CN111111682A - Efficient preparation method of hydrotreating catalyst - Google Patents
Efficient preparation method of hydrotreating catalyst Download PDFInfo
- Publication number
- CN111111682A CN111111682A CN201911401573.4A CN201911401573A CN111111682A CN 111111682 A CN111111682 A CN 111111682A CN 201911401573 A CN201911401573 A CN 201911401573A CN 111111682 A CN111111682 A CN 111111682A
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- Prior art keywords
- metal
- catalyst
- nickel
- acid
- cobalt
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- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 claims description 2
- OBWXQDHWLMJOOD-UHFFFAOYSA-H cobalt(2+);dicarbonate;dihydroxide;hydrate Chemical compound O.[OH-].[OH-].[Co+2].[Co+2].[Co+2].[O-]C([O-])=O.[O-]C([O-])=O OBWXQDHWLMJOOD-UHFFFAOYSA-H 0.000 claims description 2
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/04—Mixing
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
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- 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
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- 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
- C10G45/44—Hydrogenation of the aromatic hydrocarbons
- C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
- C10G45/48—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/50—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum or tungsten metal, or compounds thereof
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- 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
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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Abstract
The invention discloses a high-efficiency preparation method of a hydrotreating catalyst. The method comprises the steps of selecting soluble salts of VIII group transition metals nickel and/or cobalt and soluble salts of VIB group transition metals molybdenum and/or tungsten to prepare metal salt solutions, adding organic acid complexing agents and surfactants into the metal salt solutions in sequence, combining the metal salt solutions with metal ions under high-speed stirring to form metal coating, and promoting metal-organic matter particles to be dispersed in a system in a sol form to form metal colloid solutions; adding pore-expanding agent into pseudo-boehmite, mixing with the prepared metal colloid solution, preparing into semi-finished product through kneading-forming process, drying and roasting to obtain catalyst finished product. The preparation method has the advantages of short preparation flow and low cost, and meanwhile, the special particle form of the metal precursor can ensure that the aluminum hydroxide keeps weaker interaction with the metal group in the dehydration and crystal transformation process, so that the excessive combination of metal and aluminum oxide is avoided, and the activity of the prepared catalyst is high.
Description
Technical Field
The invention belongs to the field of petroleum refining, and particularly relates to an efficient preparation method of a hydrotreating catalyst.
Background
In recent years, with the increase of the requirement of the society on environmental protection, the quality standard of clean fuels is continuously improved, and various oil refining enterprises are promoted to continuously modify and upgrade hydrogenation production devices so as to meet the requirement of improving the product quality. The refinery hydrogenation unit has a strong demand for high-activity catalysts, which promotes the rapid development of the catalyst industry, and the market competition of hydrogenation catalysts is more and more intense, so that researchers are required to continuously reduce the catalyst processing cost while paying attention to the improvement of the catalyst activity in the research, development and improvement processes of the catalysts so as to meet the increasingly severe market demand.
At present, the hydrotreating catalyst used in industry is mainly prepared by adopting a loading method using alumina or modified alumina as a carrier, the preparation process comprises the steps of shaping an alumina carrier, drying the carrier, roasting the carrier, preparing a metal impregnation liquid, impregnating the carrier, drying the catalyst, roasting the catalyst, post-treating an organic matter and the like, and the production cost of the conventional hydrotreating catalyst is high due to the complex preparation process and many high-energy-consumption steps. Therefore, simplifying the processing steps is an effective method for reducing the catalyst cost, but how to simplify the preparation process while ensuring that the activity of the catalyst is not reduced, even improving the hydrogenation activity of the catalyst, is a problem which needs to be solved by researchers.
The literature reports that Huangda et al (kneading method for preparing NiMo/TiO)2Hydrodesulfurization forming catalyst [ C]A seventh Chinese functional material and an application academic conference corpus thereof, 2010.81-83) adopts a kneading method to prepare the hydrogenation catalyst of the titanium carrier: mixing aqueous solution prepared from nickel salt and molybdenum salt with H2TiO5·nH2Mixing amorphous compound of O and titanium, extruding, drying and roasting. Compared with alumina, titanium oxide has the advantage of high desulfurization activity as a hydrogenation catalyst carrier, but the disadvantages of small specific surface area and small pore volume are important factors restricting the application of the titanium oxideSurface area and pore volume.
