CN117920238A - Preparation method of hydrogenation protective agent - Google Patents
Preparation method of hydrogenation protective agent Download PDFInfo
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- CN117920238A CN117920238A CN202211307012.XA CN202211307012A CN117920238A CN 117920238 A CN117920238 A CN 117920238A CN 202211307012 A CN202211307012 A CN 202211307012A CN 117920238 A CN117920238 A CN 117920238A
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- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 65
- 239000003223 protective agent Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 84
- 239000011148 porous material Substances 0.000 claims abstract description 48
- 239000000243 solution Substances 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 35
- 229910052751 metal Inorganic materials 0.000 claims abstract description 33
- 239000002184 metal Substances 0.000 claims abstract description 33
- 238000001035 drying Methods 0.000 claims abstract description 22
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 12
- 238000007789 sealing Methods 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
- 239000011343 solid material Substances 0.000 claims abstract description 5
- 238000000926 separation method Methods 0.000 claims abstract description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 8
- 150000004706 metal oxides Chemical class 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- 238000010521 absorption reaction Methods 0.000 claims description 6
- 229920006395 saturated elastomer Polymers 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- -1 VIB group metals Chemical class 0.000 claims description 5
- 150000002739 metals Chemical class 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 238000011065 in-situ storage Methods 0.000 claims description 2
- 239000012535 impurity Substances 0.000 abstract description 6
- 229910052720 vanadium Inorganic materials 0.000 abstract description 6
- 229910052791 calcium Inorganic materials 0.000 abstract description 5
- 229910052759 nickel Inorganic materials 0.000 abstract description 5
- 238000009826 distribution Methods 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 13
- 239000003921 oil Substances 0.000 description 13
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 8
- 229910000480 nickel oxide Inorganic materials 0.000 description 8
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 8
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000010335 hydrothermal treatment Methods 0.000 description 6
- 239000011575 calcium Substances 0.000 description 5
- 238000007598 dipping method Methods 0.000 description 5
- 239000000295 fuel oil Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
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- 239000000843 powder Substances 0.000 description 3
- 101150116295 CAT2 gene Proteins 0.000 description 2
- 101100392078 Caenorhabditis elegans cat-4 gene Proteins 0.000 description 2
- 101100326920 Caenorhabditis elegans ctl-1 gene Proteins 0.000 description 2
- 101100494773 Caenorhabditis elegans ctl-2 gene Proteins 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 101100112369 Fasciola hepatica Cat-1 gene Proteins 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 101100005271 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-1 gene Proteins 0.000 description 2
- 101100005280 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-3 gene Proteins 0.000 description 2
- 101100126846 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) katG gene Proteins 0.000 description 2
- 241000219782 Sesbania Species 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical group [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 241000219793 Trifolium Species 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
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- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
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- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a preparation method of a hydrogenation protective agent, which comprises the following steps: (1) Immersing an alumina carrier precursor into an epoxypropane aqueous solution for sealing heat treatment, carrying out solid-liquid separation on the treated material, and drying and roasting the solid material to obtain an alumina carrier; (2) Sequentially impregnating the alumina carrier in the step (1) with a low-concentration hydrogenation active component impregnating solution and a high-concentration hydrogenation active component impregnating solution, and drying and roasting the impregnated material to obtain the hydrogenation protective agent. The hydrogenation protective agent has gradient active metal distribution and forms an open pore canal among flaky alumina grains, is used in the hydrotreating process of heavy residual oil, and has higher capability of removing metal impurities such as Ca, fe and the like and higher capability of removing metal Ni and V.
Description
Technical Field
The invention belongs to the field of catalytic material preparation, and particularly relates to a preparation method of a hydrogenation protective agent.
Background
The deep processing of heavy oil including residual oil is beneficial to improving the utilization rate of the heavy oil, relieving the tension trend of energy supply, reducing environmental pollution and achieving clean utilization of energy. The heavy oils such as oil residues have high contents of metal atoms such as nickel (Ni), vanadium (V), iron (Fe), and calcium (Ca) as compared with the distillate oils, and iron is concentrated in the heavy oils in the form of iron naphthenate in some heavy oils having a higher naphthenic acid content. Ni, V, fe, ca and other metal impurities easily cause scaling and blockage of a catalyst bed layer in the residual oil hydrogenation process, so that the device is forced to be stopped due to overlarge pressure drop. One of the effective ways to solve this problem is to fill the upper part of the hydrogenation catalyst with a protective agent having hydrogenation activity (i.e., hydrogenation protective agent).
