CN110773180A

CN110773180A - Hydrogenation activity protection catalyst and preparation and application thereof

Info

Publication number: CN110773180A
Application number: CN201810855734.6A
Authority: CN
Inventors: 孙淑玲; 杨清河; 胡大为; 马云海; 王振; 曾双亲; 桑小义; 戴立顺
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petrochemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petrochemical Corp
Priority date: 2018-07-31
Filing date: 2018-07-31
Publication date: 2020-02-11

Abstract

The invention relates to a hydrogenation activity protection catalyst, and a preparation method and an application thereof, wherein the hydrogenation activity protection catalyst comprises a carrier and a hydrogenation activity metal component, wherein the carrier contains alumina and a hydrogenation metal element, the hydrogenation metal element is selected from one or more of VIB group, VIII group and VB group, and the content of the hydrogenation metal element is not more than 12 wt% based on the carrier and calculated by oxide. The preparation method of the hydrogenation activity protection catalyst comprises the steps of preparing an alumina carrier containing alumina and a hydrogenation metal element and introducing a hydrogenation activity component. The hydrogenation activity protection catalyst provided by the invention is used for heavy oil processing, and shows better hydrogenation demetalization performance.

Description

Hydrogenation activity protection catalyst and preparation and application thereof

Technical Field

The invention relates to a hydrogenation protection catalyst, preparation and application thereof, in particular to a protection catalyst suitable for a fixed bed hydrogenation process, and preparation and application thereof.

Background

Along with the aggravation of the trend of heavy and inferior crude oil, the processing difficulty of crude oil is increased, the yield of light oil products is reduced, the demand of the market on high-quality light oil products is continuously increased, and environmental protection regulations are more and more strict. At present, the processing and full utilization of heavy oil, especially residual oil, is becoming a main topic of global oil refining industry attention, and the residual oil hydrogenation technology is a processing technology which is widely applied in the heavy oil processing technology, and is a well-known economic and environment-friendly deep processing technology. The residual oil contains a large amount of metal impurities such as Ni, V, Fe, Ca and the like and solid impurities, and if the impurities cannot be effectively removed, the impurities can have adverse effects on a downstream hydrogenation catalyst and can easily deactivate the downstream catalyst. One of the effective ways to solve this problem is to load a protecting agent with hydrogenation activity on the top of the hydrogenation catalyst, so the development of a protecting agent with high demetallization activity and strong metal-containing ability is one of the key technologies for heavy oil hydroprocessing.

Patent CN101890381A discloses a residual oil hydrogenation protection catalyst and its application. The catalyst has the advantages of large pore volume, large aperture, high porosity, reasonable pore distribution, larger pore opening on the outer surface, good pore canal penetrability, and more than 36 percent of pore canals with the diameter of more than 1000 nm. Especially, when the catalyst is used in a residual oil fixed bed hydrogenation method, the removed metal can be uniformly precipitated in the whole catalyst bed layer, and the impurities vanadium and calcium can be precipitated in the pore channel, so that the utilization rate of pores is improved, and the long-period operation is kept.

Patent CN00124903.7 discloses a hydrogenation protection catalyst, which contains an alumina carrier and molybdenum and/or tungsten and nickel and/or cobalt loaded on the alumina carrier, wherein the total ammonia integral adsorption heat of the alumina carrier is not more than 25 joules/gram, and the percentage of the ammonia integral adsorption heat of more than 100 kilojoules/mole of ammonia differential adsorption heat to the total ammonia integral adsorption heat is not more than 10%. Compared with the catalyst in the prior art, the protective agent has higher catalytic activity, lower carbon deposit amount, lower pore volume reduction rate, better activity stability and higher strength.

The patent CN98111379.6 discloses a hydrogenation protection catalyst and a preparation method thereof, wherein a catalyst carrier is a bimodal pore with ultra-large pore diameter and 0.1-30 mu m of pore diameter, the pore volume of the catalyst is 0.1-0.8ml/g, and the specific surface area is 0.1-20m ²The volume ratio of the metal element of VIB group is 6.65-20.0 m% and/or the metal element of VIII group is 8.71-26.13 m%. The preparation method comprises the steps of preparing the alumina carrier by adopting a particle packing method, then equivalently dipping the alumina carrier by adopting a molybdenum-containing solution and a nickel-containing solution, drying the dipped catalyst for 2-5h at the temperature of 100-550 ℃, and carrying out configuration roasting for 2-5h at the temperature of 500-550 ℃. The iron-removing rate and the strength are very high.

Disclosure of Invention

The technical problem to be solved by the invention is to provide a novel hydrogenation activity protection catalyst, a preparation method and application thereof.

Specifically, the present invention relates to the following:

the invention provides a hydrogenation activity protection catalyst, which comprises a carrier and a hydrogenation activity metal component, wherein the carrier contains alumina and hydrogenation metal elements, the hydrogenation metal elements are selected from one or more of VIB group, VIII group and VB group, and the content of the hydrogenation metal elements is not more than 12 wt% based on the carrier and calculated by oxides.

According to any one hydrogenation activity protection catalyst provided by the invention, preferably, the hydrogenation metal elements comprise at least one VIB group metal element and at least one VIII group metal element and optionally a VB group metal element, and the content of the VIB group metal element is not more than 5 wt%, the content of the VIII group metal element is not more than 2 wt%, and the content of the VB group metal element is 0-6 wt% calculated on oxide and based on the carrier.

According to any one hydrogenation activity protection catalyst provided by the invention, preferably, the carrier is in bimodal pore distribution under the conditions that the diameter is 5-20nm and the diameter is 100-500nm, the pore volume of the pores with the diameter of 5-20nm accounts for 55-80% of the total pore volume, and the pore volume of the pores with the diameter of 100-500nm accounts for 10-35% of the total pore volume; further preferably, the pore volume of pores with a diameter of 5-20nm accounts for 60-75% of the total pore volume, and the pore volume of pores with a diameter of 100-500nm accounts for 15-30% of the total pore volume.

According to any one hydrogenation activity protection catalyst provided by the invention, preferably, the pore volume of the carrier is 0.95-1.6 ml/g, and the specific surface area is 50-400 m ²Per gram; preferably, the carrier has a pore volume of 0.95 to 1.55 ml/g and a specific surface area of 80 to 350 m ²Per gram.

