CN107983405B - Preparation method of hydrogenation catalyst - Google Patents
Preparation method of hydrogenation catalyst Download PDFInfo
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- CN107983405B CN107983405B CN201610950056.2A CN201610950056A CN107983405B CN 107983405 B CN107983405 B CN 107983405B CN 201610950056 A CN201610950056 A CN 201610950056A CN 107983405 B CN107983405 B CN 107983405B
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- carrier
- hydrogenation catalyst
- compound
- acid
- water
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- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title abstract description 28
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- 238000013459 approach Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- LTPBRCUWZOMYOC-UHFFFAOYSA-N beryllium oxide Inorganic materials O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 1
- 229960003237 betaine Drugs 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- UAMZXLIURMNTHD-UHFFFAOYSA-N dialuminum;magnesium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Mg+2].[Al+3].[Al+3] UAMZXLIURMNTHD-UHFFFAOYSA-N 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- LRCFXGAMWKDGLA-UHFFFAOYSA-N dioxosilane;hydrate Chemical compound O.O=[Si]=O LRCFXGAMWKDGLA-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000000252 konjac Substances 0.000 description 1
- 235000010485 konjac Nutrition 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 239000000787 lecithin Substances 0.000 description 1
- 235000010445 lecithin Nutrition 0.000 description 1
- 229940067606 lecithin Drugs 0.000 description 1
- 235000021190 leftovers Nutrition 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 229950008882 polysorbate Drugs 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000009704 powder extrusion Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000003079 shale oil Substances 0.000 description 1
- 229960004029 silicic acid Drugs 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 229920005613 synthetic organic polymer Chemical class 0.000 description 1
- 239000011275 tar sand Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 239000002888 zwitterionic surfactant Substances 0.000 description 1
Classifications
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- B01J35/615—
-
- B01J35/635—
-
- B01J35/638—
-
- B01J35/64—
-
- 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
- C10G35/00—Reforming naphtha
- C10G35/04—Catalytic reforming
- C10G35/06—Catalytic reforming characterised by the catalyst used
-
- 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
-
- 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
Abstract
The present disclosure provides a method for preparing a hydrogenation catalyst, the method comprising: mixing the carrier precursor with a high water absorption compound and water, and then carrying out extrusion molding to obtain a carrier precursor wet strip; wherein the water absorption rate of the high water-absorbing compound is 250-1500, and the particle size of the high water-absorbing compound is less than 100 microns; drying and roasting the obtained wet carrier precursor strip in sequence to obtain a formed carrier; and loading the active metal element on the obtained molded carrier. The hydrogenation catalyst prepared by the preparation method disclosed by the invention has large metal deposition amount and deep deposition depth.
Description
Technical Field
The present disclosure relates to a method for preparing a hydrogenation catalyst.
Background
In recent years, the tendency toward crude oil heaviness and deterioration has been increasingly apparent worldwide, and at the same time, the demand for liquid fuel oil and reforming/steam cracking feedstock has been increasing. This has prompted the rapid development of heavy distillate processing techniques, of which catalysts are the most important and critical.
Catalysts for heavy oil or macromolecule conversion require a concentrated pore size distribution of the pores in the catalyst, in addition to a large pore size and sufficient pore volume.
Since catalysts for conversion of heavy oils or macromolecules are generally obtained by supporting an active ingredient having a catalytic action on a porous carrier, it is critical to prepare a catalyst having a large pore size and pore volume and a high concentration of pore size to provide a porous carrier having a large pore size and a high concentration of pore size.
Because alumina cannot form a regular crystalline structure like a molecular sieve due to the characteristics of the alumina, alumina carriers, partial silicon-aluminum materials, aluminum-magnesium materials and the like are difficult to form a uniform pore channel structure. However, it is also possible to form large pores or large specific surface area on the alumina carrier due to the stacking structure of alumina, but it is difficult to have both large pores and large specific surface area.
If the specific surface area, pore volume and pore size of several pores need to be considered uniformly for measuring the performance of the catalyst, an empirical formula for reference is (crude oil deep processing catalyst, China petrochemical press, Beijing, 1995, P231):
r＝K+0.0589S+13.2V+0.0012R
wherein r is desulfurization rate,%;
s is the specific surface area, m2/g；
V is pore volume, mL/g;
r is aperture, nm;
however, the K value alone cannot completely reflect the pore patency degree of the carrier, and is difficult to be combined with the reaction data.
The catalyst performance can be influenced in three aspects of specific surface area, pore volume and pore diameter due to the pore structure of the catalyst, and the influence of the three aspects can be different for different reactions.
It is generally believed that a large specific surface area provides more active area, resulting in more active sites; the pore volume is large, so that enough deposition volume is ensured, and even if carbon deposition of the catalyst occurs, the activity of the catalyst can still be maintained at a higher level; the pore size is directly related to whether the reactant can contact the active center, the diffusion speed of the reactant and the product, and the like. Some hydrogenation reactions are sensitive to specific surface area, i.e., the number of active sites, while some reactions have specific requirements for both pore size and pore volume, such as residual oil hydrogenation catalysts which require a catalyst with a larger pore size and also require a catalyst with an appropriately sized pore volume.
In order to improve the characteristics of the pore structure and improve the performance of the catalyst, there are many ways to improve the two parameters, either individually or simultaneously, and there are common ways: combustible pore-forming method and mixed powder extrusion method.
Combustible pore-forming methods are as follows:
chinese patent document CN1768947A proposes a preparation method of macroporous alumina, which is characterized in that in the preparation process, crop stem and hull powder is used as a pore-expanding agent, and the addition amount of the pore-expanding agent is 10-20 wt% of alumina. Compared with the prior art, the alumina carrier prepared by the method has the characteristics of large aperture, concentrated pore distribution, high mechanical strength and the like.
Chinese patent document CN102861615A proposes a preparation method of a macroporous alumina carrier, which comprises the following steps: weighing a certain amount of pseudo-boehmite dry glue powder, carbon black powder and an extrusion aid, uniformly mixing, then adding an aqueous solution containing a peptizing agent and a chemical pore-enlarging agent, uniformly mixing the obtained materials, extruding and molding, drying and roasting the molded material to obtain the alumina carrier, wherein the carbon black powder is subjected to dipping treatment by an ammonium salt aqueous solution.
Chinese patent document CN101214454A proposes a preparation method of macroporous alumina with diplopore distribution, which comprises the following specific steps: firstly, mixing alumina, pore-forming agent and solid silicon, and carrying out ball milling treatment in a ball mill; kneading the treated mixture with water solution with cationic surfactant, extrusion assistant, peptizing agent, etc. dissolved in the water solution into plastic body, and treating in water vapor atmosphere; and drying and roasting the obtained formed product to obtain the final alumina carrier. The pore-forming agent is one or a mixture of carbon black, cellulose and starch.