Patent CN1091135C discloses a heavy oil hydrotreating catalyst and a preparation method thereof. The method takes Mo-Ni as an active component, adds Ti as an active additive, and converts the Mo-Ni into gamma-Al through roasting2O3Adding an alkaline solution containing VIB metal into the aluminum hydroxide dry glue powder, fully kneading until the aluminum hydroxide dry glue powder is completely wetted by the alkaline solution, adding an acidic solution of VIII group and IVB group metals, kneading, molding, drying and roasting to obtain the catalyst. The residual oil hydrogenation catalyst prepared by the method is beneficial to uniform distribution of the auxiliary active component Ti, the specific surface area of the prepared catalyst reaches 220-260 m2/g, the pore volume reaches 0.40-0.46 ml/g, and the large pore volume and the high specific surface area are beneficial to improvement of the passing rate and the reaction efficiency of macromolecules in the residual oil hydrogenation reaction.
Patent CN 100537028C discloses a preparation method of a hydrotreating catalyst. The method is basically similar to the method of patent CN1091135C, and takes gamma-Al 2O3 as a carrier, VIB group and VIII group metals as active components, Ti and the like as active auxiliary agents, and adopts a complete kneading method to prepare the catalyst, namely, a titanium salt solution and aluminum hydroxide dry glue are mixed, and then an alkaline solution of the VIB group metals and an acidic solution of the VIII group metals are sequentially added for kneading and molding to prepare the catalyst. Such a "complete kneading method" can simplify the process flow to a certain extent, and can greatly increase the pore volume and specific surface area of the catalyst, but also has the disadvantages of restricting the application thereof: firstly, in the method, a plurality of active metals and auxiliary metals need to be respectively prepared into solutions and are sequentially mixed with aluminum hydroxide to prepare a plurality of solutions, the added water amount for an alumina precursor is large, the catalyst forming and the catalyst strength are not facilitated, the two active metal solutions are respectively acidic and alkaline, and the metal is easy to generate precipitation reaction to be accumulated on the surface of the alumina due to the drastic change of the pH value; secondly, in the prepared solution, metal ions lack effective 'coating' and protection, and the metal ions enter alumina crystal lattices in the process of alumina precursor crystal transformation and are combined with Al-OH bonds to generate an aluminum molybdate crystal phase, which is an important factor for limiting the activity of the catalyst prepared by the 'complete mixing and kneading method'.
Literature reportsOpen pore distance (novel kneading method CoMo/gamma-Al)2O3Hydrodesulfurization catalyst [ J]Petroleum institute (Petroleum processing), 2005.21(1): 6-11), studied the "wet kneading method" for preparing CoMo/gamma-Al2O3The catalyst is prepared through mixing the acid solution of metal salt and pseudoboehmite directly, forming, drying and roasting. The article concluded through experimental studies that: when the metal loading exceeds the monolayer dispersion threshold (lower metal loadings, only experimental studies, not applicable to industrial catalysts), the metallic molybdenum will combine with the alumina to form an aluminum molybdate crystalline phase, thereby reducing the metal utilization and impairing the catalyst activity. Therefore, if the method is to replace the traditional supporting method, the problem of excessive combination of metal and alumina in the preparation process needs to be solved so as to ensure the activity of the catalyst.
The hydrotreating catalyst used in industry at present is mainly prepared by a loading method using alumina or modified alumina as a carrier, and the preparation process comprises the steps of forming an alumina carrier, drying the carrier, roasting the carrier, preparing a metal impregnation liquid, impregnating the carrier, drying the catalyst, roasting the catalyst, post-treating an organic matter and the like. The production cost of the existing hydrogenation catalyst is high due to the complex preparation process flow and many high-energy-consumption steps. In recent years, researchers can simplify the preparation process to a certain extent by improving the preparation processes such as a dry mixing kneading method and a wet mixing kneading method, but the improved methods cannot solve the problems of uneven dispersion of active components, agglomeration of metal particles, excessive combination of metal and alumina and the like, so that the utilization rate of the metal is reduced, and the activity of the prepared catalyst is low, so that the industrial application of the technology cannot be realized.
Disclosure of Invention
The invention aims to provide a high-efficiency preparation method of a hydrotreating catalyst aiming at the defects of the prior art.