According to any one of the hydrogenation activity protecting catalysts provided by the present invention, preferably, the alumina is selected from bimodal porous aluminas having single or mixed crystalline phases of gamma-, η -, theta-and delta-.

According to any one hydrogenation activity protection catalyst provided by the invention, preferably, the VIB group metal element is molybdenum and/or tungsten, the VIII group metal element is cobalt and/or nickel, and the VB group metal element is vanadium and/or niobium; the VIB group metal element in the carrier is 0.1-5 wt%, preferably 1-5 wt%, and more preferably 1-4.5 wt% calculated by oxide and based on the carrier; the content of the group VIII metal element is 0.1 to 2% by weight, preferably 0.2 to 1.5% by weight, and more preferably 0.3 to 1.5% by weight; the content of the group VB metal element is 0 to 5% by weight, preferably 0 to 4% by weight.

According to any one hydrogenation activity protection catalyst provided by the invention, preferably, the hydrogenation activity metal component is selected from at least one VIB group metal component and at least one VIII group metal component and optionally a VB group metal component, the content of the VIB group metal component is not more than 6 wt%, the content of the VIII group metal component is not more than 2 wt%, and the content of the VB group metal component is 0-6 wt% calculated by oxide and based on the catalyst; further preferably, the metal component of the VIB group is selected from molybdenum and/or tungsten, the metal component of the VIII group is selected from cobalt and/or nickel, the metal element of the VB group is vanadium and/or niobium, and the content of the metal component of the VIB group is 1.5-5.5 wt%, the content of the metal component of the VIII group is 0.2-2 wt% and the content of the metal component of the VB group is 0-5 wt% calculated on oxide basis and based on the catalyst.

The invention also provides a preparation method of the hydrogenation activity protection catalyst, which is preferably any one of the hydrogenation activity protection catalysts, and the preparation method comprises the steps of preparing a carrier and loading a hydrogenation activity metal component on the carrier, wherein the preparation of the carrier comprises the steps of mixing the hydrated alumina P1 containing pseudo-boehmite and the modified product P2 of P1, and then molding, drying and roasting; the weight mixing ratio of the P1 to the P2 is 20-95: 5-80, wherein the P2 contains hydrogenation metal elements, the hydrogenation metal elements are selected from one or more of VIB group, VIII group and VB group, and the dosage of the P2 ensures that the content of the hydrogenation metal elements in the final carrier calculated by oxide is not more than 12 percent by weight; the drying conditions include: the temperature is 40-350 ℃, the time is 1-24 hours, and the roasting conditions comprise: the temperature is more than 300 to less than or equal to 900 ℃, and the time is 1 to 8 hours.

According to the preparation method of any one hydrogenation activity protection catalyst provided by the invention, preferably, the hydrogenation metal elements comprise at least one VIB group metal element, at least one VIII group metal element and optionally a VB group metal element, and the P2 is used in an amount such that the content of the VIB group metal element in oxide in the final carrier is not more than 5 wt%, the content of the VIII group metal element is not more than 2 wt% and the content of the VB group metal element is 0-6 wt%.

According to the preparation method of any one hydrogenation activity protection catalyst provided by the invention, preferably, the kappa value of P2 is 0 to less than or equal to 0.9, and the kappa is DI ₂/DI ₁，DI ₁Acid peptization index, DI, of pseudo-boehmite containing hydrated alumina P1 ₂Acid peptization index of a modification P2 of a hydrated alumina P1 containing pseudoboehmite; preferably, the P2 has a kappa value of 0 to 0.6 or less.

According to the preparation method of any one hydrogenation activity protection catalyst provided by the invention, preferably, the hydrated alumina P1 containing the pseudo-boehmite has the pore volume of 0.9-1.4 ml/g and the specific surface of 100-350 m ²Per gram, most probable pore diameter is 8-30 nm; preferably, the hydrated alumina P1 containing the pseudo-boehmite has the pore volume of 0.95-1.3 ml/g and the specific surface of 120-300 m ²A few pores with a diameter of 10-25 nm.

According to the preparation method of any one hydrogenation activity protection catalyst provided by the invention, preferably, the P2 is a particulate matter with 80-300 meshes; preferably, the P2 is a 100-200 mesh particulate.

According to the preparation method of any one hydrogenation activity protection catalyst provided by the invention, preferably, P2 is a modified substance of P1, and the method for modifying P1 into P2 comprises the following steps: (a) forming, drying and roasting the pseudo-boehmite-containing hydrated alumina P1; (b) impregnating the carrier obtained in the step (a) with impregnation liquid containing hydrogenation metal elements, drying, roasting, grinding and screening all or part of the carrier to obtain a modified substance P2, wherein the content of the hydrogenation metal elements is not more than 13 wt% based on the modified substance P2; the drying conditions of step (a) include: the temperature is 40-350 ℃, the time is 1-24 hours, and the roasting conditions comprise: the temperature is 300-900 ℃ and the time is 1-10 hours; the drying conditions of step (b) include: the temperature is 100 ℃ and 250 ℃, the time is 1-10 hours, and the roasting conditions comprise: the temperature is 360-500 ℃ and the time is 1-10 hours.

According to the preparation method of any one hydrogenation activity protection catalyst provided by the invention, preferably, the P2 is a particulate matter with 80-300 meshes in the P1 modified substance, and the P2 is further preferably a particulate matter with 100-200 meshes in the P1 modified substance.

According to the preparation method of any one hydrogenation activity protection catalyst provided by the invention, preferably, the method for loading the hydrogenation active metal component on the carrier is an impregnation method, and comprises the steps of preparing a solution containing a hydrogenation active metal component compound, impregnating the carrier with the solution, and then drying, roasting or not roasting, the hydrogenation active metal component is selected from at least one group VIB metal component, at least one group VIII metal component and optionally a group VB metal component, the concentration of the compound containing the hydrogenation active metal component in the solution and the using amount of the solution enable the content of the VIB group metal component in the final catalyst to be not more than 6 weight percent, the content of the VIII group metal component to be not more than 2.5 weight percent and the content of the VB group metal component to be 0-6 weight percent based on oxide and catalyst; the drying conditions after the loading of the hydrogenation active metal component include: the temperature is 100-140 ℃, the time is 1-6 hours, and the roasting conditions comprise: the temperature is 360-450 ℃ and the time is 2-6 hours.

