaction is 100-200 DEG C, time is 6-48 hour, wherein, the mol ratio of dispersant and active metal is 0.5-3:1, and described dispersant is that carbon number is binary or the tricarboxylic acid of 2-12;
(2) hydro-thermal reaction is filtered suspension, wash after completing, and is dried and roasting, thereby obtains Hydrobon catalyst.
CN101298047A discloses a kind of preparation method of hydrogenation catalyst, and on the carrier of this hydrogenation catalyst, load has group vib metal and group VIII metal active constituent, and this preparation method comprises:
(1) in autoclave, add carrier and the salting liquid containing group vib metal, taking inorganic acid as precipitating reagent, taking cationic surfactant as dispersant, the temperature of controlling hydro-thermal reaction is 100-200 DEG C, and the time is 12-36 hour;
(2) hydro-thermal reaction is filtered suspension, wash after completing, and be dried, roasting, obtain single-metal reforming catalyst;
(3) single-metal reforming catalyst obtaining is placed in to autoclave, adds the salting liquid of group VIII metal, taking urea as precipitating reagent, at the temperature of 50-90 DEG C, react after 4-12 hour, temperature is increased to 90-137 DEG C, then reacts 4-12 hour;
(4) after product is filtered and washed, be dried and roasting, obtain the hydrogenation catalyst of bimetallic component.
Li Jun really wait (hydrothermal modification is to NiMO/ γ-Al2O3The impact of hydrodenitrogenation catalyst structure and performance, Chinese Journal of Inorganic Chemistry, 20(6): 739-742,2004) a kind of preparation method of hydrogenation catalyst is disclosed, the method comprises with step impregnation method (NH4)6Mo7O24·4H2O and Ni (NO3)2·6H2O loads on γ-Al2O3Go up, and the product after dipping is carried out to the hydrothermal modification of 2 hours at the temperature of 140-180 DEG C. But, in research process, to find, the hydrogenation activity of catalyst prepared by employing the method still awaits further raising.
Summary of the invention
The technical problem to be solved in the present invention is on the basis of existing technology, provides a kind of new method for preparing catalyst and the catalyst of being prepared by the method and the hydrocarbon oil hydrogenation process for purification that uses this catalyst.
The present inventor finds in research process, flood a kind of hydrated alumina shaping carrier containing the compound of group vib metallic element and at least one containing the aqueous solution of the compound of group VIII metallic element with containing at least one, and the mixture after dipping is carried out to hydrothermal treatment consists, the pressure that suitably improves hydrothermal treatment consists in hydrothermal treatment consists process, can further improve the hydrofinishing performance of catalyst to hydrocarbon ils.
The content the present invention relates to comprises:
1, a kind of preparation method of hydrogenation catalyst, be included in and on a kind of shaping carrier of alumina hydrate-containing, introduce at least one group VIII metal component and at least one group vib metal component, wherein, the method for introducing at least one group VIII metal component and at least one group vib metal component on the shaping carrier of alumina hydrate-containing comprises the following steps:
(1) with containing at least one compound containing group vib metallic element and at least one shaping carrier that contains the compound of group VIII metallic element and contain or do not flood containing the aqueous solution of cosolvent described alumina hydrate-containing, obtain a kind of dip compound;
(2) dip compound step (1) being obtained carries out hydrothermal treatment consists in closed reactor, and described hydrothermal treatment consists is P at pressure0Under the condition of+Δ P, carry out, wherein, P0For the shaping carrier of described alumina hydrate-containing, the described compound that contains group vib metallic element, described containing the compound of group VIII metallic element, containing or the described cosolvent and the described aqueous solution that do not contain in the pressure that produces in hydrothermal treatment consists of water, Δ P is 0.05-15MPa; And
(3) mixture hydrothermal treatment consists being obtained carries out Separation of Solid and Liquid, and the solid phase obtaining is dried.
2, according to the method described in 1, it is characterized in that, described Δ P is 0.1-10MPa.
3, according to the method described in 2, it is characterized in that, described Δ P is 0.2-7MPa.
4, according to the method described in 3, it is characterized in that, described Δ P is 0.2-5MPa.
5, according to the method described in 1, it is characterized in that, making described hydrothermal treatment consists is P at pressure0The mode of carrying out under the condition of+Δ P comprises: in described closed reactor, pass into volatile organic matter, it is Δ P that the intake of volatile organic matter makes the pressure that described volatile organic matter produces in hydrothermal treatment consists.
6, according to the method described in 1, it is characterized in that, making described hydrothermal treatment consists is P at pressure0The mode of carrying out under the condition of+Δ P comprises: in described closed reactor, pass into non-active gas, it is Δ P that the intake of described non-active gas makes the pressure that described non-active gas produces in hydrothermal treatment consists.
7, according to the method described in 1, it is characterized in that, making described hydrothermal treatment consists is P at pressure0The mode of carrying out under the condition of+Δ P comprises: in described closed reactor, pass into volatile organic matter and non-active gas, it is Δ P that the intake of described volatile organic matter and non-active gas makes the pressure that described volatile organic matter and non-active gas produce in hydrothermal treatment consists.
8, according to the method described in 5 or 7, it is characterized in that, described volatile organic matter is polyethylene glycol, diethylene glycol, butanediol, acetic acid, maleic acid, oxalic acid, the aminotriacetic acid, 1 that normal propyl alcohol, isopropyl alcohol, ethylene glycol, glycerine, triethylene glycol, number-average molecular weight are 200-1500, one or more in 2-CDTA, citric acid, tartaric acid, malic acid and ethylenediamine.
9, according to the method described in 7 or 8, it is characterized in that, described non-active gas is nitrogen, group 0 element gas, carbon dioxide, sulfur hexafluoride and C1-C5Hydrocarbon.
10, according to the method described in 1, it is characterized in that, the maceration extract by volume in described dip compound is 1-10:1 with the ratio of carrier by weight.
