CN107442126B - Preparation method of hydrotreating catalyst - Google Patents

Preparation method of hydrotreating catalyst Download PDF

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CN107442126B
CN107442126B CN201610365739.1A CN201610365739A CN107442126B CN 107442126 B CN107442126 B CN 107442126B CN 201610365739 A CN201610365739 A CN 201610365739A CN 107442126 B CN107442126 B CN 107442126B
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carrier
alumina
soluble
heat treatment
temperature
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CN107442126A (en
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杨占林
彭绍忠
唐兆吉
姜虹
王继锋
温德荣
孙立刚
王平
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/635—0.5-1.0 ml/g
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/1044—Heavy gasoline or naphtha having a boiling range of about 100 - 180 °C
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/70—Catalyst aspects

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The invention discloses a preparation method of a hydrotreating catalyst, which comprises the steps of preparing a carbon-containing modified alumina-based carrier, loading a hydrogenation active metal component by adopting an impregnation method, and drying to obtain the hydrotreating catalyst, wherein the preparation method of the carbon-containing modified alumina-based carrier comprises the following steps: and sequentially or simultaneously introducing water-soluble silicone oil, a soluble auxiliary agent and a carbon precursor into the alumina-based carrier, and performing heat treatment to obtain the carbon-containing modified alumina-based carrier. The method can adjust the distribution of the acid center and the hydrogenation active center, so that the acid center and the hydrogenation active center are mutually coordinated, and the comprehensive performance of the hydrotreating catalyst is improved.

Description

Preparation method of hydrotreating catalyst
Technical Field
The invention relates to a preparation method of a hydrotreating catalyst, in particular to a preparation method of a hydrotreating catalyst suitable for heavy distillate oil.
Background
The supported catalyst is mostly prepared by an impregnation method, such as various hydrogenation catalysts. Alumina is often used as a support material for such catalysts. But pure Al2O3The interaction force between the active metal on the surface and the carrier is large, inactive species (such as nickel aluminate spinel) are easy to form, and the active metal is not easy to be completely vulcanized to form a II-type active phase with high hydrogenation activity. Meanwhile, the acidity of the surface of the catalyst has a great influence on the activity of the hydrogenation catalyst, and the removal of heteroatoms in the raw material requires that the catalyst has hydrogenolysis activity, which occurs on the acidic center of the catalyst, so how to weaken the strong interaction between the metal and the carrier and how to make the catalyst have proper acidity becomes the key for preparing the high-activity hydrogenation catalyst. The properties of the catalyst are determined by the carrier, so the development of a proper carrier is a key factor for the development of the catalystOne of the elements.
At present, many methods for modifying the alumina carrier are available, wherein an auxiliary agent such as silicon, phosphorus, fluorine, boron, zirconium, titanium, magnesium, gallium, vanadium, manganese, copper, zinc, etc. is introduced to improve the properties of the alumina carrier, but the properties of the alumina carrier are different or even greatly different due to different amounts, types and modes of the introduced auxiliary agent.
CN00110018.1 discloses a hydrogenation catalyst and its preparation method, the catalyst uses VIB group and VIII group metals as hydrogenation active components, the adjuvant is fluorine, at the same time, one or the mixture of boron, silicon, phosphorus, magnesium, titanium, zirconium and gallium is loaded as adjuvant, the technical key is that it is prepared by coprecipitation method.
CN200910236166.2 discloses a preparation method of a petroleum wax hydrofining catalyst. The method comprises the following steps: weighing pseudo-boehmite, adding 6-17% of silicon-containing compound and 2-20% of phosphorus-containing organic compound solution, extruding the mixture on a strip extruder for molding, drying and roasting to obtain gamma-Al containing silicon and phosphorus2O3A carrier; the silicon-containing compound being SiO2Silica sol or nanosilica at a concentration of 30% by weight.
The use of special carriers such as activated carbon can weaken the strong interaction of the metal with the carrier, but the activated carbon carrier has disadvantages of poor mechanical strength and high cost. The carrier obtained by coating carbon on the surface of alumina has high mechanical strength and can be used as a substitute of an active carbon carrier. In the prior art, the following method is often adopted to prepare the carbon-coated carrier: one method is to adopt a stainless steel reactor, rapidly heat to 873K within 3 minutes, take nitrogen as carrier gas and anthracene as carbon precursor in gamma-Al2O3Carbon is coated on the substrate; one method is to adopt the semiconductor carbon film material technology to mix gamma-Al2O3The refractory oxides are placed in a vertical quartz tube reactor, and organic substances such as hydrocarbons such as benzene and ethylene are introduced from the upper part of the reactor. The preparation method has complex process and high cost.
CN200410000952.X proposes a preparation method of a carbon-containing distillate oil hydrofining catalyst, wherein carbon in the catalyst is obtained by adding carbon black powder or a carbon precursor during carrier molding, and the weight mixing ratio of carbon to alumina is 1: 99-20: 80. because of the addition of these carbon precursors, the calcination temperature of the carrier in an oxygen-containing atmosphere cannot be too high, otherwise carbon is lost by oxidation, so that this method is not feasible for some catalysts in which the carrier needs to be treated at high temperature, and the addition of too much carbon black powder affects the strength of the catalyst, which is not suitable for large-scale application.