Further preferably, the group VIB metal component is selected from molybdenum and/or tungsten, the group VIII metal component is selected from cobalt and/or nickel, the group VB metal component is selected from vanadium and/or niobium, and the concentration and the amount of the impregnation solution are such that the group VIB metal component content, the group VIII metal component content and the group VB metal component content in the final catalyst are respectively 1.5-5.5 wt%, 0.2-2 wt% and 0-5 wt%, calculated on oxide basis and based on the catalyst.

Further, the invention also provides an application of any one hydrogenation activity protection catalyst in heavy oil hydrogenation treatment.

The hydrogenation activity protection catalyst provided by the invention can be prepared into various easily-operated molded products according to different requirements, such as spheres, honeycombs, bird nests, tablets or strips (clovers, butterflies, cylinders and the like). The shaping can be carried out in a conventional manner, for example, by one or a combination of rolling, tabletting and extrusion. In the molding, for example, extrusion molding, in order to ensure that the molding proceeds smoothly, water, an extrusion aid and/or an adhesive, with or without a pore-expanding agent, may be added to the mixture, followed by extrusion molding, followed by drying and firing. The kind and amount of the extrusion aid and peptizing agent are well known to those skilled in the art, for example, common extrusion aid may be one or more selected from sesbania powder, methyl cellulose, starch, polyvinyl alcohol, and polyvinyl alcohol, the peptizing agent may be inorganic acid and/or organic acid, and the pore-expanding agent may be one or more selected from starch, synthetic cellulose, polymeric alcohol, and surfactant. The synthetic cellulose is preferably one or more of hydroxymethyl cellulose, methyl cellulose, ethyl cellulose and hydroxy fiber fatty alcohol polyvinyl ether, the polymeric alcohol is preferably one or more of polyethylene glycol, polypropylene alcohol and polyvinyl alcohol, and the surfactant is preferably one or more of fatty alcohol polyvinyl ether, fatty alcohol amide and derivatives thereof, and an allyl alcohol copolymer and a maleic acid copolymer with the molecular weight of 200-10000.

Wherein, the acid peptization index DI in the carrier preparation refers to that after the hydrated alumina containing the pseudo-boehmite is added with nitric acid according to a certain acid-aluminum ratio, the peptized hydrated alumina containing the pseudo-boehmite is mixed with Al in a certain reaction time ₂O ₃Calculated in percent, DI ═ 1-W ₂/W ₁)×100％，W ₁And W ₂Respectively before reaction of pseudo-boehmite with acid and after reaction with acid, and Al ₂O ₃The weight of the meter.

The DI measurement comprises ⑴ determining the content of firing group (the content of firing group is the ratio of the weight after firing to the weight before firing of a certain amount of pseudoboehmite after firing at 600 ℃ for 4 hours) of alumina hydrate containing pseudoboehmite as a, ⑵ weighing the alumina hydrate W containing pseudoboehmite with an analytical balance ₀G, W ₀In an amount sufficient for Al ₂O ₃W of meter ₁Is 6 g (W) ₁/a＝W ₀) Weighing deionized water W g, W is 40.0-W ₀Adding weighed hydrated alumina containing pseudoboehmite and deionized water into a beaker to mix under stirring, ⑶ transferring 20mL of dilute nitric acid solution with the concentration of 0.74N by using a 20mL pipette, adding the acid solution into the beaker in the step (2), reacting for 8 minutes under stirring, and ⑷ centrifuging the slurry obtained after the reaction in the step (3) in a centrifugeSeparating, placing the precipitate into a weighed crucible, drying at 125 deg.C for 4 hr, calcining at 850 deg.C in a muffle furnace for 3 hr, weighing to obtain a burning sample amount W ₂G; (5) according to the formula DI ═ 1-W ₂/W ₁) X 100% calculated.

The hydrated alumina containing the pseudoboehmite can be any pseudoboehmite prepared by the prior art, and can also be a mixture of the pseudoboehmite and other hydrated alumina, and the other hydrated alumina is selected from one or more of monohydrated alumina, alumina trihydrate and amorphous hydrated alumina. In a preferred embodiment, the pseudo-boehmite content of the pseudo-boehmite-containing hydrated alumina is not less than 50%, and more preferably not less than 60%, as characterized by X-ray diffraction.

In the present invention, the pore volume, specific surface area and mode pore diameter of the pseudo-boehmite-containing hydrated alumina are characterized by BET nitrogen adsorption after the pseudo-boehmite-containing hydrated alumina is calcined at 600 ℃ for 4 hours.

The inventor of the invention also finds that the peptization index of the modified alumina P1 containing pseudo-boehmite is changed, and the carrier obtained by mixing, molding, drying and roasting the modified alumina P1 which is not heat-treated has obvious bimodal pore distribution. In particular, after the 80-300 mesh particles, preferably 100-200 mesh particles, are mixed with the non-heat-treated fraction, shaped, dried and calcined, the pore distribution of each single peak in the double peak of the resulting support is particularly concentrated. Here, the particles of 80-300 mesh, preferably 100-200 mesh particles, means particles of which the modified material is sieved (including a crushing or grinding step as necessary) and whose sieved material (undersize material) satisfies 80-300 mesh, preferably 100-200 mesh particles in a percentage (by weight) of the total amount of not less than 60%, further preferably not less than 70%.

In specific implementation, the P2 can be conveniently obtained by the following method:

⑴ the drying process is carried out to obtain P2, which comprises forming hydrated alumina P1 containing pseudo-boehmite by conventional method and impregnating active metal to prepare conventional hydrotreating catalyst, and the tail material by-produced from the drying process of the impregnated strip, for example, the tail material by-produced from the drying and shaping process of the impregnated strip (conventionally called dry waste), grinding the tail material, and sieving to obtain P2.

⑵ is obtained by calcining, and comprises forming and impregnating the hydrated alumina P1 containing pseudo-boehmite with active metal by a conventional method to prepare a conventional hydrotreating catalyst, and grinding and sieving the tailings to obtain P2, wherein the tailings are by-produced by calcining (conventionally referred to as finished waste), for example, the tailings are by-produced in the process of impregnating, strip calcining and shaping.

⑶ is obtained based on the mixing of two or more of the modifications P2 obtained by the methods described above when P2 is obtained by the mixing method, there is no limitation on the mixing ratio of the modifications P2 obtained by the methods described above respectively.