11, according to the method described in 10, it is characterized in that, the maceration extract by volume in described dip compound is 1.1-5:1 with the ratio of carrier by weight.
12, according to the method described in 11, it is characterized in that, the maceration extract by volume in described dip compound is 1.3-3:1 with the ratio of carrier by weight.
13, according to the method described in 1, it is characterized in that, the temperature of the hydrothermal treatment consists of described step (2) is 100-200 DEG C, and the time of hydrothermal treatment consists is 0.5-36 hour; The dry condition of described step (3) comprising: temperature is 100-300 DEG C, and the time is 1-12 hour.
14, according to the method described in 13, it is characterized in that, the time of the hydrothermal treatment consists of described step (2) is 1-24 hour; The dry condition of described step (3) comprising: temperature is 100-280 DEG C, and the time is 2-8 hour.
15, according to the method described in 14, it is characterized in that, the baking temperature of described step (3) is 100-250 DEG C.
16, according to the method described in 1, it is characterized in that, described group vib metal component is selected from molybdenum and/or tungsten, VIII family metal component is selected from cobalt and/or nickel, in oxide and taking catalyst as benchmark, described contain at least one containing compound of group vib metallic element and at least one containing the compound of group VIII metallic element and containing or not make the content of group vib metal component in final described catalyst containing the consumption of the concentration of each component in the aqueous solution of cosolvent, the described aqueous solution be 10-50 % by weight, the content of group VIII metal component is 1-10 % by weight.
17, according to the method described in 16, it is characterized in that, in oxide and taking catalyst as benchmark, described contain at least one containing compound of group vib metallic element and at least one containing the compound of group VIII metallic element and containing or not make the content of group vib metal component in final described catalyst containing the consumption of the concentration of each component in the aqueous solution of cosolvent, the described aqueous solution be 15-45 % by weight, the content of group VIII metal component is 1-7 % by weight.
18, according to the method described in 1, it is characterized in that, the shaping carrier of described alumina hydrate-containing contains hydrated alumina and cellulose ether, and the radially crushing strength of described shaping carrier is more than or equal to 12N/mm, and water absorption rate is 0.4-1.5, and δ value is for being less than or equal to 10%; Wherein, δ=((Q1-Q2)/Q1) × 100%, Q1 is radially crushing strength of hydrated alumina forming matter, Q2 is that hydrated alumina forming matter is through water soaking 30 minutes, through 120 DEG C of radially crushing strengths that are dried after 4 hours.
19, according to the method described in 18, it is characterized in that, the radially crushing strength of described shaping carrier is 15 Newton/millimeter～30 Newton/millimeter, and water absorption rate is that 0.6～1, δ is less than or equal to 5%.
20, according to the method described in 18 or 19, it is characterized in that, taking described shaping carrier as benchmark, in described shaping carrier, the content of cellulose ether is 0.5 % by weight～8 % by weight, and the content of hydrated alumina is 92 % by weight～99.5 % by weight.
21, according to the method described in 20, it is characterized in that, taking described shaping carrier as benchmark, the content of described cellulose ether is 1 % by weight～6 % by weight, and the content of hydrated alumina is 94 % by weight～99 % by weight.
22, according to the method described in 21, it is characterized in that, taking described shaping carrier as benchmark, the content of described cellulose ether is 2 % by weight～5 % by weight, and the content of hydrated alumina is 95 % by weight～98 % by weight.
23, the catalyst of preparing according to the method described in any one in 1-22.
24, a hydrocarbon oil hydrogenation process for purification, is included under hydrocarbon oil hydrogenation refining reaction condition, and hydrocarbon oil crude material oil is contacted with the catalyst described in 23.
The method according to this invention, in the time that described dip compound is carried out to hydrothermal treatment consists, except the shaping carrier of described alumina hydrate-containing, the described compound that contains group vib metallic element, described containing the compound of group VIII metallic element, containing or the described cosolvent and the described aqueous solution that do not contain in the pressure P of water generates0Outward, the Δ P that also exerts pressure in addition, the catalyst of preparation is when refining for hydrocarbon oil hydrogenation thus, and its performance improves.
A first aspect of the present invention provides a kind of preparation method of the catalyst with hydrogenation catalyst effect, and this preparation method is included on the shaping carrier of alumina hydrate-containing and introduces at least one group VIII metallic element, at least one group vib metallic element.
In the present invention, term " at least one " represents one or more.
In the catalyst that preparation in accordance with the present invention obtains, the content of described group VIII metallic element, group vib metallic element can carry out suitable selection according to the concrete application scenario of described catalyst. Usually, described group vib metal component is preferably molybdenum and/or tungsten, and VIII family metal component is selected from cobalt and/or nickel. In oxide and taking catalyst as benchmark, the content of described group vib metal component is preferably 10-50 % by weight, more preferably 15-45 % by weight; The content of group VIII metal component is preferably 1-10 % by weight, more preferably 1-7 % by weight.
Preparation in accordance with the present invention, the method for introducing at least one group vib metallic element and at least one group vib metallic element on the shaping carrier of alumina hydrate-containing comprises the following steps:
(1) flood the shaping carrier of described alumina hydrate-containing with a kind of aqueous solution, wherein, the described aqueous solution contain at least one containing compound of group VIII metallic element and at least one containing the compound of group vib metallic element and containing or containing cosolvent;
(2) mixture dipping being obtained carries out hydrothermal treatment consists in closed reactor, and described hydrothermal treatment consists is P at pressure0Under the condition of+Δ P, carry out; And
(3) mixture hydrothermal treatment consists being obtained carries out Separation of Solid and Liquid, and the solid phase obtaining is dried.