The mixed vermicelli extrusion method comprises the following steps:
chinese patent document CN1597117A proposes a method for preparing an alumina carrier, which is to use alumina leftovers (namely gamma-Al)2O3) Grinding into powder, kneading with carbon black powder and nitrogen-containing alkali solution or completely volatile ammonium salt alkali aqueous solution, adding aluminum hydroxide dry glue powder, and kneading into plastic body; after molding, drying and roasting, the alumina carrier is prepared. In the preparation process of the alumina carrier, inorganic acid or organic acid is not used as a peptizing agent.
Chinese patent document CN101322949A proposes a preparation method of an alumina carrier, wherein the alumina carrier adopts pseudo-boehmite powder prepared by a carbonization method and pseudo-boehmite powder prepared by an aluminum sulfate method which are mixed according to a weight ratio of 1: 0.1-5 as a precursor for preparing the alumina carrier, composite acid is used as a peptizing agent, zirconium, titanium, silicon, alkali metal, alkaline earth metal, rare earth metal, carbon black and other substances are added in a kneading process, and then the alumina carrier is prepared by molding, drying and roasting.
Chinese patent document CN103212449A proposes a hydrofining catalyst carrier and a preparation method thereof, the method is that modified diatomite, alumina powder, an adhesive and a pore-enlarging agent are mixed, and the carrier is prepared after kneading, molding, drying and roasting; the modified diatomite is prepared by soaking diatomite in alkali liquor, neutralizing with acid liquor, washing with water, and press-filtering, and the impurity amount on the surface and in the pores is greatly reduced, which is beneficial to the loading of active components.
Chinese patent document CN1103009A proposes a preparation method of an alumina carrier with double pores, which is to add carbon black and a surfactant into two aluminum hydroxide powders with different properties, to carry out kneading, extrusion molding, drying and finally to roast in an oxygen-containing airflow to prepare the required alumina carrier with double pores.
Chinese patent document CN101433863A proposes a composite oxide carrier and a preparation method thereof, the method is to co-precipitate precursors of alumina, silica and zirconia with an alkali solution, add a surfactant to improve the pore structure and the acidity and alkalinity, wash, filter and bake the obtained precipitate at high temperature to obtain composite oxide powder, and extrude the composite oxide powder to form the composite oxide carrier.
Chinese patent CN1768945A proposes an alumina carrier containing silicon and titanium and a preparation method thereof, wherein the auxiliary agent silicon in the modified alumina carrier is introduced in the gelling process of aluminum hydroxide, so that the specific surface area, the aperture and the pore volume of the alumina are greatly improved; after the gelling is finished, respectively using an acidic reagent and an alkaline reagent to adjust the pH value of the mixed slurry for multiple times, so that the obtained alumina has more concentrated pore distribution; the assistant titanium is added after gelling and before aging.
In addition to the above two main approaches, there are: the roasting temperature of the carrier is increased; the method of introducing steam and the like in the roasting process, however, the patents inevitably change the phase structure of the alumina carrier while improving the pore diameter of the carrier, thereby influencing the characteristics of active components and causing adverse effect on the performance of the catalyst.
Disclosure of Invention
The purpose of the disclosure is to provide a preparation method of a hydrogenation catalyst, and the hydrogenation catalyst prepared by the preparation method has large metal deposition amount and deep deposition depth.
In order to achieve the above object, the present disclosure provides a method for preparing a hydrogenation catalyst, the method comprising: mixing the carrier precursor with a high water absorption compound and water, and then carrying out extrusion molding to obtain a carrier precursor wet strip; wherein the water absorption rate of the high water-absorbing compound is 250-1500, and the particle size of the high water-absorbing compound is less than 100 microns; drying and roasting the obtained wet carrier precursor strip in sequence to obtain a formed carrier; and loading the active metal element on the obtained molded carrier.
Preferably, the super absorbent compound is at least one selected from the group consisting of saccharides, starch, cellulose, and high molecular polymers.
Preferably, the superabsorbent compound is a resin; the resin is at least one selected from starch resin, cellulose resin, polyacrylate resin, polyvinyl alcohol resin and polyoxyethylene resin.
Preferably, the weight ratio of carrier precursor, superabsorbent compound and water, on a dry weight basis, is 100: (0.1-5): (25-1600).
Preferably, the weight ratio of carrier precursor, superabsorbent compound and water, on a dry weight basis, is 100: (0.2-2): (50-1000).
Preferably, the preparation method of the hydrogenation catalyst further comprises: mixing the carrier precursor, the super absorbent compound, water and the peptizing agent, and then carrying out the extrusion molding; wherein the peptizing agent is hydrochloric acid aqueous solution and/or nitric acid aqueous solution, and the concentration of the peptizing agent is 0.5-5 wt%.
Preferably, the support precursor is pseudoboehmite.
Preferably, the drying conditions include: the temperature is 80-200 ℃, and the time is 1-12 hours; the roasting conditions comprise: the temperature is 350-800 ℃, the time is 1-10 hours, and the roasting atmosphere is oxygen-containing atmosphere.
Preferably, the step of loading comprises: the shaped carrier is impregnated with a solution containing at least one soluble metal compound of a group VIII metal and at least one soluble metal compound of a group VIB metal, and then dried and calcined.
Preferably, the soluble metal compound of the group VIII metal is at least one selected from the group consisting of nitrate, acetate, soluble carbonate, chloride and soluble complex of nickel, and the soluble metal compound of the group VIB metal is at least one selected from the group consisting of molybdic acid, paramolybdic acid, molybdate, paramolybdate, tungstic acid, metatungstic acid, ethyl metatungstic acid, tungstate, metatungstate and ethyl metatungstate.
Preferably, the hydrogenation catalyst has a channel characteristic index of 12 to 20; wherein the channel characteristic index is calculated by adopting a formula I: TI 0.1S/[1+5ABS (1-V)]+ logR; wherein TI is the characteristic index of the pore channel, and TI is a dimensionless numerical value; s is the specific surface area of the hydrogenation catalyst and the unit is meter2Per gram; v is the pore volume of the hydrogenation catalyst in ml/g; r is the aperture of a few pores of the hydrogenation catalyst, and the unit is angstrom; the ABS is a function of absolute value.
Preferably, the channel characteristic index is from 13 to 16.
Preferably, the specific surface area of the hydrogenation catalyst is 120-350 m2Pore volume of 0.4-1.25 ml/g, and pore diameter of several pores of 10-1000 angstrom.
The present disclosure facilitates the simultaneous increase in the specific surface area and pore volume of a hydrogenation catalyst by adding a superabsorbent compound during the preparation of the hydrogenation catalyst, while making the pore size of several pores of the hydrogenation catalyst more centralized.