In the prior art, the auxiliary agents such as active metal, Si and the like enter a bulk phase in the coprecipitation process by a coprecipitation method or are added during forming, and a plurality of substances are precipitated simultaneously, so that the same precipitation condition cannot be the optimal precipitation condition of the plurality of substances simultaneously; in the latter, addition of Si and other additives during kneading and molding is not favorable for uniform dispersion of the additives. The method adopts a molded alumina carrier and coats carbon on the surface of the alumina carrier, which is a better method for solving the problem that the active carbon is insufficient as the carrier, but the existing carbon coating method has complex preparation process and high cost and is difficult to realize large-scale industrialization, and the acidity of the carrier after carbon coating is reduced, which is not beneficial to improving the comprehensive performance of the catalyst. How to find a simple method for preparing the carbon-coated carrier and improve the performance of the catalyst becomes a difficult problem needing to be solved in the field.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method of a carbon-containing hydrotreating catalyst. The method can adjust the distribution of the acid center and the hydrogenation active center, so that the acid center and the hydrogenation active center are mutually coordinated, and the comprehensive performance of the hydrotreating catalyst is improved.
The preparation method of the hydrotreating catalyst comprises the steps of preparing a carbon-containing modified alumina-based carrier, loading a hydrogenation active metal component by adopting an impregnation method, and drying to obtain the hydrotreating catalyst, wherein the preparation method of the carbon-containing modified alumina-based carrier comprises the following steps: and sequentially or simultaneously introducing water-soluble silicone oil, a soluble auxiliary agent and a carbon precursor into the alumina-based carrier, and performing heat treatment to obtain the carbon-containing modified alumina-based carrier.
In the method, the silicon content introduced into the carrier by the water-soluble silicone oil accounts for 0.1-5.0 percent of the weight of the modified alumina-based carrier by the silicon dioxide, preferably 0.2-3.0 percent, and more preferably 0.2-1.5 percent.
In the method, the content of the soluble auxiliary agent introduced into the carrier accounts for 0.1-10.0% of the weight of the modified alumina-based carrier in terms of oxide, preferably 0.3-5.0%, and more preferably 0.5-2.0%.
In the method, the molar ratio of the introduced water-soluble silicone oil to the introduced soluble auxiliary agent in terms of silicon oxide to oxide is 0.05-80.0, preferably 0.1-15.0, and more preferably 0.3-5.0.
The water-soluble silicone oil of the method of the invention is water-soluble silicone oil, and the preferable properties are as follows: the viscosity at 25 ℃ is 200 to 7000 mPas, preferably 500 to 5000 mPas, and the cloud point is 30 to 100 ℃, preferably 40 to 65 ℃. The water-soluble silicone oil is generally obtained by adopting a method of modifying silicone oil by groups, such as polyether modified silicone oil.
In the method of the invention, the soluble auxiliary agent is one or a combination of several of compounds containing aluminum, zirconium, boron, magnesium and the like. The soluble aluminum-containing compound is one or a combination of aluminum nitrate, aluminum chloride, aluminum sulfate and the like. The soluble zirconium-containing compound is one or a combination of more of zirconium nitrate, zirconium tetrachloride, zirconium oxychloride and the like. The soluble boron-containing compound is one or a combination of more of boric acid, ammonium pentaborate, ammonium tetraborate and the like. The soluble magnesium-containing compound is one or more of magnesium acetate, magnesium chloride, magnesium nitrate, magnesium sulfate, etc.
In the preparation process of the carbon-containing catalyst carrier, the carbon content in the carrier is 0.5-15% of the weight of the carrier. The carbon precursor is an organic additive, the boiling point of the organic additive is higher than 100 ℃, and the carbon precursor is preferably one or more of oxygen-containing organic compounds, wherein the oxygen-containing organic compounds are organic matters containing at least one carbon atom and one oxygen atom. The organic compound preferably contains at least two oxygen atoms and two carbon atoms, and the number of carbon atoms of the oxygen-containing organic compound is preferably 2 to 20. The oxygen-containing moiety can be a carboxyl, carbonyl, hydroxyl moiety, or a combination thereof. These substances may be acids, such as acetic acid, oxalic acid, malonic acid, tartaric acid, malic acid, citric acid, etc., alcohols, such as ethylene glycol, propylene glycol, butylene glycol, glycerol, etc., ethers, such as diethylene glycol, dipropylene glycol, triethylene glycol, tributylene glycol, tetraethylene glycol, polyethylene glycol, etc., sugars, such as glucose, fructose, lactose, maltose, sucrose, etc., or ketones, phenols, aldehydes and lipids. In the method of the present invention, under appropriate conditions and under the action of the catalyst active metal, the above-mentioned carbon precursor undergoes complex reactions such as dehydrogenation, decomposition, carbonization, etc., to produce non-volatile carbon or coke-like products which are attached to the surfaces of the catalyst channels, and the starting material used is called carbon precursor. Under the condition that the carbon precursor is likely to be lost, the impregnation loading capacity of the carbon precursor is generally more than the theoretical requirement, and the excess is generally about 10-100%.