Preparation in accordance with the present invention, in the described aqueous solution of step (1), the described concentration that contains the compound of group VIII metallic element and contain the compound of group vib metallic element, meets concrete instructions for use (for example previously described content requirement) with the content of group VIII metallic element and group vib metallic element in the catalyst that can make finally to prepare and is as the criterion.
According to the present invention, can be dissolved in water containing the compound of group vib metallic element with at least one by the compound that conventional this area at least one is contained to group VIII metallic element, thereby prepare the described aqueous solution.
For example, the described compound containing group VIII metallic element can be the conventional water soluble compound containing group VIII metallic element in this area, and the described compound that contains group vib metallic element can be the conventional water soluble compound containing group vib metallic element in this area.
Particularly, the described compound that contains group vib metallic element can be selected from ammonium molybdate, ammonium paramolybdate, ammonium metatungstate, molybdenum oxide and tungsten oxide.
The described compound containing group VIII metallic element can be selected from the nitrate of group VIII metallic element, the chloride of group VIII metallic element, the sulfate of group VIII metallic element, the formates of group VIII metallic element, the acetate of group VIII metallic element, the phosphate of group VIII metallic element, the citrate of group VIII metallic element, the oxalates of group VIII metallic element, the carbonate of group VIII metallic element, the subcarbonate of group VIII metallic element, the hydroxide of group VIII metallic element, the phosphate of group VIII metallic element, the phosphide of group VIII metallic element, the sulfide of group VIII metallic element, the aluminate of group VIII metallic element, the molybdate of group VIII metallic element, the water-soluble oxide of the tungstates of group VIII metallic element and group VIII metallic element.
Preferably, the described compound containing group VIII metallic element is selected from the oxalates of group VIII metallic element, the nitrate of group VIII metallic element, the sulfate of group VIII metallic element, the acetate of group VIII metallic element, the chloride of group VIII metallic element, the carbonate of group VIII metallic element, the subcarbonate of group VIII metallic element, the hydroxide of group VIII metallic element, the phosphate of group VIII metallic element, the molybdate of group VIII metallic element, the water-soluble oxide of the tungstates of group VIII metallic element and group VIII metallic element.
Particularly, the described compound containing group VIII metallic element can be selected from but be not limited to: nickel nitrate, nickelous sulfate, nickel acetate, basic nickel carbonate, cobalt nitrate, cobaltous sulfate, cobalt acetate, basic cobaltous carbonate, cobalt chloride and nickel chloride.
Preparation in accordance with the present invention, the described aqueous solution of step (1) can also contain the conventional various cosolvents in this area, to improve the described compound containing group VIII metallic element and the dissolubility of the described compound that contains group vib metallic element in water; Or stablize the described aqueous solution, prevent precipitation. Described cosolvent can, for the conventional various materials that can realize above-mentioned functions in this area, be not particularly limited. For example, described cosolvent can be one or more in phosphoric acid, citric acid and ammoniacal liquor. The present invention is not particularly limited for the concentration of described ammoniacal liquor, can be that the routine of this area is selected. The consumption of described cosolvent can be that the routine of this area is selected, and usually, in the described aqueous solution, the content of described cosolvent can be 1-10 % by weight.
Preparation in accordance with the present invention, described alumina hydrate-containing shaping carrier contains hydrated alumina and cellulose ether, and the radially crushing strength of described shaping carrier is more than or equal to 12N/mm, and water absorption rate is 0.4-1.5, and δ value is for being less than or equal to 10%; Wherein, δ=((Q1-Q2)/Q1) × 100%, Q1 is radially crushing strength of hydrated alumina forming matter, Q2 is that hydrated alumina forming matter is through water soaking 30 minutes, through 120 DEG C of radially crushing strengths that are dried after 4 hours.
According to hydrated alumina forming matter provided by the invention, the radially crushing strength of preferred described article shaped is 15-30N/mm, and water absorption rate is 0.6-1, and δ is less than or equal to 5%. Wherein, δ=((Q1-Q2)/Q1) × 100%, Q1 is radially crushing strength of hydrated alumina forming matter, Q2 is hydrated alumina forming matter through water soaking 30 minutes, the radially crushing strength through 120 DEG C of heating, dryings after 4 hours. The size of δ value is representing hydrated alumina forming matter variation (or being called loss of strength rate) to crushing strength through water soaking anteroposterior diameter. In the present invention, the described article shaped radially measuring method of crushing strength is carried out according to RIPP25-90 catalyst compressive resistance determination method, has detailed introduction about the article shaped concrete steps that radially crushing strength is measured at RIPP25-90, does not repeat here.
Described water absorption rate refers to the weight value added after excessive deionized water immersion 30min for dry hydrated alumina forming matter. The present invention adopts following concrete grammar to measure: first 120 DEG C of testing samples are dried 4 hours. Take out sample, be positioned in desiccator and be cooled to room temperature, with 40 mesh standard sieve screenings, take oversize 20g(numbering: w1) testing sample, add 50g deionized water, soak 30min, filter, solid phase drains 5min, weigh solid phase weight (numbering: w2), solid phase is transferred in baking oven, and 120 DEG C of heating, dryings 4 hours, are positioned over and in desiccator, are cooled to room temperature. Water absorption rate=(w1-w2)/w1
Under the prerequisite that is enough to make radially crushing strength, water absorption rate and the loss of strength rate of article shaped to meet the demands, the present invention is not particularly limited the content of cellulose ether, in concrete embodiment, taking the total amount of hydrated alumina shaping carrier as benchmark, the content of cellulose ether is preferably 0.5-8 % by weight, more preferably 1-6 % by weight, is more preferably 2-5 % by weight. Described cellulose ether preferably in methylcellulose, HEMC, hydroxypropyl methylcellulose one or more, further preferably methylcellulose, HEMC and their mixture wherein.
According to hydrated alumina forming matter provided by the invention, wherein can contain the adjuvant component that does not affect or be of value to radially crushing strength, water absorption rate and the δ value of improving described article shaped. For example, contain starch and add component, described starch can be the powder being obtained through pulverizing by vegetable seeds arbitrarily, as sesbania powder.