In the carrier, the VIB group metal element is preferably molybdenum and/or tungsten, the VIII group metal element is preferably nickel and/or cobalt, and the VB group metal element is preferably vanadium and/or niobium. The VIB group metal element in the carrier is 0.1-5 wt%, preferably 1-5 wt%, and more preferably 1-4.5 wt% calculated by oxide and taken as reference; the content of the group VIII metal element is 0.1 to 2% by weight, preferably 0.2 to 1.5% by weight, and more preferably 0.3 to 1.5% by weight; the content of the group VB metal element is 0 to 5% by weight, preferably 0 to 4% by weight.

The hydrogenation active metal component in the catalyst provided by the invention is derived from two parts, wherein one part is a hydrogenation metal element introduced and stored in the carrier preparation process, and the other part is the hydrogenation active metal component introduced after the carrier preparation is finished. Wherein, the hydrogenation active metal component introduced after the preparation of the carrier is completed is preferably a group VIB metal component, a group VIII metal component and an optional group VB metal component, further, the group VIB metal component is preferably molybdenum and/or tungsten, the group VIII metal component is preferably nickel and/or cobalt, and the group VB metal component is preferably vanadium and/or niobium.

Preferably, the catalyst of the present invention contains the group VIB metal component in an amount of not more than 6 wt%, the group VIII metal component in an amount of not more than 2 wt%, and the group VB metal component in an amount of 0 to 6 wt%, calculated on oxide basis and based on the catalyst.

The present invention is not particularly limited to the supporting method on the premise that it is sufficient to support the hydrogenation-active metal component on the alumina support, and a preferable method is an impregnation method comprising preparing an impregnation solution of a compound containing the metal, and thereafter impregnating the alumina support with the solution. The impregnation method is a conventional method, and for example, the impregnation method can be excess liquid impregnation and pore saturation impregnation.

Wherein, the metal-containing compound is selected from one or more of water-soluble compounds (including compounds soluble in water in the presence of a cosolvent). Taking the molybdenum in the VIB group as an example, the molybdenum can be selected from one or more of molybdenum oxide, molybdate and paramolybdate, and the molybdenum oxide, ammonium molybdate and paramolybdate are preferable; tungsten of the VIB group is taken as an example, and can be selected from one or more of tungstate, metatungstate and ethyl metatungstate, and ammonium metatungstate and ethyl ammonium metatungstate are preferred; nickel of group VIII metal is exemplified and can be selected from cobalt nitrate, basic cobalt carbonate; one or more of nickel nitrate, nickel acetate, basic nickel carbonate, nickel chloride and soluble complex of nickel, preferably nickel nitrate and basic nickel carbonate; taking the group VB vanadium as an example, the vanadium can be selected from one or more of vanadium pentoxide, ammonium vanadate, ammonium metavanadate, vanadium sulfate and vanadium heteropoly acid, and the ammonium metavanadate and ammonium vanadate are preferred.

The alumina carrier provided by the invention can also contain any substance which does not affect the performance of the carrier provided by the invention or can improve the performance of the catalyst prepared by the carrier provided by the invention. If phosphorus or the like is contained, the content of the above-mentioned component is not more than 4% by weight, preferably 0.5 to 3% by weight, in terms of oxide and based on the catalyst.

When the carrier further contains phosphorus and the like, the method for introducing the phosphorus and the like can be any method, and for example, a compound containing the phosphorus and the like can be directly mixed with the pseudo-boehmite, molded and calcined; the compound containing the phosphorus and other components and the compound containing the hydrogenation active metal component are prepared into a mixed solution and then are contacted with the carrier; or preparing a compound containing phosphorus and the like into a solution separately, contacting the solution with the carrier, and roasting the solution. When the components such as phosphorus and the like and the hydrogenation active metal are introduced into the carrier separately, it is preferable to first contact the carrier with a solution containing the promoter compound and calcine it, and then contact it with a solution containing the compound of the hydrogenation active metal component, for example, by impregnation, at a calcination temperature of 400-600 deg.C, preferably 420-500 deg.C, for a calcination time of 2-6 hours, preferably 3-6 hours.

According to the heavy oil hydrotreating method provided by the present invention, the reaction conditions for the heavy oil hydrotreating are not particularly limited, and in a preferred embodiment, the reaction conditions are: the reaction temperature is 300-550 ℃, the further optimization is 330-480 ℃, the hydrogen partial pressure is 4-20 MPa, the further optimization is 6-18 MPa, and the volume space velocity is 0.1-3.0 hours ^-1More preferably 0.15 to 2 hours ^-1The hydrogen-oil volume ratio is 200-.

The hydrogenation apparatus may be any reactor sufficient to contact and react the feedstock oil with the catalyst under hydrotreating reaction conditions, for example, in the fixed bed reactor, moving bed reactor or ebullating bed reactor.

The hydroprocessing catalyst, prior to use, can be presulfided with sulfur, hydrogen sulfide or sulfur-containing feedstock, typically in the presence of hydrogen at a temperature of 140 ℃ and 370 ℃, either ex situ or in situ, to convert its supported hydrogenation-active metal component to a metal sulfide component, according to conventional methods in the art.

Compared with the catalyst provided by the prior art, the catalyst provided by the invention adopts a specific carrier containing hydrogenation metal elements, in particular to a bimodal pore alumina carrier in which the bimodal pore diameters are concentrated in a range of 5nm-20nm and 100nm-500 nm. The catalyst shows better hydrodemetallization performance when being used for heavy oil processing. The catalyst provided by the invention can be used independently or combined with other catalysts, and is particularly suitable for hydrotreating heavy oil, particularly inferior residual oil, so as to provide qualified raw oil for subsequent processes (such as a catalytic cracking process).

Detailed Description

The following examples further illustrate the invention but should not be construed as limiting it. The reagents used in the examples, except where specifically indicated, were all chemically pure reagents. The pseudoboehmite employed in the following examples includes:

p1-1: dry rubber powder (pore volume 1.3 ml/g, specific surface 350 m) from Changling catalyst division ²A few pores with a diameter of 18.8 nm. 69% on a dry basis, with a pseudoboehmite content of 65%, a gibbsite content of 4% by weight, the balance being amorphous alumina, DI value 14.8).

P1-2: dry glue powder (pore volume 1.2 ml/g, specific surface 260 m) produced by cigarette Tai Henghui chemical Co., Ltd ²Pergram, most probable pore diameter 14 nm. 71% on a dry basis, with a pseudo-boehmite content of 67%, a gibbsite content of 5% by weight, and the balance amorphous alumina, a DI value of 17.2).