The hydrogenation catalyst prepared by the method disclosed by the invention is beneficial to improving the macromolecular reaction performance, the coke deposition performance, and the metal deposition amount and the deposition depth of the hydrogenation catalyst.
In addition, in order to generate the same pore volume of the hydrogenation catalyst, the weight of the super absorbent compound adopted by the method is hundreds to thousands of times of the weight of the pore-expanding agent adopting the non-super absorbent compounds such as conventional activated carbon, cellulose, starch and the like, so that the preparation cost of the hydrogenation catalyst is greatly reduced, the carbon emission is reduced, and the requirements of green and low-carbon production are met.
Additional features and advantages of the disclosure will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present disclosure. It should be understood that the detailed description and specific examples, while indicating the present disclosure, are given by way of illustration and explanation only, not limitation.
The dry weight in this disclosure refers to the result measured after the sample is baked at 650 ℃ for 3 hours.
The present disclosure provides a method for preparing a hydrogenation catalyst, the method comprising: mixing the carrier precursor with a high water absorption compound and water, and then carrying out extrusion molding to obtain a carrier precursor wet strip; wherein the water absorption rate of the high water-absorbing compound is 250-1500, and the particle size of the high water-absorbing compound is less than 100 microns; drying and roasting the obtained wet carrier precursor strip in sequence to obtain a formed carrier; and loading the active metal element on the obtained molded carrier.
The high water absorption compound is a novel high polymer material, can absorb water which is hundreds of times to thousands of times of the self weight, and is non-toxic, harmless and pollution-free; has strong water absorption capacity and high water retention capacity, and the absorbed water can not be extruded by a simple physical method and can repeatedly release and absorb water. The composition of the super absorbent compound of the present disclosure is not particularly limited, and may be, for example, at least one selected from the group consisting of saccharides, starch, cellulose and high molecular polymers, preferably a resin; the resin is at least one selected from starch resin, cellulose resin, polyacrylate resin, polyvinyl alcohol resin and polyoxyethylene resin, preferably polyacrylate resin. The high water absorption compound can be an artificial synthetic product, a natural product and a modified product of the natural product, and can be an organic substance or an inorganic substance.
The high water-absorbing compound is added in the preparation step of the formed carrier, so that the high water-absorbing compound can expand after absorbing water to support a wet strip of a carrier precursor, the high water-absorbing compound is burnt out after roasting to generate more pore volume, the problems of carrier sintering and the like caused by overhigh local temperature generated by conventional pore-expanding agents such as activated carbon and the like during roasting can be prevented, the pore size distribution of the carrier precursor is better reserved, and in a specific implementation mode, the weight ratio of the carrier precursor to the high water-absorbing compound to water is 100: (0.1-5): (25-1600), preferably 100: (0.2-2): (50-1000). The dry weight of the carrier precursor may be obtained by calcining the carrier precursor, for example, calcining at 500 to 800 ℃ for 2 to 5 hours and then weighing.
Similar to the preparation method of the conventional hydrogenation catalyst, the preparation method of the hydrogenation catalyst may further include: mixing the carrier precursor, the super absorbent compound, water and the peptizing agent, and then carrying out the extrusion molding; wherein the peptizing agent is hydrochloric acid aqueous solution and/or nitric acid aqueous solution, and the concentration of the peptizing agent is 0.5-5 wt%. The preparation method can also comprise adding a proper amount of extrusion aid and/or adhesive during extrusion molding, and then carrying out extrusion molding.
Other extrusion aids and peptizers can be added in the carrier forming process for extrusion molding together, the types and the dosages of the extrusion aids and the peptizers have large influence on the hole concentration ratio, and the hole structure of the carrier can be changed by selecting a proper extrusion aid. The extrusion aid includes, but is not limited to, organic carboxylic acid, polyhydric alcohol, organic amine, surfactant, high molecular compound, and the like.
By organic carboxylic acid is meant a compound having a carboxyl group including, but not limited to: formic acid, acetic acid, oxalic acid, propionic acid, malonic acid, butyric acid, succinic acid, glutaric acid, adipic acid, benzoic acid, phthalic acid, phenylpropionic acid, etc., and others not listed are referred to in the "handbook of chemistry of lan" second edition, 1.26 to 1.27.
The surfactant is a substance which has fixed hydrophilic and lipophilic groups, can be directionally arranged on the surface of a solution and can obviously reduce the surface tension. Which comprises the following steps: 1. anionic surfactants such as stearic acid, sodium dodecylbenzenesulfonate and the like; 2. cationic surfactants such as quaternary ammonium compounds and the like; 3. zwitterionic surfactants, such as lecithin, amino acid type, betaine type, etc.; 4. nonionic surfactants such as fatty acid glycerides, polyols including sorbitan fatty acid (span), polysorbate (tween), polyoxyethylene type and polyoxyethylene-polyoxypropylene copolymers, and the like.
Polyol refers to an organic compound having a molecular structure containing a plurality of hydroxyl groups, and includes, but is not limited to, ethylene glycol, glycerol, butylene glycol, and the like.
The organic amine may include monoethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, urea, and the like.
The high molecular weight compound, also called polymer, refers to a compound having a relative molecular weight of more than ten thousand, which is formed by bonding a plurality of atoms or atomic groups mainly by covalent bonds. The organic polymer compounds can be classified into natural organic polymer compounds (e.g., starch, cellulose, protein, natural rubber, butadiene rubber, etc.) and synthetic organic polymer compounds (e.g., polyethylene, polyvinyl chloride, phenol resin, etc.), and their relative molecular masses can range from tens of thousands up to millions or more, but their chemical compositions and structures are relatively simple and often formed by arranging numerous (n) structural small units in a repeating manner, and the present disclosure does not limit the properties of the polymer.
The carrier precursor mentioned in the present disclosure may include silica gel, silica powder, silica gel having silica oxide or hydrated silica as a main component; molecular sieves or zeolites, carbon materials; magnesium-based materials based on magnesium oxide or hydrated magnesium oxide; titanium-based materials based on phases of titanium oxide or various hydrous titanium oxides; catalytic materials formed from any combination of the above materials may also be included.
The component of the carrier precursor of the present disclosure may be a two-component oxide such as alumina-silica, alumina-titania, alumina-magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania, titania-zirconia, or the like, and a third component may be added on the basis of the two components, without any limitation to the third component added. More components can be added on the basis of two components or three components, and the added components are not limited at all.