CN106622307a discloses a hydrogenation protecting agent and its preparation method and application, the protecting agent contains active metal component and modified hydrogenation catalyst carrier, the described modified hydrogenation catalyst carrier is formed by repeatedly and sequentially impregnating and drying carrier which is undergone the process of hydro-thermal treatment, and roasting the dried product obtained in the last time, in which the impregnating liquor used in every impregnating process contains the compound which can provide same or different acid auxiliary agent, and the number of times n is greater than or equal to 2, and when n is greater than or equal to 3, in the process from 2 nd impregnating to n-1 st impregnating, the drying temperature after every impregnating is higher than that of adjacent previous impregnating by 20-150 deg.c, and the drying time after every impregnating is longer than that of adjacent previous impregnating by 1-10 hr. The method can obtain the modified hydrogenation catalyst carrier with acid assistants distributed in a layered manner, but the pore canal on the surface of the carrier is not wide, and the diffusion of residual oil macromolecular reactants is not favored.
CN111821990a discloses a residual oil hydrogenation protecting agent carrier, a catalyst and a preparation method thereof, wherein the carrier is a modified alumina-based carrier, and the modified alumina-based carrier contains a modifying element and a first hydrogenation active metal component; the modified alumina-based carrier comprises main body modified alumina and rod-shaped modified alumina, wherein the main body modified alumina is alumina with micron-sized pore canals, and at least part of the rod-shaped modified alumina is distributed on the outer surface of the main body modified alumina and in the micron-sized pore canals with the pore diameter D of 5-10 mu m; the modifying element is vanadium, and the first hydrogenation active metal component is molybdenum. The alumina carrier prepared by the method has better pore channel penetrability, but the firmness degree of the combination of the rod-shaped alumina growing on the surface and the main alumina needs to be further improved.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method of a hydrogenation protective agent, which has gradient active metal distribution and forms an open pore canal among flaky alumina grains, is used for the hydrotreating process of heavy residual oil, and has higher capability of removing metal impurities such as Ca, fe and the like and higher capability of removing metal Ni and V.
The preparation method of the hydrogenation protective agent comprises the following steps:
(1) Immersing an alumina carrier precursor into an epoxypropane aqueous solution for sealing heat treatment, carrying out solid-liquid separation on the treated material, and drying and roasting the solid material to obtain an alumina carrier;
(2) Sequentially impregnating the alumina carrier in the step (1) with a low-concentration hydrogenation active component impregnating solution and a high-concentration hydrogenation active component impregnating solution, and drying and roasting the impregnated material to obtain the hydrogenation protective agent.
In the method of the invention, the alumina carrier precursor in the step (1) is gamma-phase alumina, and can be purchased or self-made. The alumina carrier precursor may be in the shape of a conventional alumina carrier, such as a sphere, having a particle size of generally 2-8.0mm, such as a cylindrical bar, clover, etc., having a diameter of about 0.2-3.0mm and a length of about 3-8.0mm. The gamma-phase alumina carrier preferably has a specific surface area of 120-260m 2/g, a pore volume of 0.5-1.0mL/g, a pore volume of pores with a pore diameter of less than 10nm accounting for less than 30% of the total pore volume, and a pore volume of pores with a pore diameter of 10-30nm accounting for 40% -60% of the total pore volume.
In the method of the present invention, the gamma-phase alumina support precursor of step (1) is generally prepared by the following method: kneading, shaping, drying and roasting the pseudo-boehmite to obtain the product. The kneading molding is carried out by a conventional method in the field, and an extrusion aid, a physical pore-expanding agent and a peptizing agent can be added according to the requirement in the molding process. The extrusion aid is sesbania powder, and the addition amount of the extrusion aid is 0.1-0.5 wt% of the weight of the alumina carrier. The physical pore-expanding agent is starch, activated carbon, crop straw particles and other substances, and the addition amount of the physical pore-expanding agent is 1-5 wt% of the weight of the alumina carrier. The peptizing agent is one or more of hydrochloric acid, nitric acid, sulfuric acid, acetic acid, oxalic acid and the like, and the addition amount of the peptizing agent is 0.5-1.5 wt% of the weight of the alumina carrier. The drying temperature is 100-160 ℃, and the drying time is 6-10 hours; the roasting temperature is 450-600 ℃ and the roasting time is 4-6 hours; the calcination is carried out in an oxygen-containing atmosphere, preferably in an air atmosphere.
In the method, the mass percentage concentration of the propylene oxide aqueous solution in the step (1) is 2.5-12%, preferably 4-8%, and the mass ratio of the dosage of the propylene oxide aqueous solution to the alumina carrier precursor is 3:1-10:1, preferably 4:1-8:1.