The alumina-based carrier provided by the invention is prepared by taking alumina as a main component, and optionally containing no auxiliary component or auxiliary component, wherein the auxiliary component can be one or more of fluorine, silicon, phosphorus, titanium, zirconium, boron and the like, and the content of the auxiliary component in the alumina-based carrier is below 30wt%, preferably below 20wt%, and further preferably below 15 wt%. The alumina-based carrier used in the invention is obtained by high-temperature roasting of aluminum hydroxide (such as pseudo-boehmite), and the conditions of the high-temperature roasting are as follows: roasting at 450-1000 ℃ for 1.0-20.0 h, preferably 3.0-8.0 h. The alumina-based carrier can be prepared by a conventional method, and can be prepared into a molded carrier according to the requirements of practical application, namely the alumina-based carrier is obtained by molding aluminum hydroxide and then roasting at high temperature. The carrier can be made into spherical shape, strip shape (such as clover, clover or cylindrical strip) and other suitable shapes according to the requirement, and common forming aids such as extrusion aid, peptizing acid, adhesive and the like can be added in the forming process. The properties of the alumina-based support are as follows: the specific surface area is 120-420 m2Preferably 220 to 320 m/g2(ii)/g; the pore volume is 0.4-1.3 mL/g, preferably 0.6-1.0 mL/g; the pore volume occupied by pores having a pore diameter of less than 4nm is 20% or less, preferably 10% or less, and more preferably 5% or less of the total pore volume.
In the method, the water-soluble silicone oil, the soluble auxiliary agent and the carbon precursor are introduced onto the carrier in sequence or simultaneously, namely the water-soluble silicone oil is introduced onto the carrier, then the soluble auxiliary agent is introduced onto the carrier, and finally the carbon precursor is introduced onto the carrier; or simultaneously introducing the water-soluble silicone oil and the soluble auxiliary agent onto the carrier, and then introducing the carbon precursor onto the carrier; or simultaneously introducing the water-soluble silicone oil, the soluble auxiliary agent and the carbon precursor onto the carrier. The introduction mode adopts an impregnation method, and the impregnation method can be equal-volume impregnation or excessive impregnation; the impregnation may be carried out a plurality of times or may be carried out once. For efficiency, it is preferred to use one equivalent volume of impregnation.
In the method, the heat treatment method before the introduction of the carbon precursor adopts two-stage heat treatment, wherein the temperature of the first-stage low-temperature heat treatment is 60-150 ℃, preferably 90-120 ℃, the treatment time is 0.5-20.0 h, preferably 1.0-6.0 h, the temperature of the second-stage high-temperature heat treatment is 180-400 ℃, preferably 200-350 ℃, and the treatment time is 0.5-20.0 h, preferably 1.0-6.0 h. The heat treatment may be performed in an oxygen-containing atmosphere, the oxygen concentration is not particularly limited, such as an air atmosphere, and the like, and may be performed in an inert atmosphere, such as a nitrogen atmosphere, and the like.
In the method, after the carbon precursor is introduced, one-stage high-temperature heat treatment can be adopted, and the heat treatment method can be heating treatment under the condition of oxygen-containing atmosphere (such as air), wherein the heat treatment temperature is 150-450 ℃, and the heat treatment time is 0.5-6 hours; the high-temperature heat treatment can also be carried out in an inert gas atmosphere, wherein the inert gas is one or more selected from nitrogen, argon, helium, carbon dioxide and water vapor, the heat treatment temperature is 150-500 ℃, and the heat treatment time is 0.5-8 hours. Two-stage heat treatment can also be preferably adopted, and the first-stage low-temperature heat treatment process is added, wherein the heat treatment temperature is 50-140 ℃, and the time is 0.5-6 hours. The temperature rise process of the heat treatment adopts rapid temperature rise, namely the temperature rise time reaching the heat treatment temperature is not more than 30 minutes, and preferably the temperature rise time reaching the heat treatment temperature is not more than 15 minutes. Researches show that the rapid heating is beneficial to decomposition and carbonization of organic matters, more importantly, because the heat treatment temperature is generally higher than the boiling point temperature of the organic matters, if the heating time is longer, the volatilization loss of the organic matters is more, the rapid heating method is adopted, under the catalytic action of the auxiliary agent components on the carrier, the organic matters undergo catalytic dehydrogenation reaction before desorption, the dehydrogenation reaction products have stronger interaction with the catalyst carrier and can not be separated from the carrier, the decomposition and carbonization reaction is further facilitated, the volatilization loss of the organic matters is reduced, and the utilization rate of the organic matters is improved.
The hydrogenation active metal component in the method of the present invention is an active metal component commonly used for hydrotreating catalysts, and is generally one or more of group VIB metals and group VIII metals, wherein the group VIB metals are preferably W and/or Mo, and the group VIII metals are preferably Co and/or Ni.
The hydrotreating catalyst prepared by the method disclosed by the invention has the weight of the catalyst as a reference, and the content of the modified alumina-based carrier is 55.0 wt% -94.5 wt%, preferably 58.0 wt% -90.0 wt%, the content of the VIB group metal oxide is 5.0 wt% -30.0 wt%, preferably 8.0 wt% -30.0 wt%, and the content of the VIII group metal oxide is 0.5 wt% -15.0 wt%, preferably 2.0 wt% -12.0 wt%.
In the preparation method of the hydrotreating catalyst, the hydrogenation active metal component is loaded on the carrier by an impregnation method, and can be impregnated in an equal volume, can be impregnated in an excess amount, can be impregnated in steps, can be impregnated together, and is preferably impregnated in an equal volume. Impregnation methods are well known to those skilled in the art. The carrier is impregnated with the hydrogenation active metal component solution and then dried to prepare the final catalyst. Methods for preparing catalysts are well known to the skilled worker. The impregnation solution is prepared by using compounds containing a metal of group VIB or group VIII, the concentration of the solution being adjustable by the amount of each compound used, so as to prepare the catalyst with the specified content of active components, the preparation method of the solution being well known to those skilled in the art. The drying conditions are conventional, for example, the drying temperature is 60 ℃ to 200 ℃, preferably 90 ℃ to 160 ℃, and the drying time is 0.5h to 20h, preferably 1h to 6 h.