The support precursor of the present disclosure may also have a molecular sieve or zeolite component, and the present disclosure is not limited in any way as to the type and nature of the molecular sieve. The molecular sieve may be of the X, Y, beta, ZSM-5 and similar molecular sieves with ten membered rings, as well as all molecular sieve types and structures mentioned in the http:// www. In addition to the molecular sieve of the original structure, the modified molecular sieve can also include, but is not limited to, modified molecular sieves, such as modified Y-type molecular sieve, modified BETA molecular sieve, or modified ZSM-5 molecular sieve, etc.
The modified Y-type molecular sieve mentioned in the present disclosure refers to a mode of changing the total composition and framework composition of the molecular sieve by processing the NaY molecular sieve. The composition change method comprises the steps of reducing the Na content by an ion exchange method or exchanging other elements into the molecular sieve, wherein the elements comprise rare earth elements, transition metals, Ca, Mg and the like, and the purpose is to increase the stability of the molecular sieve or adjust the acidity of the molecular sieve. The framework composition is changed by a high-temperature hydrothermal method, an organic coordination reaction method, a high-temperature gas phase reaction method, an ammonium fluosilicate liquid phase reaction method and the like, and the aim is to change the framework silicon-aluminum ratio, and the framework silicon-aluminum ratio is generally improved by framework dealumination.
The dealumination mode of the Y-type molecular sieve comprises the following steps: thermal or hydrothermal dealumination, chemical dealumination, and a combination of the two methods. Among them, the hydrothermal treatment is widely used and has been widely used in a large number of industrial applications, and is currently the most used method. Hydrothermal treatment, which first appeared in the mid sixties, typically involves calcining NH in the presence of steam or in the presence of self-generated steam4Y, thereby extracting the skeletal aluminum into non-skeletal aluminum, the skeletal silicon-aluminum ratio is increased, the unit cell constant is increased, andthe ion exchange capacity decreases. The degree of dealumination and the magnitude of the unit cell constant can be adjusted by changing the temperature, time and water vapor partial pressure of the treatment. Or multiple hydrothermal treatments to reduce the unit cell constant to
Hereinafter, the defect after dealumination is that silicon is filled, the thermal stability is improved, so the catalyst is called USY, and the USY is widely applied to industrial hydrogenation catalysts.
The chemical dealumination method comprises the following steps: EDTA complexation dealumination method and SiCl4Gas phase isomorphous substitution dealumination method, (NH)4)2SiF6Liquid phase isomorphous substitution dealumination method and organic acid (such as oxalic acid, citric acid, etc.) liquid phase complexation dealumination method. A combined hydrothermal and chemical dealumination method: generally, firstly, hydrothermal dealuminization is carried out, then non-framework aluminum is removed by a chemical dealuminization method, and residual Na in a molecular sieve system is also removed while dealuminization is carried out+。
Because the modification methods of the Y-type molecular sieve are numerous, the modification method of the modified Y-type molecular sieve is not limited in any way, and the physicochemical properties of the modified Y-type molecular sieve are not limited in any way.
Preferably, the modified Y-type molecular sieve has a unit cell constant of
Meanwhile, the preparation process of the molecular sieve has a hydrothermal treatment step.
The most preferred modified molecular sieves have unit cell constants in
In the meantime. The preparation process of the molecular sieve comprises the steps of hydrothermal treatment and chemical dealumination.
When the catalyst is used for preparing a hydrogenation catalyst, other active auxiliaries are required to be added besides hydrogenation active components, and the type and the using amount of the other active auxiliaries are not limited in any way in the disclosure. If used in a non-hydrogenation catalyst, there may or may not be a hydrogenation component.
The present disclosure does not impose any limitation on the addition of other acidic materials other than the non-amorphous mesoporous acidic material and the modified Y-type molecular sieve. The acidic material may be one or more selected from zeolite-type molecular sieves, non-zeolite molecular sieves, which are commonly used as active components of cracking catalysts in the prior art, and the present disclosure does not impose any limitation on the kind and amount of the molecular sieve used. For example, one or more selected from ZRP, Y zeolite, mordenite, ZSM-5, MCM-41, omega, ZSM-12 and MCM-22 zeolite molecular sieves. One or more of Y zeolite, mordenite and ZSM-5 are preferred. The molecular sieve may be a commercially available product or may be prepared by conventional techniques.
The carrier precursor can be made into various easily-operated forming products according to different requirements, such as microspheres, spheres, tablets or strips. The molding may be carried out by a conventional method, for example, in the case of a composite support of a molecular sieve and an inorganic refractory oxide, it may be prepared by mixing the molecular sieve with the refractory inorganic oxide or a precursor thereof, extrusion molding and calcination. The precursor of the heat-resistant inorganic oxide refers to a compound capable of forming the heat-resistant inorganic oxide after being calcined, and generally refers to one or more of hydroxide, hydrated oxide, gel and sol containing the oxide and the hydroxide of the hydroxide. For example, the precursor of alumina may be selected from one or more of various hydrated aluminas and alumina sols.
In a preferred embodiment, the shaped support comprises at least one member selected from the group consisting of alumina, silica, magnesia, titania, zirconia, carbon and zeolite, preferably having an alumina content of 95 to 100 wt.%, based on the weight of alumina and based on the weight of the shaped support on a dry basis. The carrier precursor means: by itself, or after addition of some other component, may serve as a material for the catalyst. The carrier precursor may be a single component or a mixture of components. The support precursor may comprise a single component such as (hydrated) alumina, (hydrated) silica, magnesia, titania, zirconia, carbon components, and any combination thereof. It may be in a crystalline state or an amorphous state. Wherein the crystalline state includes, but is not limited to, molecular sieve or zeolite components. The composition and nature of the molecular sieve or zeolite contained in the support precursor is not limited by this disclosure, including but not limited to Y-zeolite, BETA zeolite, ZSM-5 and other molecular sieves containing ten membered rings. In addition to silica alumina type molecular sieves, other non-silica alumina type molecular sieves are included. The shaped support may become a catalyst after the active component is added, and the present disclosure does not impose any limitation on the composition and nature of the active component.
Preferably, the carrier precursor is pseudoboehmite, such as pseudoboehmite of Shandong, pseudoboehmite of Changling, and the like.
Drying and calcining are well known to those skilled in the art, and for example, the drying conditions may include: the temperature is 80-200 ℃, and the time is 1-12 hours; the temperature of the roasting is 350-800 ℃, preferably 450-650 ℃, the roasting time is 1-10 hours, preferably 2-8 hours, the atmosphere in the roasting process is arbitrary, and can contain water vapor, or does not contain, and can be an oxygen-containing atmosphere, such as air atmosphere, or can be nitrogen, argon or other gases, or can be any combination of gases in various proportions, and oxygen-containing atmosphere is preferred to burn off the high water-absorbing compound.