In the process of the present invention, the sealing heat treatment in step (1) is carried out in a closed vessel, preferably an autoclave, which is a two-step sealing heat treatment, i.e., a sealing heat treatment at 60 to 100℃for 1 to 4 hours, followed by a treatment at 110 to 180℃and preferably 120 to 160℃for 14 to 20 hours, preferably 16 to 20 hours.
In the method of the invention, the drying temperature in the step (1) is 100-160 ℃, the drying time is 2-8 hours, the roasting temperature is 750-950 ℃, the roasting time is 4-6 hours, and the roasting is carried out in an oxygen-containing atmosphere, preferably in an air atmosphere.
In the method, the alumina carrier obtained in the step (1) comprises main alumina and flaky alumina grains which grow on the outer surface of the main alumina in situ, wherein the flaky alumina grains have a parallelepiped structure, and the grain size is 100-400nm; the flaky alumina grains are piled up on the outer surface of the main alumina body to form pores with the diameter of 40-300 nm. The coverage rate of the flaky alumina grains on the outer surface of the main body alumina is 85% -100%, wherein the coverage rate refers to the percentage of the surface occupied by the flaky alumina grains on the outer surface of the main body alumina to the outer surface of the main body alumina.
In the method of the present invention, the low-concentration hydrogenation active component impregnation liquid and the high-concentration hydrogenation active component impregnation liquid in the step (2) may be active metal components adopted by conventional residuum hydrotreating catalysts, and are generally group VIB metals and/or group VIII metals, wherein the group VIB metals are preferably Mo and/or W, and the group VIII metals are preferably Co and/or Ni. The content of the VIB group metal in the low-concentration hydrogenation active component impregnating solution is 6.5-15.0 g/100mL based on metal oxide, the content of the VIII group metal is 1.5-6.0 g/100mL based on metal oxide, and the dosage of the low-concentration hydrogenation active component impregnating solution is 70-90% of the saturated water absorption capacity of the alumina carrier. The content of the VIB group metal in the high-concentration hydrogenation active component impregnating solution is 4.5-8.5 g/100mL calculated by metal oxide, the content of the VIII group metal is 1.2-3.5g/100mL calculated by metal oxide, and the dosage of the high-concentration hydrogenation active component impregnating solution is 25-35% of the saturated water absorption capacity of the alumina carrier. The hydrogenation active components in the low-concentration hydrogenation active component impregnating solution and the high-concentration hydrogenation active component impregnating solution can be the same or different; the sum of the dosage of the low-concentration hydrogenation active component impregnating solution and the high-concentration hydrogenation active component impregnating solution is the saturated water absorption capacity of the alumina carrier.
In the method, the drying temperature in the step (2) is 100-160 ℃, the drying time is 2-8 hours, the roasting temperature is 450-550 ℃, and the roasting time is 4-6 hours.
The hydrogenation protective agent prepared by the method is suitable for the hydrogenation treatment process of heavy residual oil.
Compared with the prior art, the invention has the following advantages:
(1) The pore canal of the outer surface of the alumina carrier used in the hydrogenation protective agent is formed by stacking flaky grain alumina, flaky particles are easy to contact with residual oil reaction raw materials on one hand, the reaction activity of the catalyst is improved, and on the other hand, the pore canal structure formed by interweaving and stacking flaky particles is wide, so that macromolecular reactants can be easily diffused into the carrier. Meanwhile, the flaky alumina has uniform grain structure, strong binding force with the surface of the carrier, firm pore canal, simple preparation process of the used alumina carrier and easy industrial production.
(2) The invention sequentially uses the active component impregnating solutions with different concentrations to impregnate the carrier, so that the active metal content of the central part of the final catalyst is relatively high, and the active metal content of the surface layer is relatively low. In the hydrogenation reaction process, the flaky particles on the surface and pore channels formed by stacking the flaky particles can effectively remove Ca, fe and other metal impurities in the residual oil raw material, and the pore channels in the catalyst are favorable for removing Ni, V and other metal impurities in the residual oil raw material.
Drawings
FIG. 1 is a low-magnification SEM image of an alumina carrier prepared in example 3.
FIG. 2 is a high-magnification SEM image of an alumina carrier prepared in example 3.
FIG. 3 is a low-magnification SEM image of the alumina carrier prepared in comparative example 2.
FIG. 4 is a high-magnification SEM image of the alumina carrier prepared in comparative example 2.
Detailed Description
The technical scheme and effect of the present invention will be further described with reference to the following examples, but is not limited thereto. Wherein, in the invention, wt% represents mass fraction.