Described hydrated alumina is selected from any hydrated alumina that can be used as adsorbent and catalyst carrier precursor, for example, can be boehmite, boehmite, aluminium hydroxide, three water-aluminum hydroxides, preferably boehmite.
According to the preparation method of hydrated alumina forming matter provided by the invention, described forming method can be prior art arbitrarily, and to this, the present invention is not particularly limited. For example, described forming method can be the forming method of extrusion, spraying, round as a ball, compressing tablet and their combination. For ensureing carrying out smoothly of moulding, in the time of moulding, can in material (being the mixture of hydrated alumina and cellulose ether), introduce auxiliary agent and water etc. herein, for example, in the time adopting the moulding of extrusion method, comprise described hydrated alumina and cellulose ether are mixed with water, extrusion aid, then extrusion molding, obtain wet bar, then drying obtains article shaped of the present invention. Described auxiliary agent is selected from starch, and described starch can be the powder being obtained through pulverizing by vegetable seeds arbitrarily, as sesbania powder. The method that preferred forming method is extruded moulding.
Preparation in accordance with the present invention, in step (1), is not particularly limited for the method for dipping, can be that the routine of this area is selected, for example: the saturated infusion process in hole and excessive dipping method (, supersaturation infusion process). Preferably, the method according to this invention, described dipping is excessive dipping. The saturated infusion process in described hole and excessive infusion process are known in the field, for example, in concrete enforcement, it is 1-10:1 with the ratio of carrier by weight that described excessive dipping makes by the maceration extract by volume in the dip compound being formed by maceration extract and described carrier; Be preferably 1.1-5:1; More preferably 1.3-3:1. Preparation in accordance with the present invention, in step (1), number of times for dipping is also not particularly limited, it can be single-steeping, also can be for repeatedly flooding, in the catalyst finally obtaining, the content of group vib metallic element and group VIII metallic element can meet instructions for use (for example previously described content range) and be as the criterion.
Preparation in accordance with the present invention, in step (2), described hydrothermal treatment consists is P at pressure0Under the condition of+Δ P, carry out.
In the present invention, P0For the shaping carrier of described alumina hydrate-containing, the described compound that contains group vib metal, described contain the compound of group vib metal, containing or the described cosolvent and the described aqueous solution that do not contain in the pressure that produces in hydrothermal treatment consists of water.
The method according to this invention, in described hydrothermal treatment consists process, for carrying out pressure in the closed container of hydrothermal treatment consists except P0, also comprise Δ P outward, wherein, Δ P is 0.05-15MPa. Preferably, Δ P is 0.1-10MPa. From the catalytic activity of catalyst and the angle of the internal pressure that described closed container bears of the final preparation of balance, more preferably 0.2-7MPa of Δ P, more preferably 0.2-5MPa of Δ P.
In the present invention, pressure is all in gauge pressure.
Can adopt the conventional the whole bag of tricks in this area to make described hydrothermal treatment consists is P at pressure0Under the condition of+Δ P, carry out.
In one embodiment of the invention, making described hydrothermal treatment consists is P at pressure0The mode of carrying out under the condition of+Δ P comprises: under the existence of at least one volatile organic matter, carry out described hydrothermal treatment consists, it is Δ P that the addition of described volatile organic matter makes the pressure that described volatile organic matter produces in hydrothermal treatment consists.
Can adopt variety of way to make described hydrothermal treatment consists under the existence of described volatile organic matter, carry out (, carrying out thering is described volatile organic matter in the closed container of hydrothermal treatment consists). For example, described volatile organic matter can be added to the mixture that the aqueous solution for flooding described porous carrier or dipping obtain, thereby described hydrothermal treatment consists is carried out under the existence of volatile organic matter. The angle of the catalytic activity of the catalyst of preparing from further raising, the method according to this invention is preferably added volatile organic matter in the mixture that obtains of dipping, thereby described hydrothermal treatment consists is carried out under the existence of volatile organic matter.
In this embodiment, conventional various volatile organic matters can be added in closed container, as long as described volatile organic matter can improve the pressure in the closed container that carries out described hydrothermal treatment consists under hydrothermal treatment consists condition, make pressure in described closed container within scope mentioned above.
In the present invention, described volatile organic matter can be transformed into the material of gaseous state and/or under hydrothermal treatment consists condition, can be produced the material of gas by liquid state for various under hydrothermal treatment consists condition. For example, described volatile organic matter can be selected from the polyethylene glycol that alcohol, acid, amine and number-average molecular weight are 200-1500. Preferably, described volatile organic matter is selected from C1-C30Fatty alcohol, C2-C30Aliphatic acid, C2-C30Fatty amine, C6-C30Alkane and the number-average molecular weight polyethylene glycol that is 200-1500. More preferably, described volatile organic matter is selected from C1-C12Fatty alcohol, C2-C10Aliphatic acid, C2-C12Fatty amine, C6-C12Alkane and the number-average molecular weight polyethylene glycol that is 200-1500. Further preferably, described volatile organic matter is selected from C1-C8Fatty alcohol, C2-C5Aliphatic acid, C2-C7Fatty amine and C6-C11Alkane.
Particularly, described volatile organic matter can be selected from polyethylene glycol, diethylene glycol, butanediol, acetic acid, maleic acid, oxalic acid, the aminotriacetic acid, 1 that normal propyl alcohol, isopropyl alcohol, ethylene glycol, glycerine, triethylene glycol, number-average molecular weight are 200-1500,2-CDTA, tartaric acid, malic acid, ethylenediamine, hexane and isomers thereof, heptane and isomers thereof, octane and isomers thereof and decane and isomers thereof.