Therefore, the invention starts from the aspect of solving the technical problems, firstly, the active components and the alumina support structure are mixed and formed in one step, the process flow is simplified, the intermediate steps of high energy consumption and strong heat release such as carrier drying, roasting and impregnation loading are omitted, and the processing cost is effectively reduced; secondly, an active metal precursor solution is prepared into a semi-sol system by introducing a surfactant, the surfactant is adsorbed on the surfaces of molybdate radical and tungstate radical negative ions to coat metal ions, the particle size is increased, the steric effect of the surfactant is utilized to weaken the combination effect of active components and alumina, the active components are prevented from entering a lattice structure of the alumina in the crystal transformation process of the aluminum hydroxide, and meanwhile, the dispersion effect of the surfactant also prevents the agglomeration of the active metal components in carrier pore channels, thereby being beneficial to the improvement of metal dispersity.
The invention solves the technical problems by the following technical scheme:
a high-efficiency preparation method of a hydrotreating catalyst comprises the following steps:
1) selecting soluble salts of VIII group transition metals nickel and/or cobalt and VIB group transition metals molybdenum and/or tungsten to prepare metal salt solutions, adding organic acid complexing agents and surfactants into the metal salt solutions in sequence, combining the metal salt solutions with metal ions under high-speed stirring to form metal coating, and promoting metal-organic matter particles to be dispersed in a system in a sol form to form metal colloid solutions;
2) adding a pore-expanding agent into the pseudo-boehmite, mixing with the metal colloid solution prepared in the step 1), preparing a semi-finished product through a kneading-forming process, and drying and roasting to obtain a catalyst finished product;
the adding amount of the metal salt in the step 1) is determined according to the composition of the finished catalyst, and the catalyst comprises the following components: the content of nickel oxide and/or cobalt oxide is 2-12 wt%, the content of molybdenum oxide and/or tungsten oxide is 6-28 wt%, and the balance is aluminum oxide; the adding proportion of the organic acid complexing agent is that the molar ratio of the organic acid complexing agent to the metal nickel and/or cobalt is (0.6-1.5): 1; the addition amount of the surfactant in the solution is 1-20 g/100 mL.
In the preparation method of the invention, preferably, the soluble salt of metallic nickel in the step 1) is one or more of nickel nitrate, nickel acetate, nickel oxalate, nickel carbonate and basic nickel carbonate, the soluble salt of metallic cobalt is one or more of cobalt nitrate, cobalt carbonate and basic cobalt carbonate, the soluble salt of metallic molybdenum is one or more of ammonium paramolybdate, phosphomolybdic acid and ammonium phosphomolybdate, and the soluble salt of metallic tungsten is one or more of phosphotungstic acid, silicotungstic acid and ammonium metatungstate.
In the preparation method of the invention, preferably, the polyhydroxy acid used in the step 1) is one or more of lactic acid, oxalic acid, citric acid, tartaric acid and malic acid; the surfactant is one or more of polyvinyl alcohol (PVA), polyethylene glycol (PEG)10000, polyvinylpyrrolidone (PVP) and Polyacrylamide (PAM).
The method for producing the catalyst of the present invention requires the pseudo-boehmite according to step 2) to have a pore volume of not less than 0.90mL/g and a specific surface area of not less than 320m2(ii)/g; the binder is one or more of sesbania gum powder, hydroxypropyl methylcellulose, soluble starch and activated carbon.
In the preparation method of the catalyst, in the drying and roasting processes in the step 2), the drying temperature is preferably 90-120 ℃, the drying time is preferably 2-8 hours, the roasting temperature is preferably 450-600 ℃, and the roasting time is preferably 1-4 hours.
The invention also provides a catalyst prepared by the preparation method, wherein the pore volume of the catalyst is not less than 0.40mL/g, and the specific surface area is not less than 200m2(iv)/g, mechanical strength not less than 150N/cm.
The invention also provides the application of the hydrotreating catalyst in the hydrotreating process of any inferior raw material of secondary processing diesel oil, vacuum wax oil, coking wax oil and medium-low temperature coal tar.
The preparation method of the catalyst provided by the invention can be used for preparing the hydrotreating catalyst of distillate oil of atmospheric and vacuum devices and distillate oil of secondary processing of devices such as coking, catalytic cracking and the like.
Compared with the conventional loading method, the preparation method of the catalyst provided by the invention has the advantages that the preparation process flow is shortened, the high-energy-consumption steps are reduced, and the processing cost is effectively reduced; compared with the existing methods such as a complete kneading method, a wet kneading method and the like, the prepared catalyst has moderate bonding degree of active metal and alumina, uniform metal dispersion and high utilization rate, solves the problem that the catalyst prepared by the method is lower than that prepared by a conventional loading method, and simultaneously has simple and convenient preparation process operation and controllable process, and can meet the requirements of industrial production and application.