Examples 1 to 6 illustrate the P1 modified product P2 and the process for preparing the carrier of the present invention.

Example 1: 5000 g of P1-1 is weighed, and then 7200 ml of aqueous solution containing 50 ml of nitric acid (product of Tianjin chemical reagent, Mitsui) is added, and a butterfly-shaped strip with the external diameter phi of 1.4mm is extruded on a double-screw extruder. Drying the wet strips at 120 ℃ for 4 hours to obtain dry strips, roasting the dry strips at 600 ℃ for 4 hours to obtain carriers, impregnating the carriers with a solution containing nickel nitrate and molybdenum oxide by adopting a saturated impregnation method to obtain wet strips containing active metals Ni and Mo, drying the wet strips at 120 ℃ for 4 hours to obtain dry strips, shaping and sieving the dry strips, grinding dry strip materials (generally called industrial dry strip waste materials) with the length of less than 2mm, sieving the dry strips, and screening the dry strips by 100-200 meshes to obtain a modified P2A of P1-1. The k value of P2A is shown in Table 1. NiO content 2 wt.% on P2A calculated as oxide, MoO ₃The content is 10% by weight.

Example 2: 1000 g of the dried strip containing the active metals Ni and Mo obtained in example 1 were weighed and calcined at 400 ℃ for 4 hours to obtain P1-1 modified product P2B. The k value of P2B is shown in Table 1.

Example 3: 200 g each of P2A obtained in example 1 and P2B obtained in example 2 were uniformly mixed to obtain P2C which is a modified product of P1-1. The k value of P2C is shown in Table 1.

Example 4: 1000 g of P1-2 is weighed, then 10 ml of aqueous solution 1440 ml containing nitric acid (product of Tianjin chemical reagent, three factories) is added, and a butterfly-shaped strip with the external diameter phi of 1.4mm is extruded on a double-screw extruder. Drying the wet strips at 120 ℃ for 4 hours, roasting the wet strips at 800 ℃ for 4 hours to obtain a carrier, impregnating the carrier with a solution containing cobalt nitrate and molybdenum oxide by adopting a saturated impregnation method to obtain wet strips containing active metals Co and Mo, drying the wet strips at 120 ℃ for 4 hours to obtain dry strips, shaping and sieving the dry strips, grinding and sieving dry strip materials (generally called industrial dry strip waste materials) with the length of less than 2mm, and sieving the dry strips by taking 100-200 meshes to obtain a modified P2D of P1-2. The k value of P2D is shown in Table 1. CoO content 3 wt.% on P2D calculated as oxide, MoO ₃The content was 15% by weight.

Example 5: 1000 g of the dried strip containing the active metals Co and Mo obtained in example 4 were weighed and calcined at 500 ℃ for 4 hours to obtain P1-2 modified product P2E. The k value of P2E is shown in Table 1.

Example 6: 5000 g of P1-1 is weighed, and then 7200 ml of aqueous solution containing 50 ml of nitric acid (product of Tianjin chemical reagent, Mitsui) is added, and a butterfly-shaped strip with the external diameter phi of 1.4mm is extruded on a double-screw extruder. Drying the wet strips at 120 ℃ for 4 hours to obtain dry strips, roasting the dry strips at 600 ℃ for 4 hours to obtain carriers, impregnating the carriers with a solution containing nickel nitrate and ammonium vanadate by adopting a saturated impregnation method to obtain wet strips containing active metals Ni and V, drying the wet strips at 120 ℃ for 4 hours to obtain dry strips, shaping and sieving the dry strips, grinding dry strip materials (generally called industrial dry strip waste materials) with the length of less than 2mm, sieving the dry strips, and screening the dry strip materials with the size of 100-200 meshes to obtain a modified P2F of P1-1. The kappa values of P2F are shown in Table 1. NiO content 2 wt.% in P2F calculated as oxide, V ₂O ₅The content is 10% by weight.

TABLE 1

Examples	Raw materials	κ
			1	P2A	0.7
2	P2B	0.5
			3	P2C	0.6
4	P2D	0.4
			5	P2E	0.3
6	P2F	0.7

Examples 7-14 illustrate the preparation of bimodal porous alumina supports for the preparation of the protected catalysts of the present invention. Comparative examples 1-3 illustrate the preparation of conventional protected catalyst supports.

Example 7: 800 g of P1-1 was weighed, mixed with 200 g of the raw material P2A prepared in example 1, and then added with 1440 ml of aqueous solution containing 10 ml of nitric acid (product of Tianjin chemical reagent Co., Ltd.), and then extruded on a twin-screw extruder into butterfly-shaped strips with the outer diameter of phi 3.4 mm. The wet strands were dried at 120 ℃ for 4 hours to give moldings, and the moldings were calcined at 600 ℃ for 3 hours to give a support Z1. The properties of vector Z1 are listed in Table 2.

Example 8: weighing 700 g of P1-1, uniformly mixing with 300 g of the raw material P2B prepared in the embodiment 2, adding 1440 ml of aqueous solution containing Tianjin chemical reagent III) and extruding into butterfly-shaped strips with the outer diameter phi of 3.4mm on a double-screw extruder. The wet strands were dried at 120 ℃ for 4 hours to give moldings, and the moldings were calcined at 600 ℃ for 3 hours to give a support Z2. The properties of vector Z2 are listed in Table 2.

Example 9: 900 g of P1-1 is weighed and evenly mixed with 100 g of the raw material P2C prepared in the embodiment 3, then 10 ml of aqueous solution 1440 ml containing Tianjin chemical reagent III) is added, and a butterfly-shaped strip with the external diameter phi of 3.4mm is extruded on a double-screw extruder. The wet strands were dried at 120 ℃ for 4 hours to give moldings, and the moldings were calcined at 750 ℃ for 3 hours to give a support Z3. The properties of vector Z3 are listed in Table 2.

Comparative example 1: weighing 1000 g of P1-1, adding a product of Tianjin chemical reagent III) nitrate into 10 ml of aqueous solution 1440 ml, and extruding into butterfly-shaped strips with the outer diameter phi of 3.4mm on a double-screw extruder. The wet strands were dried at 120 ℃ for 4 hours to give moldings, and the moldings were calcined at 600 ℃ for 3 hours to give a support DZ 1. The properties of vector DZ1 are listed in Table 2.