The method according to this invention, the consumption of described volatile organic matter is not particularly limited, and can carry out suitable selection according to the kind of the Δ P value of expection and the volatile organic matter using, and repeats no more herein.
In another embodiment of the invention, making described hydrothermal treatment consists is P at pressure0The mode of carrying out under the condition of+Δ P comprises: under the existence of at least one non-active gas, carry out described hydrothermal treatment consists, it is Δ P that the addition of described non-active gas makes the pressure that described non-active gas produces in hydrothermal treatment consists.
In the present invention, described non-active gas refers in hydrothermal treatment consists process can not there is not chemically interactive gas with porous carrier, the compound containing group VIII metal, the compound that contains group vib metal, compound and the water of cosolvent, can be the conventional various non-active gas in this area. Preferably, described non-active gas is selected from nitrogen, group 0 element gas (for example: argon gas), carbon dioxide, sulfur hexafluoride and C1-C5Hydrocarbon. Further preferably, described non-active gas is selected from nitrogen and group 0 element gas.
According to this embodiment, can be in the process of hydrothermal treatment consists, to carrying out passing into non-active gas in the closed container of hydrothermal treatment consists, making the pressure in described closed container is P0+ Δ P; Also can be carrying out before hydrothermal treatment consists, to carrying out passing into described non-active gas in the closed container of described hydrothermal treatment consists, then close described container and carry out hydrothermal treatment consists.
According to another embodiment of the present invention, making described post processing is P at pressure0The mode of carrying out under the condition of+Δ P comprises: under the existence of at least one volatile organic matter and at least one non-active gas, carry out described hydrothermal treatment consists, it is Δ P that total addition of described volatile organic matter and non-active gas makes the gross pressure that described volatile organic matter and non-active gas produce in hydrothermal treatment consists.
In this embodiment, the kind of described volatile organic matter and described non-active gas and using method as mentioned before, do not repeat them here.
The method according to this invention, although adopt above-mentioned three kinds of modes all can realize the object of the catalytic activity that improves the final catalyst obtaining, but the activity of the catalyst being obtained by preparation method of the present invention from further raising and the angle of ease-to-operate, preparation in accordance with the present invention is preferably carried out described hydrothermal treatment consists or under the existence of volatile organic matter and non-active gas, is carried out described hydrothermal treatment consists under the existence of non-active gas, so that described hydrothermal treatment consists is P at pressure0Under the condition of+Δ P, carry out. More preferably, described hydrothermal treatment consists is carried out under the existence of non-active gas.
Preparation in accordance with the present invention, the time of described hydrothermal treatment consists and temperature can be that the routine of this area is selected, as long as the pressure of described hydrothermal treatment consists meets previously described requirement. Preferably, the temperature of described hydrothermal treatment consists can be 100-200 DEG C; The time of described hydrothermal treatment consists can be 0.5-36 hour, is preferably 1-24 hour.
Preparation in accordance with the present invention also comprises step (3): the mixture that hydrothermal treatment consists is obtained carries out Separation of Solid and Liquid, and the solid phase obtaining is dried. Preparation method of the present invention is not particularly limited for the method for Separation of Solid and Liquid, can be that the routine of this area is selected, for example: can be filtration, standing separation or centrifugation. The present invention is also not particularly limited for described dry condition, can be that the routine of this area is selected. Usually, described dry condition comprises: temperature can be 100-300 DEG C, is preferably 100-280 DEG C, more preferably 100-250 DEG C; Time can be 1-12 hour, is preferably 2-8 hour.
Preparation in accordance with the present invention can also comprise carries out roasting by the dry solid matter obtaining. The condition of described roasting can be that the routine of this area is selected. Usually, the condition of described roasting comprises: temperature can be 350-550 DEG C, is preferably 400-500 DEG C; Time can be 1-8 hour, is preferably 2-6 hour.
A second aspect of the present invention provides a kind of catalyst being obtained by preparation method of the present invention. Catalyst according to the invention for example,, when the hydrofinishing for hydrocarbon ils (: the hydrodesulfurization of hydrocarbon ils or hydrodenitrogeneration), has higher catalytic activity.
Thus, a third aspect of the present invention provides the application of a kind of catalyst according to the invention in hydrocarbon oil hydrogenation is refining.
A fourth aspect of the present invention provides a kind of hydrofinishing process, and the method is included under hydrofinishing condition, and hydrocarbon ils is contacted with catalyst provided by the invention.
Hydrofinishing process according to the present invention is applicable to the subtractive process such as hydrodesulfurization, hydrodenitrogeneration of various hydrocarbon oil crude materials. Described hydrocarbon oil crude material can be for example one or more in gasoline, diesel oil, lubricating oil, kerosene and naphtha; Also can be one or more in reduced crude, decompression residuum, pertroleum wax and Fischer-Tropsch synthesis oil.
The present invention is that the catalyst of the application of the invention improves the active of catalyst in unifining process, is not particularly limited for all the other conditions of hydrofinishing process, can be that the routine of this area is selected. Usually, described hydrorefined condition comprises: temperature can be 300-400 DEG C; In gauge pressure, pressure can be 1.0-8.0MPa; When the liquid of hydrocarbon ils, volume space velocity can be 0.5-3.0 hour-1; Hydrogen to oil volume ratio can be 100-700.
According to hydrofinishing process of the present invention, described catalyst preferably adopts the conventional method of this area to carry out presulfurization before use. Usually, the condition of described presulfurization can comprise: under hydrogen exists, at the temperature of 360-400 DEG C, carry out the presulfurization of 2-4 hour with one or more in sulphur, hydrogen sulfide, carbon disulfide, DMDS or polysulfide. According to hydrofinishing process of the present invention, described presulfurization can be carried out outward at hydrogenation reactor, also can original position sulfuration in hydrogenation reactor.
Detailed description of the invention
Describe the present invention in detail below in conjunction with embodiment.