The application of the hydrotreating catalyst has the following reaction conditions: the total reaction pressure is 3.0-18.0 MPa, and the liquid hourly space velocity is 0.2h-1~4.0h-1The volume ratio of hydrogen to oil is 200: 1-2000: 1, and the reaction temperature is 230-430 ℃.
In the preparation process of the catalyst, on one hand, the carbon precursor is decomposed under the promotion action of the auxiliary agent component, so that harsh treatment conditions are avoided, the surface of the catalyst carrier is covered, the surface property of the catalyst carrier is adjusted, and the purpose of improving the service performance of the catalyst is achieved; on the other hand, a small amount of specific water-soluble silicone oil is used for impregnating the alumina-based carrier, the water-soluble silicone oil is loaded on a specific position on the surface of the alumina-based carrier under the action of hydrophilic and hydrophobic groups of the water-soluble silicone oil, and auxiliary components which are simultaneously or later impregnated are uniformly dispersed around silicon-oxygen groups, and through proper heat treatment, the loaded Si and the auxiliary components can better coordinate to form more uniformly distributed silicon hydroxyl groups on the specific position on the surface of the carrier, so that more acidic centers with proper acidity are formed on the surface of the carbon-coated carrier, and the subsequent regulation of the distribution of hydrogenation active centers formed by the loaded active metal and the coordination of the hydrogenation active centers and the acidic centers on the surface of the carrier are facilitated, thereby improving the service performance of the catalyst.
The hydrotreating catalyst prepared by the method is particularly suitable for hydrogenation impurity removal (such as sulfur, nitrogen and the like) catalysts of heavy distillate oil, and particularly has greatly improved hydrodenitrogenation activity.
Detailed Description
In the present invention, cloud point is a temperature at which an aqueous solution of a water-soluble silicone oil having a mass concentration of 1% is heated to a turbidity, and then heating is stopped, and the aqueous solution is observed to turn clear from the turbidity with stirring.
According to the preparation method of the carbon-containing modified alumina-based carrier provided by the invention, the following steps can be adopted:
1. preparing a soluble auxiliary agent into a solution A, wherein the content of the auxiliary agent is 0.1g/100 mL-32 g/100mL calculated by an oxide;
2. preparing water-soluble silicone oil into a solution B, wherein the concentration of the water-soluble silicone oil is 0.1g/100 mL-20 g/100mL calculated by silicon oxide;
3. mixing a soluble auxiliary agent and water-soluble silicone oil to prepare a solution C, wherein the content of the auxiliary agent is 0.1g/100 mL-16 g/100mL calculated by oxide, and the concentration of the water-soluble silicone oil is 0.1g/100 mL-10 g/100mL calculated by silicon oxide;
4. introducing a water-soluble silicone oil and an auxiliary agent onto the alumina-based support in at least one of the following ways:
I. impregnating the alumina-based carrier with the solution C, preferably after the maintenance, and then carrying out two-stage heat treatment to obtain a modified alumina-based carrier;
II. Impregnating the alumina-based carrier with the solution B, preferably after the maintenance, carrying out low-temperature heat treatment, then impregnating the solution A, preferably after the maintenance, and carrying out two-stage heat treatment to obtain a modified alumina-based carrier;
5. introducing a carbon precursor onto the alumina-based support in at least one of the following ways:
I. introducing a carbon precursor solution on the basis of I or II in step 4, and carrying out heat treatment to obtain a carbon-containing modified alumina-based carrier;
II. Soaking the alumina-based carrier by using the solution B, preferably performing low-temperature heat treatment after the alumina-based carrier is cultured, and then soaking the mixed solution of the solution A and the carbon precursor, and performing heat treatment to obtain a carbon-containing modified alumina-based carrier;
and III, impregnating the alumina-based carrier with a mixed solution of the solution C and the carbon precursor, preferably after the culture and the heat treatment to obtain the carbon-containing modified alumina-based carrier.
In the method of the present invention, the heat treatment may be carried out in an oxygen-containing atmosphere, and the oxygen concentration is not particularly limited, such as an air atmosphere, and the like, and may be carried out in an inert atmosphere, such as a nitrogen atmosphere, and the like.
The method of the invention does not specifically limit the curing time after the solution is dipped, the curing time is based on the condition that the uniform adsorption of the water-soluble silicone oil and the soluble auxiliary agent can be ensured, and a person skilled in the art can judge according to the viscosity condition of the solution and the adsorption condition of the solution to determine the curing time.
The technical solutions of the present invention are further described below by way of examples, but the present invention should not be construed as being limited to these examples. In the invention, the wt% is mass fraction, and is air atmosphere without special indication.
In the examples, the water-soluble silicone oil A used was SiO produced by Qingdao Xingheng New Silicone Material Co215wt%, viscosity (25 ℃) of 1500-5000 mPa.s and cloud point of 47 ℃; the water-soluble silicone oil B is produced by Laiyang Shuming chemical Co., Ltd, SiO2The content is 9wt%, the viscosity (25 ℃) is 500-1500 mPa.s, and the cloud point is 45-55 ℃; water-soluble silicone oil C was produced by Silybum Saint Pamp organosilicon science and technology Co., Ltd, SiO2The content is 30wt%, the viscosity (25 ℃) is 600-5000 mPa.s, and the cloud point is 42-46 ℃.