Example 10: 800 g of P1-2 was weighed, mixed with 200 g of the raw material P2D prepared in example 4, and then added with 1440 ml of aqueous solution containing 10 ml of nitric acid (product of Tianjin chemical reagent Co., Ltd.), and then extruded on a twin-screw extruder into butterfly-shaped strips with the outer diameter of phi 3.4 mm. The wet strands were dried at 120 ℃ for 4 hours to give moldings, and the moldings were calcined at 700 ℃ for 3 hours to give a support Z4. The properties of vector Z4 are listed in Table 2.

Example 11: 900 g of P1-1 is weighed and evenly mixed with 100 g of the raw material P2E prepared in the embodiment 5, then 10 ml of aqueous solution 1440 ml containing Tianjin chemical reagent III) is added, and a butterfly-shaped strip with the external diameter phi of 3.4mm is extruded on a double-screw extruder. The wet strands were dried at 120 ℃ for 4 hours to give moldings, and the moldings were baked at 800 ℃ for 3 hours to give a support Z5. The properties of vector Z5 are listed in Table 2.

Example 12: 850 g of P1-2 was weighed, mixed with 150 g of the raw material P2C prepared in example 3, added with 1440 ml of aqueous solution containing Tianjin chemical reagent III) and extruded into butterfly-shaped strips with the outer diameter phi of 3.4mm on a twin-screw extruder. The wet strands were dried at 120 ℃ for 4 hours to give moldings, and the moldings were calcined at 650 ℃ for 3 hours to give a support Z6. The properties of vector Z6 are listed in Table 2.

Comparative example 2: weighing 1000 g of P1-2, adding a product of Tianjin chemical reagent III) nitrate into 10 ml of aqueous solution 1440 ml, and extruding into butterfly-shaped strips with the outer diameter phi of 3.4mm on a double-screw extruder. The wet strands were dried at 120 ℃ for 4 hours to give moldings, and the moldings were calcined at 650 ℃ for 3 hours to give a support DZ 2. The properties of vector DZ2 are listed in Table 2.

Example 13: 900 g of P1-2 was weighed, mixed with 100 g of the raw material P2D prepared in example 4, added with 1440 ml of aqueous solution containing Tianjin chemical reagent III) and extruded into butterfly-shaped strips with the outer diameter phi of 3.4mm on a twin-screw extruder. The wet strands were dried at 120 ℃ for 4 hours to give moldings, and the moldings were calcined at 700 ℃ for 3 hours to give a support Z7. The properties of vector Z7 are listed in Table 2.

Example 14: 800 g of P1-1 was weighed, mixed with 200 g of the raw material P2F prepared in example 6, and then added with 1440 ml of aqueous solution containing 10 ml of nitric acid (product of Tianjin chemical reagent Co., Ltd.), and then extruded on a twin-screw extruder into butterfly-shaped strips with the outer diameter of 1.4 mm. The wet strands were dried at 120 ℃ for 4 hours to give moldings, and the moldings were calcined at 600 ℃ for 3 hours to give a support Z8. The properties of vector Z8 are listed in Table 2.

Comparative example 3: according to the method provided by the patent CN101890381A example 7, butterfly-shaped strips with the outer diameter of 3.4mm are extruded on a double-screw extruder. The wet strands were dried at 120 ℃ for 4 hours to give moldings, and the moldings were calcined at 700 ℃ for 3 hours to give a support DZ 3. The properties of vector DZ3 are listed in Table 2.

TABLE 2

Examples 15 to 22 are provided to illustrate the hydrogenation activity protecting catalyst and the preparation method thereof according to the present invention.

Wherein, the content of the hydrogenation active metal component in the catalyst is measured by an X-ray fluorescence spectrometer (all instruments are 3271 type X-ray fluorescence spectrometers of Japan science and electronics industries Co., Ltd., and the specific method is shown in petrochemical industry analysis method RIPP 133-90).

Example 15: 200 g of vector Z1 was taken and 220 ml of MoO-containing solution was added ₃22 g/L of NiO 5 g/L of ammonium heptamolybdate and nickel nitrate mixed solution is soaked for 1 hour, dried for 4 hours at the temperature of 120 ℃ and roasted for 3 hours at the temperature of 400 ℃, and the hydrogenation activity protection catalyst C1 is obtained, and the composition of C1 is shown in Table 3.

Example 16: 200 g of vector Z2 was taken and 220 ml of MoO-containing solution was added ₃10 g/L of NiO 2 g/L of ammonium heptamolybdate and nickel nitrate mixed solution is soaked for 1 hour, dried for 4 hours at the temperature of 120 ℃ and roasted for 3 hours at the temperature of 400 ℃, and the hydrogenation activity protection catalyst C2 is obtained, and the composition of C2 is shown in Table 3.

Example 17: 200 g of vector Z3 was taken and 220 ml of MoO-containing solution was added ₃34 g/L and CoO 8 g/L of a mixed solution of ammonium heptamolybdate and cobalt nitrate are immersed for 1 hour, dried for 4 hours at 120 ℃ and calcined for 3 hours at 400 ℃ to obtain the hydrogenation activity protection catalyst CZ3, and the composition of C3 is shown in Table 3.

Comparative example 4: 200 g of vector DZ1 was taken and 220 ml of MoO-containing solution was added ₃48 g/L of mixed solution of ammonium heptamolybdate and cobalt nitrate with 10 g/L of CoO is soaked for 1 hour, dried for 4 hours at the temperature of 120 ℃ and roasted for 2 hours at the temperature of 400 ℃ to obtain the hydrogenation activity protection catalyst DC1, and the composition of DC1 is shown in Table 3.

Comparative example 5: 200 g of DZ2 was taken and 220 ml of MoO was added ₃48 g/L of NiO 10 g/L of mixed solution of ammonium heptamolybdate and nickel nitrate is soaked for 1 hour, dried for 4 hours at the temperature of 120 ℃ and roasted for 2 hours at the temperature of 400 ℃ to obtain the hydrogenation activity protection catalystThe compositions of the agents DC2, DC2 are listed in Table 3.