In following examples and comparative example, adopt the 3271E type Xray fluorescence spectrometer being purchased from Rigaku electric machine industry Co., Ltd., the content of each element in catalyst is analyzed to mensuration.
In following examples and comparative example, adopt gas chromatography to measure sulfur content and the nitrogen content in the product that carries out the raw material of hydrodesulfurization reaction and obtain.
In following examples and comparative example, adopt relative hydrodesulfurization activity to carry out the hydrodesulfurization activity of evaluate catalysts, computational methods are using hydrodesulfurization reaction as 1.65 order reaction processing, are calculated as follows the reaction rate constant k (X) of catalyst XHDS：
In formula, volume space velocity when LHSV is the liquid while carrying out hydrofining reaction,
Hydrodesulfurization activity with catalyst D-3 (is designated as k (D-3)HDS) be benchmark, be calculated as follows the relative hydrodesulfurization activity of catalyst X:
In following examples and comparative example, adopt relative hydrodenitrogenationactivity activity to carry out the hydrodenitrogenationactivity activity of evaluate catalysts X, computational methods are that hydrodenitrogeneration is reacted as 1 order reaction processing, are calculated as follows the reaction rate constant k (X) of catalystHDN：
In formula, volume space velocity when LHSV is the liquid while carrying out hydrofining reaction,
Hydrodenitrogenationactivity activity with catalyst D-3 (is designated as k (D-3)HDN) be benchmark, be calculated as follows the relative hydrodenitrogenationactivity activity of catalyst X:
Embodiment 1-2 obtains hydrated alumina shaping carrier for what illustrate prepared by the present invention.
Embodiment 1
Get the boehmite powder 100g that catalyst Chang Ling branch company produces, add 4.0g methylcellulose, 3.0g sesbania powder and 95mL deionized water, be fully uniformly mixed, by banded extruder kneading evenly after, extruded moulding obtains the wet article shaped of aluminium hydroxide. Wet hydrogen aluminium oxide article shaped is positioned over to 150 DEG C of dry alumina hydrate-containing shaping carrier S1 that obtain for 12 hours in baking oven. Radially crushing strength, water absorption rate and the δ value (loss of strength rate) of measuring dry aftershaping carrier S 1, the results are shown in table 1.
Embodiment 2
Get the boehmite SB powder 100g that Sasol company produces, add 3.0g HEMC, 2g hydroxypropyl methylcellulose, 3.0g sesbania powder and 90mL deionized water, fully be uniformly mixed, by banded extruder kneading evenly after, extruded moulding obtains moulding bar. Aluminium hydroxide moulding bar is positioned over 250 DEG C of dry hydrated alumina shaping carrier S2 that obtain for 4 hours in baking oven. Radially crushing strength, water absorption rate and the δ value of measuring dry aftershaping carrier S 2, the results are shown in table 1.
Comparative example 1
Get the boehmite powder 100g that catalyst Chang Ling branch company produces, add red fuming nitric acid (RFNA) 2.5mL, 3.0g sesbania powder and 95mL deionized water, be fully uniformly mixed, by banded extruder kneading evenly after, extruded moulding obtains moulding bar. Moulding bar be positioned in baking oven 80 DEG C dry 4 hours. Obtain shaping carrier DZ1, measure radially crushing strength, water absorption rate and the δ value of DZ1, the results are shown in table 1.
Comparative example 2
Get boehmite shaping carrier dried strip S3 in comparative example 1 through 600 DEG C of roastings 4 hours, obtain shaping carrier DZ2, measure radially crushing strength, water absorption rate and the δ value of DZ2, the results are shown in table 1.
Table 1
* butt: the 600 DEG C of roastings 4 hours in Muffle furnace of alumina hydrate-containing shaping carrier, the percentage of the ratio of the weight after roasting before the weight of carrier and this carrier roasting.
Embodiment 3-7 is for illustrating method for preparing catalyst provided by the invention and the catalyst of being prepared by the method.
Embodiment 3
50 grams of ammonium molybdates are joined in 120 ml waters, add under thermal agitation, drip concentration be 25% ammoniacal liquor until ammonium molybdate dissolves, then add 30 grams of cobalt nitrates and 10 grams of ammonium fluorides, after stirring and dissolving, add 20 milliliters of ethanol, then add water and be settled to 200 milliliters. Adopt the maceration extract by volume in 100 grams of carrier S 1(dip compounds of the above-mentioned aqueous solution dipping of excessive dipping method with the ratio of carrier to be by weight: 2.0), dip time is 0.1 hour. The mixture that dipping is obtained is placed in autoclave, carries out hydrothermal treatment consists, and the condition of hydrothermal treatment consists comprises: temperature is 150 DEG C, and the time is 4 hours; Pressure is 0.7MPa, wherein, and P0=0.5MPa, △ P=0.2MPa. The mixture that hydrothermal treatment consists is obtained is cooled to room temperature, after filtration, the solid obtaining is dried to 2 hours at 120 DEG C, then 450 DEG C of roastings 3 hours, obtains catalyst according to the invention B-1. The composition of catalyst B-1 is in table 3.
Embodiment 6
15 grams of basic cobaltous carbonates, 30 grams of molybdenum trioxides are joined in 120 ml waters, follow to stir to add 10 grams of phosphoric acid and 8 grams of boric acid, heating stirring and dissolving, adds 15 milliliters of isopropyl alcohols, then adds water and is settled to 200 milliliters. Adopt the maceration extract by volume that the above-mentioned aqueous solution of method of excessive dipping floods in 100 grams of carrier S 1(dip compounds with the ratio of carrier to be by weight: 2.0), dip time is 0.2 hour. The mixture that dipping is obtained is placed in autoclave and carries out hydrothermal treatment consists, and the condition of hydrothermal treatment consists comprises: temperature is 200 DEG C; Time is 10 hours; Pressure is 2.1MPa, wherein, and P0=1.5MPa, △ P=0.6MPa. The mixture that hydrothermal treatment consists is obtained is cooled to room temperature, after filtration, the solid obtaining is dried to 2 hours at 120 DEG C, thereby obtains catalyst according to the invention B-2. The composition of catalyst B-2 is in table 3.