The pore structure of the aluminum hydroxide dry glue powder used in the examples and comparative examples is shown in table 1:
TABLE 1 pore Structure of aluminum hydroxide Dry glue powder used in examples and comparative examples
Figure 167004DEST_PATH_IMAGE001
Example 1
3800g of macroporous aluminum hydroxide dry glue powder and 200g of SB powder are taken, and 160g of citric acid and sesbania powder are added respectively and mixed evenly. Then 2900g of dilute aqueous nitric acid solution was added uniformly, wherein the nitric acid concentration was 2.9 wt%. Kneading the materials for 15min, grinding for 20min, and extruding with 1.7 mm-diameter clover orifice plate. Drying at 120 deg.C for 4 hr, and calcining at 500 deg.C for 4 hr. The calcined support was designated as Z.
The physicochemical properties of the alumina support Z are shown in table 2:
TABLE 2 physicochemical Properties of the alumina Carrier Z
Figure 770636DEST_PATH_IMAGE002
Example 2
Weighing 14.3g of zirconium nitrate, adding a proper amount of deionized water to dissolve the zirconium nitrate to ensure that the volume is 105mL, and preparing a solution A1; weighing 12.6g of water-soluble silicone oil A, adding a proper amount of deionized water to dissolve the water-soluble silicone oil A to make the volume of the water-soluble silicone oil A105 mL, and preparing a solution B1; under stirring, 35mL of the B1 solution was slowly poured into 35mL of the A1 solution, and an appropriate amount of deionized water was added to make the final volume 78mL, to prepare a C1 solution.
And uniformly spraying 100g of alumina carrier Z with the solution C1, preserving for 10 hours, and then carrying out heat treatment at 110 ℃ for 2 hours and 240 ℃ for 3 hours to obtain the modified carrier S1.
Taking 100g of alumina carrier Z, diluting 35mL of solution B1 to 78mL with deionized water, uniformly spraying the solution B1 to the carrier Z, preserving the solution for 10 hours, carrying out heat treatment at 100 ℃ for 2 hours, then diluting 35mL of solution A1 to 76mL with deionized water, uniformly spraying the solution B1 to the carrier Z, preserving the solution for 3 hours, carrying out heat treatment at 110 ℃ for 2 hours, and carrying out heat treatment at 240 ℃ for 3 hours to obtain the modified carrier S2.
Preparing two parts of aqueous solution by using 26g of glycerol respectively, then impregnating carriers S1 and S2 in equal volumes respectively, standing for 2 hours, raising the temperature to 200 ℃ from room temperature in 10 minutes in an air atmosphere, and keeping the temperature for 2 hours to obtain carbon-containing carriers which are named as S1C and S2C respectively.
Impregnating S1C and S2C with impregnating solution containing Mo, Ni and P in equal volume respectively, and drying at 130 ℃ for 3h to obtain catalysts respectively marked as CAT1 and CAT 2.
Example 3
4.9g of zirconium oxychloride and 9.4g of water-soluble silicone oil B are weighed, and a proper amount of deionized water is added to dissolve the zirconium oxychloride and the water-soluble silicone oil B to ensure that the volume of the zirconium oxychloride and the water-soluble silicone oil B is 78mL, so that a solution C2 is prepared.
And uniformly spraying 78mL of solution C2 on 100g of alumina carrier Z, preserving for 10 hours, and then carrying out heat treatment at 110 ℃ for 2 hours and at 240 ℃ for 3 hours to obtain the modified carrier S3. Preparing an aqueous solution by using 18.0g of polyvinyl alcohol, soaking S3 in the aqueous solution in an equal volume, standing for 4 hours, heating from room temperature to 80 ℃ in 5 minutes under a nitrogen atmosphere, keeping the temperature for 2 hours, heating from 80 ℃ to 300 ℃ in 10 minutes, and keeping the temperature for 1.5 hours to obtain the carbon-containing carrier named as S3C.
Weighing 4.9g of zirconium oxychloride, 9.4g of water-soluble silicone oil B and 18.0g of polyvinyl alcohol, adding a proper amount of deionized water to dissolve the zirconium oxychloride, wherein the volume of the zirconium oxychloride is 78mL, soaking 100g of alumina carrier Z in the solution in an equal volume, maintaining the solution for 10 hours, heating the solution to 80 ℃ from room temperature in 5 minutes under the nitrogen atmosphere, keeping the temperature for 2 hours, heating the solution to 300 ℃ from 80 ℃ in 10 minutes, keeping the temperature for 1.5 hours, and naming the obtained carbon-containing carrier as S4C.
Impregnating S3C and S4C with impregnating solution containing Mo, Ni and P in equal volume respectively, and drying at 130 ℃ for 3h to obtain catalysts respectively marked as CAT3 and CAT 4.
Example 4
Weighing 1.7g of water-soluble silicone oil C, adding a proper amount of deionized water to dissolve the water-soluble silicone oil C to ensure that the volume is 78mL, uniformly spraying the water-soluble silicone oil C on 100g of alumina carrier Z, preserving the mixture for 10 hours, carrying out heat treatment at 100 ℃ for 2 hours, soaking a mixed solution prepared from 3.6g of zirconium nitrate, 8g of polyvinyl alcohol and 16g of glycerol in an equal volume, standing the mixture for 5 hours, heating the mixture to 80 ℃ from room temperature within 5 minutes in an air atmosphere, keeping the temperature for 2 hours, heating the mixture to 200 ℃ within 10 minutes, keeping the temperature for 1 hour, and naming the obtained carbon-containing carrier as S5C.