Comparative example 6: 200 g of vector DZ3 was taken and 500 ml of MoO-containing solution was added ₃38 g/L of NiO 10 g/L of ammonium heptamolybdate and nickel nitrate mixed solution is soaked for 1 hour, dried for 4 hours at the temperature of 120 ℃ and roasted for 3 hours at the temperature of 400 ℃ to obtain the hydrogenation activity protection catalyst DC3, and the composition of DC3 is shown in Table 3.

Example 18;

200 g of vector Z4 was taken and 220 ml of MoO-containing solution was added ₃1 g/L of NiO 2 g/L of ammonium heptamolybdate and nickel nitrate mixed solution is soaked for 1 hour, dried for 4 hours at the temperature of 120 ℃, and roasted for 3 hours at the temperature of 400 ℃, so that the hydrogenation activity protection catalyst C4 is obtained, and the composition of C4 is shown in Table 3.

Example 19:

200 g of Z5 was taken and 220 ml of MoO was added ₃9 g/L of NiO 4 g/L of ammonium heptamolybdate and nickel nitrate mixed solution is soaked for 1 hour, dried for 4 hours at 120 ℃ and roasted for 3 hours at 400 ℃ to obtain the hydrogenation activity protection catalyst C5, and the composition of C5 is shown in Table 3.

Example 20:

200 g of Z6 was taken and 220 ml of WO were added ₃9 g/L, CoO 6 g/L mixed solution of ammonium tungstate and cobalt nitrate, 1 hour, 120 ℃ oven drying for 4 hours, 400 ℃ baking for 3 hours, get hydrogenation activity protection catalyst C6, C6 composition is listed in Table 3.

Example 21:

200 g of Z7 was taken and 220 ml of MoO was added ₃8 g/l, V ₂O ₅12 g/l of a mixed solution of ammonium heptamolybdate and ammonium vanadate is soaked for 1 hour, dried at 120 ℃ for 4 hours and calcined at 400 ℃ for 3 hours to obtain a hydrogenation activity protection catalyst C7, and the composition of C7 is shown in Table 3.

Example 22:

200 g of Z8 was taken and 220 ml of MoO was added ₃8 g/L of NiO 6 g/L of ammonium heptamolybdate and nickel nitrate mixed solution is soaked for 1 hour, dried for 4 hours at the temperature of 120 ℃ and roasted for 3 hours at the temperature of 400 ℃, and the hydrogenation activity protection catalyst C8 is obtained, and the composition of C8 is shown in Table 3.

TABLE 3

Examples 23 to 30

Examples 23-30 illustrate the demetallization rate of the hydroprocessing catalyst provided by the present invention.

The protective agent was evaluated on a 100 ml small fixed bed reactor using kowitte slag as the raw material.

The catalyst C1-C8 was crushed into particles of 2-3 mm in diameter, the catalyst loading was 100 ml. The reaction conditions are as follows: the reaction temperature is 380 ℃, the hydrogen partial pressure is 14 MPa, and the liquid hourly space velocity is 0.7 h ^-1The hydrogen-oil volume ratio was 1000, and a sample was taken after 200 hours of reaction.

The specific calculation method of the demetallization rate and the desulfurization rate is as follows:

the properties of the stock oils are shown in Table 4, and the evaluation results are shown in Table 5.

Comparative examples 7 to 9

The demetallization rate and desulfurization rate of catalysts DC1, DC2 and DC3 were evaluated in the same manner as in examples, and the results are shown in Table 5.

TABLE 4

Raw oil name	Cowitte slag
		Density (20 ℃), kg/m ³	0.998
Average molecular weight	804
		Carbon residue,% (m)	15.9
Four Components,% (m)
		Saturation fraction	20
Aromatic component	49.3
		Glue	23
Asphaltenes	7.7
		S，m％	5.0
N，m％	0.21
		Ni，ppm	26.5
V，ppm	80

TABLE 5

The results given in table 5 are those obtained after the reaction was evaluated for 200 hours, and a comparison shows that the hydrodemetallization activity of the hydrogenation protection catalyst provided by the present invention is significantly higher than that of the reference catalyst, compared to the reference catalyst.

Claims

1. A hydrogenation activity protection catalyst comprises a carrier and a hydrogenation activity metal component, wherein the carrier contains alumina and hydrogenation metal elements, the hydrogenation metal elements are selected from one or more of VIB group, VIII group and VB group, and the content of the hydrogenation metal elements is not more than 12 wt% based on the carrier and calculated by oxides.

2. The hydrogenation activity protecting catalyst according to claim 1, wherein the hydrogenation metallic elements comprise at least one VIB group metallic element, at least one VIII group metallic element and optionally a VB group metallic element, and the content of the VIB group metallic element is not more than 5 wt%, the content of the VIII group metallic element is not more than 2 wt% and the content of the VB group metallic element is 0-6 wt% calculated on oxide basis and based on the carrier.

3. The hydroactivity protection catalyst of claim 2, wherein the group vib metal element is molybdenum and/or tungsten, the group viii metal element is cobalt and/or nickel, and the group VB metal element is vanadium and/or niobium; the VIB group metal element in the carrier is 0.1-5 wt%, preferably 1-5 wt%, and more preferably 1-4.5 wt% calculated by oxide and based on the carrier; the content of the group VIII metal element is 0.1 to 2% by weight, preferably 0.2 to 1.5% by weight, and more preferably 0.3 to 1.5% by weight; the content of the group VB metal element is 0 to 5% by weight, preferably 0 to 4% by weight.

4. The hydrogenation activity protecting catalyst according to claim 1 or 3, wherein the carrier exhibits a bimodal pore distribution at a diameter of 5-20nm and a diameter of 100-500nm, the pore volume of the pores having a diameter of 5-20nm accounts for 55-80% of the total pore volume, and the pore volume of the pores having a diameter of 100-500nm accounts for 10-35% of the total pore volume, as characterized by mercury intrusion method; preferably, the pore volume of pores with a diameter of 5-20nm accounts for 60-75% of the total pore volume, and the pore volume of pores with a diameter of 100-500nm accounts for 15-30% of the total pore volume.

5. A hydrogenation activity protecting catalyst according to claim 1 or 3, wherein the carrier has a pore volume of 0.95 to 1.6 ml/g and a specific surface area of 50 to 400 m ²Per gram; preferably, the carrier has a pore volume of 0.95 to 1.55 ml/g and a specific surface area of 80 to 350 m ²Per gram.

6. A hydrogenation activity protecting catalyst according to any one of claims 1 to 5, wherein the alumina is selected from bimodal pore aluminas having single or mixed crystalline phases of γ -, η -, θ -and δ -.