Methods for supporting the active metal element on the shaped support are well known to those skilled in the art in light of this disclosure, and for example, an aqueous solution of a compound containing the active metal element may be contacted with the shaped support, dried, and calcined. The method of contacting the aqueous solution of the compound containing the active metal element with the shaped support is preferably to impregnate the shaped support with an aqueous solution of the compound containing the hydrogenation active component. The temperature of the impregnation is not particularly limited in the present disclosure, and may be various temperatures that the impregnation solution can reach. The time for the impregnation is not particularly limited as long as the desired amount of the compound containing the hydrogenation active component can be supported on the shaped support, and for example, the temperature for the impregnation may be 5 to 150 ℃ and the time for the impregnation may be 0.5 to 12 hours. The drying temperature can be 80-350 ℃, preferably 100-300 ℃, and more preferably 105-250 ℃; the drying time may be 0.5 to 24 hours, preferably 1 to 24 hours, and more preferably 2 to 12 hours. The roasting temperature can be 350-600 ℃, and preferably 400-550 ℃; the calcination time may be 1 to 10 hours, preferably 2 to 8 hours.
The active metal element-containing compound may be a conventional active metal element-containing compound used in the preparation of hydrogenation catalysts, and may for example comprise at least one soluble metal compound of a group VIII metal and at least one soluble metal compound of a group VIB metal.
The soluble metal compound of the group VIII metal is known to those skilled in the art, and may be selected from one or more of nitrate, acetate, soluble carbonate, chloride and soluble complex of the group VIII metal. Preferably, the soluble metal compound of the group VIII metal is one or more of a nitrate, an acetate, a soluble carbonate, a chloride and a soluble complex of nickel.
The types of the soluble compounds of the group VIB metal are well known to those skilled in the art, and preferably, the soluble compounds of the group VIB metal comprise one or more of molybdic acid, paramolybdic acid, molybdate and paramolybdate and one or more of tungstic acid, metatungstic acid, ethyl metatungstic acid, tungstate, metatungstate and ethyl metatungstate.
The pore characteristic index of the hydrogenation catalyst prepared by the method can be 12-20; wherein the channel characteristic index is calculated by adopting a formula I: TI 0.1S/[1+5ABS (1-V)]+ logR; wherein TI is the characteristic index of the pore channel, and TI is a dimensionless numerical value; s is the specific surface area of the hydrogenation catalyst and the unit is meter2Per gram; v is the pore volume of the hydrogenation catalyst in ml/g; r is the aperture of a few pores of the hydrogenation catalyst, and the unit is angstrom; the ABS is a function of absolute value.
For a hydrogenation catalyst for macromolecular raw oil, the pore diameter, the pore volume, the specific surface area and the like are all very important, but the indexes are correlated, and a conventional correlation formula is as follows:
k × pore volume is specific surface area × pore diameter;
k is generally 30000-40000;
wherein the unit of pore volume is mL/g, and the unit of specific surface area is m2Per g, pore diameter unit of
The size of the K value reflects the arrangement mode of the basic units in the carrier.
In order to accurately describe the characteristics of the hydrogenation catalyst, the disclosure defines a new index, namely a channel characteristic index ti (transport index), by calculating:
TI＝0.1S/[1+5ABS(1-V)]+logR。
the hydrogenation catalyst has high channel characteristic index, on one hand, the microstructure of the carrier precursor is controlled by optimizing the production condition of the carrier precursor, and on the other hand, the proper forming mode and forming condition are adopted to maintain and expand the channel of the hydrogenation catalyst to the maximum extent.
In accordance with the present disclosure, to further satisfy the requirement of hydrogenation reaction, the specific surface area of the hydrogenation catalyst can be 120-350 m2A/g, preferably of 210-350 m2The pore volume may be from 0.4 to 1.25 ml/g, preferably from 0.9 to 1.25 ml/g, and the pore diameter may be from 10 to 1000 angstroms, preferably 100 and 150 angstroms.
According to the present disclosure, the active metal element may include at least one selected from group VIII metal elements, which may be iron, cobalt, and nickel, and group VIB metal elements, which may be chromium, molybdenum, and tungsten, for example, the active metal element may include tungsten and nickel, with or without molybdenum; the molybdenum content is generally not greater than 15 wt%, the tungsten content is generally not greater than 35 wt%, and the nickel content is generally not greater than 10 wt%, calculated as the oxide and based on the weight of the hydrogenation catalyst on a dry basis; preferably, the content of molybdenum is 0-15 wt%, the content of tungsten is 4-35 wt%, and the content of nickel is 1-10 wt% calculated by oxide and based on the dry weight of the hydrogenation catalyst; more preferably, the content of molybdenum is 3-10 wt%, the content of tungsten is 5-32 wt%, and the content of nickel is 2-8 wt%, calculated on oxide basis and based on the dry weight of the hydrogenation catalyst.
The specific surface area of the hydrogenation catalyst in the disclosure is determined by national standard GB/T19587-2004 of the people's republic of China, the pore volume and the pore size distribution of the hydrogenation catalyst are determined by RIPP 151-90 of petrochemical engineering analysis method (RIPP test method), and the RIPP standard method can be specifically referred to petrochemical engineering analysis method, edition such as Yangcui, 1990 edition. The probable pore size is the pore size corresponding to the highest peak in the pore size distribution, specifically, the BET method measures the pore structure of a sample, and a distribution curve of the differential of specific pore volume to pore size (dV/dr) with pore size can be obtained, and the differential of specific pore volume to pore size (dV/dr) corresponding to a certain pore size represents the pore volume corresponding to pores in the vicinity of the pore size, where the pore size corresponding to the highest dV/dr is referred to as the probable pore size. If a plurality of possible pore diameters exist, the possible pore diameter corresponding to the maximum specific pore volume is taken.
The hydrogenation catalyst provided by the present disclosure is suitable for hydrodemetallization of hydrocarbon feedstocks, particularly those metal types that are prone to surface layer deposition, such as iron, calcium, and the like, to reduce the metal content of the hydrocarbon feedstock. The hydrocarbon feedstock may be various heavy mineral oils or synthetic oils or their mixed distillates, such as vacuum gas oil, demetallized oil, atmospheric residue, deasphalted vacuum residue, coker distillate, shale oil, tar sand oil, coal liquefaction oil.
The hydrogenation catalysts provided in this disclosure may be presulfided with sulfur, hydrogen sulfide or sulfur-containing feedstock in the presence of hydrogen at a temperature of 140 ℃ and 370 ℃ prior to use, either outside the reactor or in situ within the reactor, to convert them to the sulfide form, according to conventional methods in the art.
When the hydrogenation catalyst prepared by the preparation method of the hydrogenation catalyst provided by the disclosure is used for hydrodemetallization of hydrocarbon raw materials, the hydrogenation catalyst can be used under the conventional hydrodemetallization process conditions, such as the reaction temperature of 200-,the reaction pressure is 3-24 MPa, preferably 4-15 MPa, and the liquid hourly space velocity is 0.1-30 hr-1The molar ratio of hydrogen to oil is 15-35.