Weighing 1.7g of water-soluble silicone oil C, 3.6g of zirconium nitrate, 8g of polyvinyl alcohol and 16g of glycerol, adding a proper amount of deionized water to dissolve the water-soluble silicone oil C, ensuring the volume to be 78mL, then uniformly spraying the water-soluble silicone oil C on 100g of alumina carrier Z, preserving the health for 10 hours, carrying out heat treatment at 100 ℃ for 2 hours in an air atmosphere, heating the temperature to 80 ℃ from room temperature for 5 minutes, keeping the temperature for 2 hours, heating the temperature to 200 ℃ from 80 ℃ for 10 minutes, and keeping the temperature for 1 hour to obtain the carbon-containing carrier named as S6C.
Impregnating S5C and S6C with impregnating solution containing Mo, Ni and P in equal volume respectively, and drying at 130 ℃ for 3h to obtain catalysts respectively marked as CAT5 and CAT 6.
Comparative example 1
And (3) taking 190g of macroporous aluminum hydroxide dry glue powder and 10g of SB powder, adding 8g of citric acid and sesbania powder respectively, and uniformly mixing. Weighing 13.2g of water-soluble silicone oil B and 6.9g of zirconium oxychloride, then adding the water-soluble silicone oil B and the zirconium oxychloride into the nitric acid aqueous solution, and uniformly stirring to obtain 155g of acid solution, wherein the concentration of the nitric acid is 2.7 wt%. Kneading the materials for 15min, grinding for 20min, and extruding with 1.7 mm-diameter clover orifice plate. Drying at 120 deg.C for 4 hr, and calcining at 500 deg.C for 4 hr. The calcined support was designated DS 1.
The carbonaceous support prepared by replacing the support S3 in example 3 with the support DS1 was designated DS1C and the catalyst was designated DCAT 1.
Comparative example 2
4.2g of water-soluble silicone oil A is weighed, and an appropriate amount of deionized water is added to dissolve the water-soluble silicone oil A to ensure that the volume is 78mL, so that a solution B2 is prepared. And (3) uniformly spraying 100g of alumina carrier Z with the solution B2, preserving for 10 hours, and then carrying out heat treatment at 110 ℃ for 2 hours and at 240 ℃ for 3 hours to obtain the modified carrier DS 2.
The carbonaceous support prepared by replacing the support S2 in example 2 with the support DS2 was designated DS2C and the catalyst was designated DCAT 2.
Comparative example 3
4.6g of zirconium nitrate is weighed, and is dissolved by adding a proper amount of deionized water to ensure that the volume is 78mL, so as to prepare A2 solution. And (3) uniformly spraying 100g of alumina carrier Z with the solution A2 on the alumina carrier, preserving for 10 hours, and then carrying out heat treatment at 110 ℃ for 2 hours and at 240 ℃ for 3 hours to obtain the modified carrier DS 3.
The carbonaceous support prepared by replacing the support S2 in example 2 with the support DS3 was designated DS3C and the catalyst was designated DCAT 3.
Comparative example 4
Compared with the preparation method of the carrier S2 in the example 2, the comparative example introduces the zirconium salt firstly and then introduces the water-soluble silicone oil, and the specific process is as follows:
taking 100g of alumina carrier Z, diluting 35mL of A1 solution to 78mL by using deionized water, uniformly spraying the solution on the carrier, carrying out heat treatment at 100 ℃ for 2h after curing for 3h, then diluting 35mL of solution B1 to 76mL by using deionized water, uniformly spraying the solution on the carrier Z, carrying out heat treatment at 110 ℃ for 2h, and carrying out heat treatment at 240 ℃ for 3h to obtain the modified carrier DS 4.
The carbonaceous support prepared by replacing the support S2 in example 2 with the support DS4 was designated DS4C and the catalyst was designated DCAT 4.
Comparative example 5
Preparing an aqueous solution by using 26g of glycerol, soaking 100g of alumina carrier Z in the aqueous solution in the same volume, standing for 2 hours, raising the temperature to 200 ℃ from room temperature for 10 minutes in an air atmosphere, and keeping the temperature for 2 hours to obtain the carbon-containing carrier, wherein the record is DS 5C.
The catalyst obtained by impregnating DS5C with an impregnating solution containing Mo, Ni and P in equal volume and drying at 130 ℃ for 3h is respectively marked as DCAT 5.
Table 3 examples and comparative examples alumina carrier properties
Figure DEST_PATH_IMAGE003
TABLE 3
Figure 701683DEST_PATH_IMAGE004
The carbon content analysis method comprises the following steps: the X-ray diffraction result shows that the organic matter on the catalyst carrier has been carbonized, the high temperature combustion method is adopted to determine the carbon content of the sample, and the carbon is combusted in the high purity oxygen atmosphere to generate CO2，CO2And (4) conveying the gas into a chromatogram, and detecting and analyzing the gas by a thermal conductivity cell to calculate the carbon content of the sample.