7. A hydrogenation activity protecting catalyst according to claim 1, wherein the hydrogenation activity metal component is selected from at least one group vib metal component and at least one group viii metal component and optionally a group VB metal component, the group vib metal component being present in an amount of not more than 6 wt%, the group viii metal component being present in an amount of not more than 2 wt% and the group VB metal component being present in an amount of 0 to 6 wt%, calculated as oxides and based on the catalyst; preferably, the metal component of the VIB group is selected from molybdenum and/or tungsten, the metal component of the VIII group is selected from cobalt and/or nickel, and the content of the metal component of the VIB group is 1.5-5.5 wt%, the content of the metal component of the VIII group is 0.2-2 wt% and the content of the metal component of the VB group is 0-5 wt% calculated on oxide and based on the catalyst.

8. A preparation method of a hydrogenation activity protection catalyst comprises the steps of preparing a carrier and loading a hydrogenation activity metal component on the carrier, wherein the preparation of the carrier comprises the steps of mixing hydrated alumina P1 containing pseudo-boehmite and a modified product P2 of P1, and then forming, drying and roasting; the weight mixing ratio of the P1 to the P2 is 20-95: 5-80, wherein the P2 contains hydrogenation metal elements, the hydrogenation metal elements are selected from one or more of VIB group, VIII group and VB group, and the dosage of the P2 ensures that the content of the hydrogenation metal elements in the final carrier calculated by oxide is not more than 12 percent by weight; the drying conditions include: the temperature is 40-350 ℃, the time is 1-24 hours, and the roasting conditions comprise: the temperature is more than 300 to less than or equal to 900 ℃, and the time is 1 to 8 hours.

9. The process of claim 8 wherein the hydrogenation metal comprises at least one group VIB metal element, at least one group VIII metal element, and optionally a group VB metal element, and P2 is used in an amount such that the final support contains no more than 5 wt.% of the group VIB metal element, no more than 2 wt.% of the group VIII metal element, and 0-6 wt.% of the group VB metal element, on an oxide basis.

10. The method according to claim 8 or 9, wherein the group vib metal element is molybdenum and/or tungsten, the group viii metal element is cobalt and/or nickel, and the group VB metal element is vanadium and/or niobium; p2 is used in an amount such that the amount of group VIB metal element in the final support, calculated as oxide, is from 0.1 to 5% by weight, preferably from 1 to 5% by weight, more preferably from 1 to 4.5% by weight; the content of the group VIII metal element is 0.1 to 2% by weight, preferably 0.2 to 1.5% by weight, and more preferably 0.3 to 1.5% by weight; the content of the group VB metal element is 0 to 5% by weight, preferably 0 to 4% by weight.

11. The method of claim 8 or 9, wherein P2 has a k value of 0 to 0.9 or less, and wherein the k is DI ₂/DI ₁，DI ₁Acid peptization index, DI, of pseudo-boehmite containing hydrated alumina P1 ₂Acid peptization index of a modification P2 of a hydrated alumina P1 containing pseudoboehmite; preferably, the P2 has a kappa value of 0 to 0.6 or less.

12. The method of claim 8 or 9, wherein the aluminum pseudoboehmite is containedThe pore volume of the hydrated alumina P1 of the stone is 0.9-1.4 ml/g, and the specific surface is 100-350 m ²Per gram, most probable pore diameter is 8-30 nm; preferably, the hydrated alumina P1 containing the pseudo-boehmite has the pore volume of 0.95-1.3 ml/g and the specific surface of 120-300 m ²A few pores with a diameter of 10-25 nm.

13. The method of claim 8 or 9, wherein the P2 is 80-300 mesh particulate matter; preferably, the P2 is a 100-200 mesh particulate.

14. The method of claim 8 or 9, wherein P2 is a modification of P1, and the method of modifying P1 to P2 comprises the steps of: (a) forming, drying and roasting the pseudo-boehmite-containing hydrated alumina P1; (b) impregnating the carrier obtained in the step (a) with impregnation liquid containing hydrogenation metal elements, drying, roasting, grinding and screening all or part of the carrier to obtain a modified substance P2, wherein the content of the hydrogenation metal elements is not more than 13 wt% based on the modified substance P2; the drying conditions of step (a) include: the temperature is 40-350 ℃, the time is 1-24 hours, and the roasting conditions comprise: the temperature is 300-900 ℃ and the time is 1-10 hours; the drying conditions of step (b) include: the temperature is 100 ℃ and 250 ℃, the time is 1-10 hours, and the roasting conditions comprise: the temperature is 360-500 ℃ and the time is 1-10 hours.

15. The method as claimed in claim 14, wherein the P2 is 80-300 mesh particles in P1 modification, and the P2 is preferably 100-200 mesh particles in P1 modification.

16. The process as claimed in claim 8 or 9, wherein the process for supporting the hydrogenation-active metal component on the carrier is an impregnation process comprising preparing a solution containing a hydrogenation-active metal component compound and impregnating the carrier with the solution, followed by drying, calcining or not, the hydrogenation-active metal component being selected from at least one group vib metal component, at least one group viii metal component and optionally a group VB metal component, the concentration of the hydrogenation-active metal component containing compound in the solution and the amount of the solution being such that the content of the group vib metal component in the final catalyst is not more than 6 wt%, the content of the group viii metal component is not more than 2.5 wt% and the content of the group VB metal component is from 0 to 6 wt%, calculated as oxides and based on the catalyst;

the drying conditions after the loading of the hydrogenation active metal component include: the temperature is 100-140 ℃, the time is 1-6 hours, and the roasting conditions comprise: the temperature is 360-450 ℃, and the time is 2-6 hours;

preferably, the group VIB metal component is selected from molybdenum and/or tungsten, the group VIII metal component is selected from cobalt and/or nickel, the group VB metal component is selected from vanadium and/or niobium, calculated by oxide and based on the catalyst, the concentration of the compound containing the hydrogenation active metal component in the solution and the amount of the solution are such that the content of the group VIB metal component in the final catalyst is 1.5-5.5 wt%, the content of the group VIII metal component is 0.2-2 wt% and the content of the group VB metal component is 0-5 wt%.

17. Use of a hydrogenation activity protecting catalyst as claimed in any one of claims 1 to 7 in the hydroprocessing of heavy oils.