Drawings
FIG. 1 is an XRD crystal phase spectrum of the hydrogenation catalyst prepared by the high-efficiency preparation method of the invention.
Detailed Description
The features of the present invention will be further illustrated by the following specific examples, but are not limited to the following examples. The percentages referred to below are percentages by weight.
Example 1
And adding 54g of ammonium paramolybdate, 32g of nickel nitrate and 17g of citric acid into 150mL of deionized water, stirring and dissolving, dissolving 18g of surfactant polyvinyl alcohol into 100mL of boiling water, and uniformly mixing and stirring a surfactant aqueous solution and a metal solution to obtain a transparent glue solution, wherein the mark is Y-1.
278g of pseudo-boehmite is taken, 8g of hydroxypropyl methyl cellulose is added, the mixture is put into a kneader and kneaded for 20min, the metal colloid solution Y-1 prepared in the first step is uniformly added into the kneaded material, the kneading is continued for 40min until the material has uniform color and moderate dryness and wetness and can be agglomerated by finger kneading, and then the kneaded material is taken out and extruded into strips for forming.
Drying the formed small strips at 120 ℃ for 4h, and roasting at 480 ℃ for 3h to obtain the finished product of the catalyst TS-1. The catalyst physical properties are shown in Table 1.
Example 2
And adding 54g of ammonium paramolybdate, 27g of nickel acetate and 22g of tartaric acid into 150mL of deionized water, stirring and dissolving, dissolving 15g of surfactant polyacrylamide into 100mL of deionized water, and uniformly mixing and stirring a surfactant aqueous solution and a metal solution to obtain a transparent glue solution, wherein the mark is Y-2.
And (2) adding 278g of pseudo-boehmite into 8g of sesbania powder, putting into a kneading machine for kneading for 20min, uniformly adding the metal colloid solution Y-2 prepared in the first step into the kneaded material, continuing kneading for 35min until the material is uniform in color, moderate in dryness and humidity and capable of being agglomerated by finger kneading, taking out, extruding and molding.
Drying the formed small strips at 120 ℃ for 4h, and roasting at 480 ℃ for 3h to obtain the finished product of the catalyst TS-2. The physical properties of the catalyst are shown in Table 1, and the crystal phase analysis of the catalyst is shown in FIG. 1.
Example 3
Adding 39g of ammonium metatungstate, 27g of ammonium paramolybdate, 27g of nickel acetate and 15g of malic acid into 150mL of deionized water, stirring and dissolving, dissolving 26g of surfactant polyethylene glycol (10000) into 100mL of deionized water, and uniformly mixing and stirring a surfactant aqueous solution and a metal solution to obtain a transparent glue solution, which is marked as Y-3.
And (3) adding 278g of pseudo-boehmite into 8g of soluble starch, putting into a kneader, kneading for 20min, uniformly adding the metal colloid solution Y-3 prepared in the first step into the kneaded material, continuously kneading for 45min until the material is uniform in color, moderate in dryness and wetness and capable of being agglomerated by finger kneading, taking out, extruding and molding.
Drying the formed small strips at 120 ℃ for 4h, and roasting at 480 ℃ for 3h to obtain the finished product of the catalyst TS-3. The catalyst physical properties are shown in Table 1.
Example 4
Adding 25g of phosphotungstic acid, 32g of nickel nitrate and 12g of oxalic acid into 150mL of deionized water, stirring and dissolving, dissolving 21g of surfactant polyvinylpyrrolidone into 100mL of deionized water, and uniformly mixing and stirring a surfactant aqueous solution and a metal solution to obtain a transparent glue solution, wherein the transparent glue solution is marked as Y-4.
And (2) adding 278g of pseudo-boehmite into 8g of active carbon, putting into a kneader, kneading for 20min, uniformly adding the metal colloid solution Y-4 prepared in the first step into the kneaded material, continuously kneading for 50min until the material is uniform in color, moderate in dryness and wetness, and capable of being agglomerated by finger kneading, taking out, extruding and forming.
Drying the formed small strips at 120 ℃ for 4h, and roasting at 480 ℃ for 3h to obtain the finished product of the catalyst TS-3. The catalyst physical properties are shown in Table 1.
Comparative example 1
The catalyst with the same metal content is prepared by adopting a conventional loading method.