TABLE 4 composition of the catalyst
Figure DEST_PATH_IMAGE005
TABLE 4
Figure 456013DEST_PATH_IMAGE006
Example 6
This example is an activity evaluation experiment of catalysts CAT 1-CAT 6 and comparative catalysts DCAT 1-DCAT 5.
The catalyst activity evaluation experiment was performed on a 100mL small scale hydrogenation unit, and the catalyst was presulfided prior to activity evaluation. The evaluation conditions of the catalyst are that the total reaction pressure is 10.0MPa, and the liquid hourly volume space velocity is 1.0h-1Hydrogen-oil volume ratio 800: 1, the reaction temperature is 380 ℃. Properties of the raw oil for the activity evaluation test are shown in Table 5, and the results of the activity evaluation are shown in Table 6.
TABLE 5 Properties of the feed oils
Figure DEST_PATH_IMAGE007
TABLE 6 evaluation results of catalyst Activity
Figure DEST_PATH_IMAGE009
TABLE 6 continuation
Catalyst and process for preparing same DCAT1 DCAT2 DCAT3 DCAT4 DCAT5
Relative denitrification activity,% 112 114 108 119 100
Relative desulfurization activity of% 109 113 107 117 100
As can be seen from Table 6, the hydrodesulfurization and denitrification activities, particularly the hydrodenitrogenation activities, were greatly improved with the hydrotreating catalyst of the present invention as compared with the comparative catalyst.

Claims (29)

1. A preparation method of a hydrotreating catalyst is characterized by comprising the following steps: the preparation method comprises the steps of preparing a carbon-containing modified alumina-based carrier, loading a hydrogenation active metal component by adopting an impregnation method, and drying to obtain a hydrotreating catalyst, wherein the preparation method of the carbon-containing modified alumina-based carrier comprises the following steps: introducing water-soluble silicone oil, a soluble auxiliary agent and a carbon precursor into the alumina-based carrier in sequence or simultaneously to prepare a carbon-containing modified alumina-based carrier;
wherein, the introduction mode of sequentially or simultaneously introducing the water-soluble silicone oil, the soluble auxiliary agent and the carbon precursor into the alumina-based carrier is to adopt an impregnation method;
wherein, the silicon content introduced into the carrier by the water-soluble silicone oil accounts for 0.2 to 1.5 percent of the weight of the modified alumina-based carrier by the weight of silicon dioxide; the content of the soluble auxiliary agent introduced into the carrier accounts for 0.1 to 10.0 percent of the weight of the modified alumina-based carrier in terms of oxide; in the preparation process of the carbon-containing catalyst carrier, the carbon content in the carrier is 0.5-15% of the weight of the carrier;
wherein the soluble auxiliary agent is one or a combination of more of aluminum-containing compounds, zirconium-containing compounds, boron-containing compounds and magnesium-containing compounds.
2. The method of claim 1, wherein: the content of the soluble auxiliary agent introduced into the carrier accounts for 0.3 to 5.0 percent of the weight of the modified alumina-based carrier in terms of oxide.
3. The method of claim 1, wherein: the content of the soluble auxiliary agent introduced into the carrier accounts for 0.5 to 2.0 percent of the weight of the modified alumina-based carrier in terms of oxide.
4. The method of claim 1, wherein: the molar ratio of the introduced water-soluble silicone oil to the introduced soluble auxiliary agent in terms of silicon oxide to oxide is 0.05-80.0.
5. The method of claim 1, wherein: the molar ratio of the introduced water-soluble silicone oil to the introduced soluble auxiliary agent in terms of silicon oxide to oxide is 0.1-15.0.
6. The method of claim 1, wherein: the molar ratio of the introduced water-soluble silicone oil to the introduced soluble auxiliary agent in terms of silicon oxide to oxide is 0.3-5.0.
7. The method of claim 1, wherein: the water-soluble silicone oil is water-soluble silicone oil and has the following properties: the viscosity at 25 ℃ is 200 to 7000mPa.s, and the cloud point is 30 to 100 ℃.
8. The method of claim 1, wherein: the water-soluble silicone oil is water-soluble silicone oil and has the following properties: the viscosity at 25 ℃ is 500-5000 mPa.s, and the cloud point is 40-65 ℃.
9. The method of claim 1, wherein: the soluble aluminum-containing compound is one or a combination of more of aluminum nitrate, aluminum chloride and aluminum sulfate, the soluble zirconium-containing compound is one or a combination of more of zirconium nitrate, zirconium tetrachloride and zirconium oxychloride, the soluble boron-containing compound is one or a combination of more of boric acid, ammonium pentaborate and ammonium tetraborate, and the soluble magnesium-containing compound is one or a combination of more of magnesium acetate, magnesium chloride, magnesium nitrate and magnesium sulfate.
10. The method of claim 1, wherein: the carbon precursor is one or more of acetic acid, oxalic acid, malonic acid, tartaric acid, malic acid, citric acid, ethylene glycol, propylene glycol, butanediol, glycerol, diethylene glycol, dipropylene glycol, triethylene glycol, tributylene glycol, tetraethylene glycol, polyethylene glycol, glucose, fructose, lactose, maltose and sucrose.
11. The method of claim 1, wherein: the alumina-based carrier is prepared by taking alumina as a main component, and does not contain an auxiliary agent component or contains the auxiliary agent component, wherein the auxiliary agent component is one or more of fluorine, silicon, phosphorus, titanium, zirconium and boron, and the content of the auxiliary agent component in the alumina-based carrier is below 30 wt%.