The present disclosure is further illustrated by the following examples, but is not to be construed as being limited thereby.
The method for measuring the water absorption rate of the high water absorption compound in the embodiment of the disclosure is as follows: weighing a certain amount of high water absorption compound dried for 2 hours at 120 ℃, putting the high water absorption compound into a beaker, adding deionized water, keeping the deionized water to be over the high water absorption compound, filtering the mixture by using a funnel after the high water absorption compound is saturated, weighing, and calculating the water absorption rate Q by adopting the following formula:
q ═ W1-W0)/W0, wherein,
w1 is the weight of superabsorbent compound after water absorption and W0 is the weight of superabsorbent compound before water absorption.
Comparative example 1
Taking 150g of fine pseudo-boehmite powder (taken from Shandong aluminum works, the solid content (600 ℃/3h) is 69.5 wt%, the same below), adding 128mL of nitric acid solution with the concentration of 3.5 wt%, kneading for 20 minutes, extruding into cylindrical strips with the diameter of 1.8mm, drying for 8 hours at the temperature of 120 ℃, roasting for 3 hours at the temperature of 600 ℃, and marking as a forming carrier DA, wherein the physicochemical properties of the forming carrier DA are shown in Table 1.
Preparing a mixed dipping solution of nickel nitrate (analytically pure, Beijing Yili chemical reagent factory) and ammonium metatungstate (industrial products, from Changling catalyst factory) according to the tungsten oxide content of 17.0 wt% and the nickel oxide content of 3.8 wt% in the catalyst based on the dry weight, dipping the carrier DA by a pore saturation method, drying the carrier DA at 120 ℃ for 4 hours, roasting the carrier DA at 410 ℃ for 3 hours, and keeping the air flow not less than 130 cubic meters/(kg. h) during roasting to obtain the hydrogenation catalyst, which is marked as the hydrogenation catalyst DA. The physicochemical properties of the hydrogenation catalyst DA are shown in table 1.
Comparative example 2
The preparation method comprises the steps of taking 140g of SB powder (produced by SASOL Germany, and having a solid content (600 ℃/3h) of 73.5 weight percent), adding 123mL of nitric acid solution with a concentration of 2 weight percent, kneading for 20 minutes, extruding into cylindrical strips with a diameter of 1.8mm, drying at 120 ℃ for 8 hours, and roasting at 600 ℃ for 3 hours to obtain a formed carrier DB, wherein the physical and chemical properties of the formed carrier DB are shown in Table 1.
Preparing a mixed dipping solution of nickel nitrate (analytically pure, Beijing Yili chemical reagent factory) and ammonium metatungstate (industrial product, from Changling catalyst factory) according to the tungsten oxide content of 15.0 wt% and the nickel oxide content of 1.5 wt% in the catalyst based on the dry weight, dipping and molding the carrier DB by adopting a pore saturation method, drying at 120 ℃ for 3 hours, then roasting at 400 ℃ for 3 hours, and keeping the air flow not less than 150 cubic meters/(kilogram hour) during roasting to obtain the hydrogenation catalyst, wherein the record is as the hydrogenation catalyst DB. The physicochemical properties of the hydrogenation catalyst DB are shown in Table 1.
Comparative example 3
The preparation method comprises the steps of taking 140g of CL powder (pseudo-boehmite powder, produced by catalyst Changling division, with the solid content (600 ℃/3h) of 72.0 wt%, the same below), adding 135mL of nitric acid solution with the concentration of 3 wt%, kneading for 20 minutes, extruding into a cylindrical strip with the diameter of 1.8mm, drying at 120 ℃ for 8 hours, roasting at 600 ℃ for 3 hours, and marking as a forming carrier DC, wherein the physicochemical properties of the forming carrier DC are shown in Table 1.
Preparing a mixed dipping solution of nickel nitrate (analytically pure, Beijing Yili chemical reagent factory) and ammonium metatungstate (industrial product, from Changling catalyst factory) according to the tungsten oxide content of 14.0 wt% and the nickel oxide content of 4.7 wt% in the catalyst based on the dry weight, dipping and molding the carrier DC by adopting a pore saturation method, drying at 120 ℃ for 5 hours, then roasting at 390 ℃ for 3 hours, and keeping the air flow not less than 170 cubic meters/(kilogram hour) during roasting to obtain the hydrogenation catalyst, wherein the mark is the hydrogenation catalyst DC. The physicochemical properties of the hydrogenation catalyst DC are shown in table 1.
Comparative example 4
50.0g of fine pseudo-boehmite powder and 84.0g of Siral40 powder (produced by SASOL Germany, the solid content (600 ℃/3h) is 77.5 wt%, the silicon oxide content is 41.2%) are taken, 122mL of nitric acid solution with the concentration of 3.5 wt% is added, the mixture is kneaded for 20 minutes and extruded into cylindrical strips with the diameter of 1.8mm, the cylindrical strips are dried for 8 hours at the temperature of 120 ℃, and then are roasted for 3 hours at the temperature of 600 ℃, the cylindrical strips are marked as a forming carrier DD, and the physicochemical properties of the forming carrier DD are shown in Table 1.
Preparing a mixed dipping solution of nickel nitrate (analytically pure, Beijing Yili chemical reagent factory) and ammonium metatungstate (industrial products from Changling catalyst factory) according to the content of tungsten oxide and the content of nickel oxide of 2.5 weight percent in the catalyst by dry weight, dipping the formed carrier DD by a pore saturation method, drying the carrier DD at 120 ℃ for 5 hours, then roasting the carrier DD at 400 ℃ for 3 hours, and keeping the air flow not less than 110 cubic meters/(kilogram hour) during roasting to obtain the catalyst, which is marked as hydrogenation catalyst DD. The physicochemical properties of the hydrogenation catalyst DD are shown in table 1.
Example 1
Adding 5g of xanthan gum powder into a 250ml three-neck flask, measuring 50ml of water, adding the obtained mixture, adjusting the pH value of a system to 11-12, heating in a constant-temperature water bath at 70 ℃, activating for 1h, and cooling to about 45 ℃ for later use. 25g of acrylic acid were neutralized with a 30% strength NaOH solution in an ice-water bath to a pH of 7. The neutralized acrylic acid is added in N2Dropping into the xanthan gum solution under protection, simultaneously adding 0.35g of initiator potassium persulfate, then adding 0.1g of cross-linking agent N, N' -methylene-bisacrylamide, and raising the temperature to 55 ℃ for reaction for 2 hours. And (3) cutting the product into small particles by using scissors under the soaking of alcohol, then putting the small particles into a constant-temperature oven, drying the small particles for 2 hours at the temperature of 80 ℃, grinding the small particles and sieving the small particles with a 200-mesh sieve to obtain the super absorbent resin, wherein the water absorption capacity Q of the super absorbent resin is 300.