Embodiment 7
20 grams of basic nickel carbonates are joined in 150 ml waters, follow to stir to add 8 grams of phosphoric acid, heating stirring and dissolving, follows stirring to add respectively 12 grams of ammonium molybdates and 110 grams of ammonium metatungstates, adds water and be settled to 200 milliliters after dissolving. Adopt the maceration extract by volume that the above-mentioned aqueous solution of method of excessive dipping floods in 100 grams of carrier S 2(dip compounds with the ratio of carrier to be by weight: 2.0), dip time is 0.5 hour. The mixture that dipping is obtained is placed in autoclave, carries out hydrothermal treatment consists, and the condition of hydrothermal treatment consists comprises: temperature is 100 DEG C; Time is 24 hours; In hydrothermal treatment consists process, to passing into nitrogen in autoclave, to make the pressure in autoclave be 5.2MPa, wherein, and P0=0.2MPa, △ P=5.0MPa. The mixture that hydrothermal treatment consists is obtained is cooled to room temperature, after filtration, the solid obtaining is dried to 2 hours at 120 DEG C, is then dried 3 hours again at 200 DEG C, obtains catalyst according to the invention B-3, and the composition of catalyst B-3 is in table 3.
Embodiment 8
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 7, different, in hydrothermal treatment consists process, it is 10.2MPa that the intake of nitrogen makes the pressure in autoclave, wherein, and P0=0.2MPa, Δ P=10.0MPa, obtains catalyst according to the invention B-4, and the composition of catalyst B-4 is shown in table 3.
Comparative example 3
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 7, different, in hydrothermal treatment consists process, in autoclave, do not pass into nitrogen, the pressure in autoclave be 0.2MPa(, Δ P=0), obtain catalyst D-1, it forms shown in table 3.
Embodiment 9
50 grams of ammonium molybdates are joined in 120 ml waters, add that under thermal agitation, to drip concentration be that ammoniacal liquor to the ammonium molybdate of 25 % by weight dissolves, then add 30 grams of cobalt nitrates, after stirring and dissolving, add 20 milliliters of ethanol, then add water and be settled to 200 milliliters. Adopt the maceration extract by volume in 100 grams of carrier S 2(dip compounds of the above-mentioned aqueous solution dipping of excessive dipping method with the ratio of carrier to be by weight: 2.0), dip time is 0.1 hour. The mixture that dipping is obtained is placed in autoclave, carries out hydrothermal treatment consists, and the condition of hydrothermal treatment consists comprises: temperature is 150 DEG C, time is 4 hours, in hydrothermal treatment consists process, to passing into argon gas in autoclave, to make the pressure in autoclave be 2.5MPa, wherein, and P0=0.5MPa, wherein, the pressure that ethanol produces is 0.2MPa to Δ P=2.0MPa(, the pressure that argon gas produces is 1.8MPa). The mixture that hydrothermal treatment consists is obtained is cooled to room temperature, after filtration, the solid obtaining is dried to 2 hours at 120 DEG C, then 450 DEG C of roastings 3 hours, obtains catalyst according to the invention B-5. The composition of catalyst B-5 is shown in table 3.
Comparative example 4
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 1, different, adopt carrier DZ2, in autoclave, do not add ethanol and ammonium fluoride, in hydrothermal treatment consists process, the pressure in autoclave be 0.5MPa(wherein, Δ P=0), obtain catalyst D-2, it forms shown in table 3.
Table 3
Remarks: on metal, amount is for catalyst is through 550 DEG C of roastings XRF analysis result after 4 hours.
Embodiment 8-12 is for illustrating application and the hydrofinishing process of catalyst according to the invention.
Embodiment 8-12
The catalyst that respectively prepared by Evaluation operation example 3-7 on 30 milliliters of diesel hydrotreating units.
Raw materials used as follows:
Raw material: Middle East straight-run diesel oil
S content: 9700wppm
N content: 97wppm
Density (20 DEG C): 0.8321g/cm3
Refraction index (20 DEG C): 1.4658
Use following process condition:
Volume space velocity: the 2.0h when liquid of hydrocarbon ils-1
Hydrogen to oil volume ratio: 300
Pressure: 3.2MPa
Reaction temperature: 330 DEG C
Comparative example 5-6
Adopt the method identical with embodiment 10-14 to carry out hydrofinishing, different, catalyst is catalyst prepared by comparative example 3-4, and result is shown in table 4.
Table 4
The result demonstration of table 4, prepared according to the methods of the invention catalyst demonstrates higher catalytic activity in the hydrofinishing of hydrocarbon ils.
Claims (24)
1. the preparation method of a hydrogenation catalyst, be included in and on a kind of shaping carrier of alumina hydrate-containing, introduce at least one group VIII metal component and at least one group vib metal component, wherein, the method for introducing at least one group VIII metal component and at least one group vib metal component on the shaping carrier of alumina hydrate-containing comprises the following steps:
(1) with containing at least one compound containing group vib metallic element and at least one shaping carrier that contains the compound of group VIII metallic element and contain or do not flood containing the aqueous solution of cosolvent described alumina hydrate-containing, obtain a kind of dip compound;
(2) dip compound step (1) being obtained carries out hydrothermal treatment consists in closed reactor, and described hydrothermal treatment consists is P at pressure0Under the condition of+Δ P, carry out, wherein, P0For the shaping carrier of described alumina hydrate-containing, the described compound that contains group vib metallic element, described containing the compound of group VIII metallic element, containing or the described cosolvent and the described aqueous solution that do not contain in the pressure that produces in hydrothermal treatment consists of water, Δ P is 0.2-15MPa; And
(3) mixture hydrothermal treatment consists being obtained carries out Separation of Solid and Liquid, and the solid phase obtaining is dried.