Adding 278g of pseudo-boehmite into 8g of sesbania powder, and putting into a kneader for kneading for 20 min; dissolving 6g of concentrated nitric acid in 250mL of deionized water, uniformly adding the prepared dilute nitric acid solution into the kneaded material, continuously kneading for 30min, taking out, extruding and molding. And drying the formed small strips at 120 ℃ for 6h, and roasting at 550 ℃ for 3h to obtain the alumina carrier.
Dissolving 48g of molybdenum oxide, 13g of basic nickel carbonate and 22g of citric acid in an ammonia solution, stabilizing and clarifying, and then fixing the volume to 160mL to obtain a metal impregnation liquid, loading the metal impregnation liquid on the carrier prepared in the first step by adopting an isometric impregnation method, curing at room temperature for 7 hours, drying at 120 ℃ for 4 hours, and roasting at 480 ℃ for 3 hours to obtain the finished catalyst RS-1. The physical properties of the catalyst are shown in Table 1, and the crystal phase analysis of the catalyst is shown in FIG. 1.
Comparative example 2
The catalyst with the same metal composition is prepared by adopting a complete kneading method described in the prior patent.
Dissolving 48g of molybdenum oxide in 160ml of ammonia water solution, and marking as alkaline solution-1; 32g of nickel nitrate and 10g of acetic acid are dissolved in 100ml of deionized water, and the solution is marked as an acidic solution-2.
Adding 278g of aluminum hydroxide dry glue powder into 8g of sesbania powder, putting the mixture into a kneading machine, uniformly mixing, adding an alkaline solution-1, continuously kneading until the powder is uniformly wetted, adding an acidic solution-2, kneading for 40min, taking out the material after the material is plastic, extruding and forming. Drying the formed small strips at 120 ℃ for 4h, and roasting at 480 ℃ for 3h to obtain the finished catalyst RS-2. The physical properties of the catalyst are shown in Table 1, and the crystal phase analysis of the catalyst is shown in FIG. 1.
Examples 5 to 8
This example demonstrates the hydrogenation performance of the catalyst provided by the invention for poor quality catalytic diesel.
The poor quality catalytic diesel oil produced by a catalytic cracking unit of a refinery is used as a reaction raw material, and the main properties of the raw material are shown in table 2.
A100 mL fixed bed hydrogenation device is adopted to respectively evaluate the hydrogenation reaction performance of the catalysts TS-1, TS-2, TS-3 and TS-4, and the upper end of a catalyst bed layer is filled with an equal amount of hydrogenation protective agent.
Catalyst sulfurization conditions: using a composition containing 3% CS2At the airspeed of 1.0h-1Hydrogen-oil volume ratio of 500:1, pressure of 8.5MPa,the catalyst is presulfided.
And (3) vulcanization temperature rise program: introducing pre-vulcanized oil at 120 ℃ and stabilizing for 2 hours; raising the temperature to 150 ℃ at a speed of 15 ℃/h, and carrying out constant-temperature vulcanization for 4 h; raising the temperature to 230 ℃ at the speed of 6 ℃/h, and carrying out constant-temperature vulcanization for 10 h; heating to 290 ℃ at the speed of 6 ℃/h, and carrying out constant-temperature vulcanization for 6 h; heating to 340 ℃ at the speed of 10 ℃/h, and carrying out constant-temperature vulcanization for 6 h; and finally, naturally cooling to 200 ℃, and switching reaction raw materials.
Reaction operating conditions are as follows: pressure of 8.5MPa, average reaction temperature of 350 ℃, hydrogen-oil volume ratio of 700: 1, volume space velocity of 1.0h-1. The evaluation results are shown in Table 2.
Comparative examples 3 to 4
This comparative example illustrates the reaction performance of the catalyst prepared by the process of this patent compared to the catalysts prepared in comparative examples 1 and 2. Evaluation experiments of the comparative agents were conducted in the same manner as in examples 5 to 8, and the catalyst evaluation results are shown in Table 2.
TABLE 1 analysis of physical Properties of the catalyst
As can be seen from an XRD crystal phase analysis spectrogram in figure 1, compared with a catalyst RS-1 prepared by a conventional loading method, the catalyst RS-2 prepared by a 'complete mixing kneading method' has an obvious aluminum molybdate crystal phase peak at an angle of 2 theta of about 25 degrees, while the catalyst TS-2 prepared by the method has no obvious aluminum molybdate peak, and an XRD curve of the catalyst is basically close to that of the loading method, which shows that the method can effectively inhibit excessive combination with active metals in the aluminum hydroxide crystal transformation process.