12. The method of claim 11, wherein: the content of the auxiliary agent component in the alumina-based carrier is less than 20 wt%.
13. The method of claim 11, wherein: the content of the auxiliary agent component in the alumina-based carrier is below 15 wt%.
14. The method of claim 1, wherein: the alumina-based carrier is obtained by roasting aluminum hydroxide at high temperature, and the conditions of the high-temperature roasting are as follows: roasting for 1.0-20.0 h at 450-1000 ℃, wherein the properties of the alumina-based carrier are as follows: the specific surface area is 120-420 m2(ii)/g; the pore volume is 0.4-1.3 mL/g; the pore volume of pores with a pore diameter of less than 4nm accounts for less than 20% of the total pore volume.
15. The method of claim 1, wherein: the alumina-based carrier is obtained by roasting aluminum hydroxide at high temperature, and the conditions of the high-temperature roasting are as follows: roasting at 450-1000 ℃ for 3.0-8.0 h; the properties of the alumina-based support are as follows: the specific surface area is 220-320 m2(ii)/g; the pore volume is 0.6-1.0 mL/g; the pore volume of pores with a pore diameter of less than 4nm accounts for less than 10% of the total pore volume.
16. The method of claim 15, wherein: the pore volume of pores with a pore diameter of less than 4nm accounts for less than 5% of the total pore volume.
17. The method of claim 1, wherein: the water-soluble silicone oil, the soluble auxiliary agent and the carbon precursor are introduced onto the carrier sequentially or simultaneously, namely the water-soluble silicone oil is introduced onto the carrier, then the soluble auxiliary agent is introduced onto the carrier, and finally the carbon precursor is introduced onto the carrier; or simultaneously introducing the water-soluble silicone oil and the soluble auxiliary agent onto the carrier, and then introducing the carbon precursor onto the carrier; or simultaneously introducing the water-soluble silicone oil, the soluble auxiliary agent and the carbon precursor onto the carrier.
18. The method of claim 1, wherein: the introduction mode adopts an impregnation method, and equal-volume impregnation or excessive impregnation can be carried out; multiple impregnations or one impregnation may be used.
19. The method of claim 17, wherein: and finally introducing a carbon precursor, and carrying out two-stage heat treatment on the alumina-based carrier before introducing the carbon precursor, wherein the temperature of the first-stage low-temperature heat treatment is 60-150 ℃, the treatment time is 0.5-20.0 h, the temperature of the second-stage high-temperature heat treatment is 180-400 ℃, and the treatment time is 0.5-20.0 h.
20. The method of claim 17, wherein: finally introducing a carbon precursor, and carrying out two-stage heat treatment on the alumina-based carrier before introducing the carbon precursor, wherein the temperature of the first-stage low-temperature heat treatment is 90-120 ℃, and the treatment time is 1.0-6.0 h; the temperature of the second-stage high-temperature heat treatment is 200-350 ℃, and the treatment time is 1.0-6.0 h.
21. The method of claim 19, wherein: after the carbon precursor is introduced, a high-temperature heat treatment is adopted, wherein the heat treatment method is to heat under the condition of oxygen-containing atmosphere, the heat treatment temperature is 150-450 ℃, and the heat treatment time is 0.5-6 hours; or the heat treatment is carried out in an inert gas atmosphere, wherein the inert gas is one or more selected from nitrogen, argon, helium, carbon dioxide and water vapor, the heat treatment temperature is 150-500 ℃, and the heat treatment time is 0.5-8 hours.
22. The method of claim 21, wherein: after the carbon precursor is introduced, a low-temperature heat treatment process is added before a high-temperature heat treatment, wherein the heat treatment temperature is 50-140 ℃, and the time is 0.5-6 hours.
23. The method according to claim 21 or 22, characterized in that: the temperature rise process of the heat treatment adopts rapid temperature rise, namely the temperature rise time reaching the heat treatment temperature is not more than 30 minutes.
24. The method according to claim 21 or 22, characterized in that: the temperature rise process of the heat treatment adopts rapid temperature rise, namely the temperature rise time reaching the heat treatment temperature is not more than 15 minutes.
25. The method of claim 1, wherein: the hydrogenation active metal component is an active metal component commonly used for a hydrotreating catalyst and is one or more of VIB group metals and VIII group metals.
26. The method of claim 25, wherein: the VIB group metal is W and/or Mo, and the VIII group metal is Co and/or Ni.
27. A catalyst prepared by the process of any one of claims 1 to 26, characterized in that: based on the weight of the catalyst, the content of the modified alumina-based carrier is 55.0 wt% -94.5 wt%, the content of the VIB group metal oxide is 5.0 wt% -30.0 wt%, and the content of the VIII group metal oxide is 0.5 wt% -15.0 wt%.
28. A catalyst prepared by the process of any one of claims 1 to 26, characterized in that: based on the weight of the catalyst, the content of the modified alumina-based carrier is 58.0-90.0 wt%; the content of the VIB group metal oxide is 8.0 wt% -30.0 wt%; the content of the VIII group metal oxide is 2.0 wt% -12.0 wt%.
29. Use of a hydroprocessing catalyst as defined in claim 27 or 28, characterized in that: the reaction conditions were as follows: the total reaction pressure is 3.0-18.0 MPa, and the liquid hourly space velocity is 0.2h-1~4.0h-1The volume ratio of hydrogen to oil is 200: 1-2000: 1, and the reaction temperature is 230-430 ℃.
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