Taking 0.5g of super absorbent resin, adding 400mL of deionized water under stirring, mixing with 140g of CL powder after the solution becomes jelly-like paste, adding 115mL of nitric acid solution with the concentration of 1.5 weight percent, kneading for 20 minutes, extruding into a cylindrical strip with the diameter of 1.8mm, drying for 8 hours at 120 ℃, roasting for 3 hours at 600 ℃, and marking as a formed carrier A, wherein the physical and chemical properties of the formed carrier A are shown in Table 1.
Preparing a mixed dipping solution of nickel nitrate (analytically pure, Beijing Yili chemical reagent factory) and ammonium metatungstate (industrial product, from Changling catalyst factory) according to the tungsten oxide content of 13.5 wt% and the nickel oxide content of 2.6 wt% in the catalyst based on the dry weight, dipping the carrier A by adopting a pore saturation method, drying the carrier A at 120 ℃ for 5 hours, roasting the carrier A at 400 ℃ for 3 hours, and keeping the air flow not less than 140 cubic meters/(kg.h) during roasting to obtain the catalyst, which is marked as hydrogenation catalyst A. The physicochemical properties of the hydrogenation catalyst A are shown in Table 1.
Example 2
Adding 5g of xanthan gum powder into a 250ml three-neck flask, measuring 50ml of water, adding the obtained mixture, adjusting the pH value of a system to 11-12, heating in a constant-temperature water bath at 70 ℃, activating for 1h, and cooling to about 45 ℃ for later use. 25g of acrylic acid were neutralized with a 30% strength NaOH solution in an ice-water bath to a pH of 7. The neutralized acrylic acid is added in N2Dropping into the xanthan gum solution under protection, simultaneously adding 0.35g of initiator potassium persulfate, then adding 0.15g of cross-linking agent N, N' -methylene-bisacrylamide, and raising the temperature to 55 ℃ for reaction for 2 hours. And (3) cutting the product into small particles by using scissors under the soaking of alcohol, then putting the small particles into a constant-temperature oven, drying the small particles for 2 hours at the temperature of 80 ℃, grinding the small particles and sieving the small particles with a 200-mesh sieve to obtain the super absorbent resin, wherein the water absorption capacity Q of the super absorbent resin is measured to be 800.
Taking 0.5g of super absorbent resin, adding 600mL of deionized water under stirring, mixing the solution with 140g of CL powder after the solution becomes jelly-like paste, adding 115mL of nitric acid solution with the concentration of 1.5 weight percent, kneading for 20 minutes, extruding into a cylindrical strip with the diameter of 1.8mm, drying for 8 hours at 120 ℃, roasting for 3 hours at 600 ℃, and marking as a molded carrier B, wherein the physical and chemical properties of the molded carrier B are shown in Table 1.
Preparing a mixed dipping solution of nickel nitrate (analytically pure, Beijing Yili chemical reagent factory) and ammonium metatungstate (industrial product, from Changling catalyst factory) according to the tungsten oxide content of 13.5 wt% and the nickel oxide content of 2.6 wt% in the catalyst based on the dry weight, dipping the carrier B by a pore saturation method, drying the carrier B at 120 ℃ for 5 hours, roasting the carrier B at 400 ℃ for 3 hours, and keeping the air flow not less than 140 cubic meters/(kg.h) during roasting to obtain the catalyst which is marked as hydrogenation catalyst B. The physicochemical properties of the hydrogenation catalyst B are shown in Table 1.
Example 3
Adding 5g of xanthan gum powder into a 250ml three-neck flask, measuring 50ml of water, adding the obtained mixture, adjusting the pH value of a system to 11-12, heating in a constant-temperature water bath at 70 ℃, activating for 1h, and cooling to about 45 ℃ for later use. 25g of acrylic acid were neutralized with a 30% strength NaOH solution in an ice-water bath to a pH of 7. Will be neutralizedAcrylic acid in N2Dropping into the xanthan gum solution under protection, simultaneously adding 0.35g of initiator potassium persulfate, then adding 0.2g of cross-linking agent N, N' -methylene-bisacrylamide, and raising the temperature to 55 ℃ for reaction for 2 hours. And (3) cutting the product into small particles by using scissors under the soaking of alcohol, then putting the small particles into a constant-temperature oven, drying the small particles at 80 ℃ for 2 hours, grinding the small particles and sieving the small particles with a 200-mesh sieve to obtain the super absorbent resin, wherein the water absorption multiplying power Q of the super absorbent resin is measured to be 1200.
Taking 0.5g of super absorbent resin, adding 800mL of deionized water under stirring, mixing the solution with 140g of CL powder after the solution becomes jelly-like paste, adding 115mL of nitric acid solution with the concentration of 1.5 weight percent, kneading for 20 minutes, extruding into a cylindrical strip with the diameter of 1.8mm, drying for 8 hours at 120 ℃, roasting for 3 hours at 600 ℃, and marking as a molded carrier C, wherein the physical and chemical properties of the molded carrier C are shown in Table 1.
Preparing a mixed dipping solution of nickel nitrate (analytically pure, Beijing Yili chemical reagent factory) and ammonium metatungstate (industrial product, from Changling catalyst factory) according to the tungsten oxide content of 13.5 wt% and the nickel oxide content of 2.6 wt% in the catalyst based on the dry weight, dipping the carrier C by a pore saturation method, drying the carrier C at 120 ℃ for 5 hours, roasting the carrier C at 400 ℃ for 3 hours, and keeping the air flow not less than 140 cubic meters/(kg.h) during roasting to obtain the catalyst which is marked as hydrogenation catalyst C. The physicochemical properties of hydrogenation catalyst C are shown in Table 1.
Comparative example 5
Taking 5.0g of konjac flour (produced by Xian Dafengshou Biotechnology Co., Ltd., water absorption rate of 120), adding 20mL of room-temperature deionized water, uniformly mixing, adding 350mL of 60 ℃ deionized water while stirring to obtain a paste, adding 140g of SB powder, adding 125mL of 1.8 wt% nitric acid solution, kneading for 20 minutes, extruding into cylindrical strips with the diameter of 1.8mm, drying at 120 ℃ for 8 hours, roasting at 600 ℃ for 3 hours, and marking as a formed carrier DE, wherein the physicochemical properties of the formed carrier DE are shown in Table 1.