2. method according to claim 1, is characterized in that, described Δ P is 0.2-10MPa.
3. method according to claim 2, is characterized in that, described Δ P is 0.2-7MPa.
4. method according to claim 3, is characterized in that, described Δ P is 0.2-5MPa.
5. method according to claim 1, is characterized in that, making described hydrothermal treatment consists is P at pressure0The mode of carrying out under the condition of+Δ P comprises: in described closed reactor, pass into volatile organic matter, it is Δ P that the intake of volatile organic matter makes the pressure that described volatile organic matter produces in hydrothermal treatment consists.
6. method according to claim 1, is characterized in that, making described hydrothermal treatment consists is P at pressure0The mode of carrying out under the condition of+Δ P comprises: in described closed reactor, pass into non-active gas, it is Δ P that the intake of described non-active gas makes the pressure that described non-active gas produces in hydrothermal treatment consists.
7. method according to claim 1, is characterized in that, making described hydrothermal treatment consists is P at pressure0The mode of carrying out under the condition of+Δ P comprises: in described closed reactor, pass into volatile organic matter and non-active gas, it is Δ P that the intake of described volatile organic matter and non-active gas makes the pressure that described volatile organic matter and non-active gas produce in hydrothermal treatment consists.
8. according to the method described in claim 5 or 7, it is characterized in that, described volatile organic matter is polyethylene glycol, diethylene glycol, butanediol, acetic acid, maleic acid, oxalic acid, the aminotriacetic acid, 1 that normal propyl alcohol, isopropyl alcohol, ethylene glycol, glycerine, triethylene glycol, number-average molecular weight are 200-1500, one or more in 2-CDTA, citric acid, tartaric acid, malic acid and ethylenediamine.
9. method according to claim 7, is characterized in that, described non-active gas is nitrogen, group 0 element gas, carbon dioxide, sulfur hexafluoride and C1-C5Hydrocarbon.
10. method according to claim 1, is characterized in that, the maceration extract by volume in described dip compound is 1-10:1 with the ratio of carrier by weight.
11. methods according to claim 10, is characterized in that, the maceration extract by volume in described dip compound is 1.1-5:1 with the ratio of carrier by weight.
12. methods according to claim 11, is characterized in that, the maceration extract by volume in described dip compound is 1.3-3:1 with the ratio of carrier by weight.
13. methods according to claim 1, is characterized in that, the temperature of the hydrothermal treatment consists of described step (2) is 100-200 DEG C, and the time of hydrothermal treatment consists is 0.5-36 hour; The dry condition of described step (3) comprising: temperature is 100-300 DEG C, and the time is 1-12 hour.
14. methods according to claim 13, is characterized in that, the time of the hydrothermal treatment consists of described step (2) is 1-24 hour; The dry condition of described step (3) comprising: temperature is 100-280 DEG C, and the time is 2-8 hour.
15. methods according to claim 14, is characterized in that, the baking temperature of described step (3) is 100-250 DEG C.
16. methods according to claim 1, it is characterized in that, described group vib metal component is selected from molybdenum and/or tungsten, VIII family metal component is selected from cobalt and/or nickel, in oxide and taking catalyst as benchmark, described at least one compound containing group vib metallic element and at least one concentration that contains the compound of group VIII metallic element and contain or do not contain each component in the aqueous solution of cosolvent of containing, it is 10-50 % by weight that the consumption of the described aqueous solution makes the content of group vib metal component in final described catalyst, the content of group VIII metal component is 1-10 % by weight.
17. methods according to claim 16, it is characterized in that, in oxide and taking catalyst as benchmark, described contain at least one containing compound of group vib metallic element and at least one containing the compound of group VIII metallic element and containing or not make the content of group vib metal component in final described catalyst containing the consumption of the concentration of each component in the aqueous solution of cosolvent, the described aqueous solution be 15-45 % by weight, the content of group VIII metal component is 1-7 % by weight.
18. methods according to claim 1, it is characterized in that, the shaping carrier of described alumina hydrate-containing contains hydrated alumina and cellulose ether, and the radially crushing strength of described shaping carrier is more than or equal to 12N/mm, water absorption rate is 0.4-1.5, and δ value is for being less than or equal to 10%; Wherein, δ=((Q1-Q2)/Q1) × 100%, Q1 is radially crushing strength of hydrated alumina forming matter, Q2 is that hydrated alumina forming matter is through water soaking 30 minutes, through 120 DEG C of radially crushing strengths that are dried after 4 hours.
19. methods according to claim 18, is characterized in that, the radially crushing strength of described shaping carrier is 15 Newton/millimeter～30 Newton/millimeter, and water absorption rate is that 0.6～1, δ is less than or equal to 5%.
20. according to the method described in claim 18 or 19, it is characterized in that, taking described shaping carrier as benchmark, in described shaping carrier, the content of cellulose ether is 0.5 % by weight～8 % by weight, and the content of hydrated alumina is 92 % by weight～99.5 % by weight.
21. methods according to claim 20, is characterized in that, taking described shaping carrier as benchmark, the content of described cellulose ether is 1 % by weight～6 % by weight, and the content of hydrated alumina is 94 % by weight～99 % by weight.
22. methods according to claim 21, is characterized in that, taking described shaping carrier as benchmark, the content of described cellulose ether is 2 % by weight～5 % by weight, and the content of hydrated alumina is 95 % by weight～98 % by weight.
23. catalyst of preparing according to the method described in any one in claim 1-22.
24. 1 kinds of hydrocarbon oil hydrogenation process for purification, are included under hydrocarbon oil hydrogenation refining reaction condition, and hydrocarbon oil crude material oil is contacted with the catalyst described in claim 23.
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