TABLE 2 evaluation results of catalysts
The comparative evaluation results in table 2 verify the actual reactivity levels of the catalysts prepared by the method of the present invention and the comparative catalysts, and the results show that: compared with RS-2 under the same condition, the catalytic diesel oil hydrogenated by the catalyst prepared by the method has lower contents of sulfur, nitrogen and aromatic hydrocarbon, wherein the quality of the diesel oil products hydrogenated by the catalysts prepared in the examples 2 and 3 is better than that of the catalyst prepared by the conventional loading method, and the catalyst prepared by the method has good hydrogenation activity and application value.
Claims (7)
1. A high-efficiency preparation method of a hydrotreating catalyst is characterized by comprising the following steps: the method comprises the following steps:
1) selecting soluble salts of VIII group transition metals nickel and/or cobalt and VIB group transition metals molybdenum and/or tungsten to prepare metal salt solutions, adding organic acid complexing agents and surfactants into the metal salt solutions in sequence, combining the metal salt solutions with metal ions under high-speed stirring to form metal coating, and promoting metal-organic matter particles to be dispersed in a system in a sol form to form metal colloid solutions;
2) adding a pore-expanding agent into the pseudo-boehmite, mixing with the metal colloid solution prepared in the step 1), preparing a semi-finished product through a kneading-forming process, and drying and roasting to obtain a catalyst finished product;
the addition amount of the metal salt in the step 1) is determined according to the composition of the finished catalyst, and the catalyst comprises the following components: the content of nickel oxide and/or cobalt oxide is 2-12 wt%, the content of molybdenum oxide and/or tungsten oxide is 6-28 wt%, and the balance is aluminum oxide; the adding proportion of the organic acid complexing agent is that the molar ratio of the organic acid complexing agent to the metal nickel and/or cobalt is (0.6-1.5): 1; the addition amount of the surfactant in the solution is 1-20 g/100 mL.
2. The method for efficiently preparing the hydrotreating catalyst according to claim 1, characterized in that the soluble salt of metallic nickel is one or more of nickel nitrate, nickel acetate, nickel oxalate, nickel carbonate and basic nickel carbonate, the soluble salt of metallic cobalt is one or more of cobalt nitrate, cobalt carbonate and basic cobalt carbonate, the soluble salt of metallic molybdenum is one or more of ammonium paramolybdate, phosphomolybdic acid and ammonium phosphomolybdate, and the soluble salt of metallic tungsten is one or more of phosphotungstic acid, silicotungstic acid and ammonium metatungstate.
3. The efficient preparation method of the hydrotreating catalyst according to claim 1, characterized in that the organic acid complexing agent in step 1) is one or more of lactic acid, oxalic acid, citric acid, tartaric acid, and malic acid, and the surfactant is one or more of polyvinyl alcohol, polyethylene glycol 10000, polyvinylpyrrolidone, and polyacrylamide.
4. The process for efficiently producing the hydrotreating catalyst according to claim 1, wherein the pseudo-boehmite described in the step 2) is required to have a pore volume of not less than 0.90mL/g and a specific surface area of not less than 320m2(ii)/g; the binder is one or more of sesbania gum powder, hydroxypropyl methylcellulose, soluble starch and activated carbon.
5. The efficient preparation method of the hydrotreating catalyst according to claim 1, characterized in that the drying and roasting processes in step 2) are carried out at a drying temperature of 90-120 ℃ for 2-8 hours and at a roasting temperature of 450-600 ℃ for 1-4 hours.
6. A catalyst prepared by the process for efficiently producing a hydrotreating catalyst according to claim 1, characterized in that the catalyst has a pore volume of not less than 0.40mL/g, a specific surface area of not less than 200m2/g and a mechanical strength of not less than 150N/cm.
7. The use of the hydrotreating catalyst according to claim 6 in the hydrotreating process of any inferior raw material of secondary processing diesel oil, vacuum wax oil, coker wax oil and medium-low temperature coal tar.
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| CN113908865A (en) * | 2021-10-25 | 2022-01-11 | 中国海洋石油集团有限公司 | Selective hydrogenation dearomatization catalyst, preparation method and application thereof |
| CN116139895A (en) * | 2022-12-31 | 2023-05-23 | 中国海洋石油集团有限公司 | Preparation method of sulfuration type hydrodemetallization catalyst |
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