Preparing a mixed dipping solution of nickel nitrate (analytically pure, Beijing Yili chemical reagent factory) and ammonium metatungstate (industrial product, from Changling catalyst factory) according to the tungsten oxide content of 13.5 wt% and the nickel oxide content of 2.6 wt% in the catalyst based on the dry weight, dipping and molding the carrier DE by adopting a pore saturation method, drying the carrier DE at 120 ℃ for 5 hours, and then roasting the carrier DE at 400 ℃ for 3 hours, wherein the air flow is kept not less than 140 cubic meters/(kg. h) during roasting to obtain the catalyst, which is marked as hydrogenation catalyst DE. The physicochemical properties of the hydrogenation catalyst DE are shown in Table 1.
Evaluation of hydrogenation catalyst
The raw material oil used for evaluation was Yanshan Chang Yi, and iron naphthenate was added in an amount of 10 wt% and CS was added in an amount of 3 wt%2。
The specific properties of the Yanshan normal second-line raw oil are as follows: the density (20 ℃ C.) was 0.8256g/cm3The mass fraction of sulfur is 0.32 percent, and the mass fraction of nitrogen is 29 mu g/g; distillation range (D-86), IBP 177 ℃, 10% 218 ℃, 30% 247 ℃, 50% 261 ℃, 70% 273 ℃, 90% 294 ℃, FBP 322 ℃.
Evaluation Using an autoclave, 400mL of the formulated feed oil was charged into the autoclave, and after the catalyst examples and comparative examples (both 3.5g) were placed in a basket and pressure-tested under sealed conditions, H was added2The pressure is increased to 6.0MPa, the temperature is increased to 360 ℃, the catalyst is taken down after continuous reaction for 6 hours, and the amount of iron deposited on the catalyst and the deposition depth of the iron are analyzed through toluene extraction, and specific results are shown in Table 2. The amount of iron was measured by means of a ZSX Primus II X-ray fluorescence spectrometer of Japan, and the depth of iron deposition was measured by means of a Scanning Electron Microscope (SEM) under a field emission environment of Quanta 200F, FEI.
As can be seen from tables 1-2, the use of the hydrogenation catalyst provided by the present disclosure enables to increase the amount of metal deposition and the depth of deposition of the hydrogenation catalyst, as compared to the comparative example.
TABLE 1
TABLE 2
| Examples | Catalyst and process for preparing same | Iron deposition amount/weight% | Depth of iron deposition/μm |
| Comparative example 1 | DA | 2.53 | 80 |
| Comparative example 2 | DB | 1.86 | 72 |
| Comparative example 3 | DC | 2.98 | 120 |
| Comparative example 4 | DD | 2.16 | 74 |
| Example 1 | A | 6.82 | 270 |
| Example 2 | B | 6.41 | 257 |
| Example 3 | C | 7.38 | 285 |
| Comparative example 5 | DE | 2.33 | 72 |
Claims (11)
1. A method of preparing a hydrogenation catalyst, the method comprising:
mixing the carrier precursor with a high water absorption compound and water, and then carrying out extrusion molding to obtain a carrier precursor wet strip; wherein the water absorption rate of the high water-absorbing compound is 250-1500, and the particle size of the high water-absorbing compound is less than 100 microns; the high water-absorbing compound is cellulose resin;
drying and roasting the obtained wet carrier precursor strip in sequence to obtain a formed carrier;
and loading the active metal element on the obtained molded carrier.
2. The method of claim 1, wherein the weight ratio of carrier precursor, superabsorbent compound, and water, on a dry basis, is 100: (0.1-5): (25-1600).
3. The method of claim 1, wherein the weight ratio of carrier precursor, superabsorbent compound, and water, on a dry basis, is 100: (0.2-2): (50-1000).
4. The method of claim 1, wherein the method of preparing the hydrogenation catalyst further comprises: mixing the carrier precursor, the super absorbent compound, water and the peptizing agent, and then carrying out the extrusion molding; wherein the peptizing agent is hydrochloric acid aqueous solution and/or nitric acid aqueous solution, and the concentration of the peptizing agent is 0.5-5 wt%.
5. The method of claim 1, wherein the support precursor is pseudoboehmite.
6. The method of claim 1, wherein the drying conditions comprise: the temperature is 80-200 ℃, and the time is 1-12 hours; the roasting conditions comprise: the temperature is 350-800 ℃, the time is 1-10 hours, and the roasting atmosphere is oxygen-containing atmosphere.
7. The method of claim 1, wherein the step of loading comprises: the shaped carrier is impregnated with a solution containing at least one soluble metal compound of a group VIII metal and at least one soluble metal compound of a group VIB metal, and then dried and calcined.
8. The process according to claim 7, wherein the soluble metal compound of the group VIII metal is at least one selected from the group consisting of nitrates, acetates, soluble carbonates, chlorides and soluble complexes of nickel, and the soluble metal compound of the group VIB metal is at least one selected from the group consisting of molybdic acid, paramolybdic acid, molybdates, paramolybdates, tungstic acid, metatungstic acid, ethyl metatungstic acid, tungstates, metatungstates and ethyl metatungstates.
9. The process of claim 1, wherein the hydrogenation catalyst has a channel characteristic index of from 12 to 20; wherein the channel characteristic index is calculated by adopting a formula I:
wherein the content of the first and second substances,TIis an index of the characteristic of the channel,TIis a dimensionless number;Sis the specific surface area of the hydrogenation catalyst in meters2Per gram;Vpore volume of the hydrogenation catalyst in ml/g;Rmay be the pore size of the hydrogenation catalyst in angstroms; the ABS is a function of absolute value.
10. The method of claim 9, wherein the cell characteristic index is 13-16.
11. The process as claimed in claim 1 or 9, wherein the hydrogenation catalyst has a specific surface area of 120-350 m2Pore volume of 0.4-1.25 ml/g, and pore diameter of several pores of 10-1000 angstrom.
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| CN104646009A (en) * | 2013-11-22 | 2015-05-27 | 中国石油天然气股份有限公司 | Inferior heavy oil hydrodesulfurization catalyst and preparation method thereof |
| CN104927911A (en) * | 2014-03-21 | 2015-09-23 | 中国石油化工股份有限公司 | Hydrotreatment method of hydrocarbon oil raw material with high content of iron and calcium |
| CN105709711A (en) * | 2014-12-04 | 2016-06-29 | 中国石油化工股份有限公司 | Preparation method for alumina carrier |
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| CN104646009A (en) * | 2013-11-22 | 2015-05-27 | 中国石油天然气股份有限公司 | Inferior heavy oil hydrodesulfurization catalyst and preparation method thereof |
| CN104927911A (en) * | 2014-03-21 | 2015-09-23 | 中国石油化工股份有限公司 | Hydrotreatment method of hydrocarbon oil raw material with high content of iron and calcium |
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