BET method: the pore structure of the carrier of the examples and the comparative examples is characterized by physical adsorption-desorption by using N 2, and the specific operation is as follows: and (3) characterizing the structure of the sample hole by adopting an ASAP-2420 type N 2 physical absorption-desorption instrument. And (3) taking a small amount of sample, vacuum-treating for 3-4 hours at 300 ℃, and finally placing the product under the condition of low temperature (-200 ℃) of liquid nitrogen for nitrogen adsorption-desorption test. Wherein the specific surface area is obtained according to BET equation, and the distribution ratio of pore volume and pore diameter below 30nm is obtained according to BJH model.
The microstructure of the alumina carrier is characterized by applying a scanning electron microscope, and the specific operation is as follows: the JSM-7500F scanning electron microscope is adopted to characterize the microstructure of the carrier, the accelerating voltage is 5KV, the accelerating current is 20 mu A, and the working distance is 8mm.
The most probable pore size measurement: and taking the pore diameter of the material as an abscissa, taking the change rate of pore volume along with the pore diameter as an ordinate to obtain a pore diameter differential distribution curve, wherein the peak value in the curve is the most probable pore diameter.
Preparation of alumina support precursor:
Weighing 500 g of pseudo-boehmite (prepared by an aluminum alkoxide method), adding 3g of sesbania powder and 5g of carbon black powder, uniformly mixing, adding an appropriate amount of acetic acid solution with the mass concentration of 0.5% into the mixture, uniformly kneading, extruding and molding, drying the molded material at 120 ℃ for 8 hours, roasting at 550 ℃ for 5 hours to prepare an alumina carrier precursor S0, wherein the specific surface area of the alumina carrier precursor is 145m 2/g, the pore volume is 0.87mL/g, the pore volume of pores with the diameter smaller than 10nm accounts for 28% of the total pore volume, and the pore volume of pores with the diameter of 15-30nm accounts for 51% of the total pore volume.
Example 1
(1) 100G of alumina carrier precursor S0 is weighed, 520 g of propylene oxide solution with the mass concentration of 6.5% is added, the mixed material is transferred into an autoclave, the autoclave is placed into an oven after sealing for sealing treatment for 3 hours at 75 ℃, then the temperature is raised to 145 ℃ for sealing treatment for 18 hours, the treated material is cooled, washed and filtered, the solid material is dried for 8 hours at 120 ℃, the solid material is baked for 5 hours at 850 ℃, and the alumina carrier S1 is prepared, and the scanning electron microscope image of the outer surface of the carrier is shown in figures 1 and 2.
(2) Weighing 50 g of alumina carrier S1, placing the carrier in a spray-dipping roller pot, spraying and dipping the alumina carrier by using active component dipping liquid I with the concentration of molybdenum oxide of 9.1g/100mL and the concentration of nickel oxide of 2.4g/100mL, then continuously spraying and dipping the alumina carrier by using active component dipping liquid II with the concentration of molybdenum oxide of 6.0g/100mL and the concentration of nickel oxide of 1.4g/100mL to saturate the carrier adsorption, drying the dipped material at 120 ℃ for 5 hours, roasting at 450 ℃ for 5 hours, and obtaining a hydrogenation protective agent Cat-1, wherein the catalyst property is shown in table 1.
Example 2
The procedure of example 1 was followed except that the propylene oxide concentration in step (1) was 5.3%, the amount of the solution was 640 g, and the carrier calcination temperature was 900℃after the hydrothermal treatment was conducted at 85℃for 2 hours and then at 135℃for 19 hours. The concentration of molybdenum oxide in the active component impregnating solution I is 10.1g/100mL, the concentration of nickel oxide is 2.6g/100mL, the solution dosage is 24mL, the concentration of molybdenum oxide in the active component impregnating solution II is 5.5g/100mL, the concentration of nickel oxide is 1.3g/100mL, and the hydrogenation protective agent Cat-2 is prepared, and the catalyst properties are shown in Table 1.
Example 3
The procedure of example 1 was followed except that the propylene oxide concentration in step (1) was 4.2%, the amount of the solution was 750 g, and the carrier calcination temperature was 950℃after the hydrothermal treatment was conducted at 65℃for 4 hours and then at 120℃for 20 hours. The concentration of molybdenum oxide in the active component impregnating solution I in the step (2) is 9.6g/100mL, the concentration of nickel oxide in the active component impregnating solution I is 2.5g/100mL, the solution dosage is 22.5mL, the concentration of molybdenum oxide in the active component impregnating solution II is 5.0g/100mL, the concentration of nickel oxide in the active component impregnating solution II is 1.2g/100mL, and the hydrogenation protective agent Cat-3 is prepared, wherein the catalyst properties are shown in Table 1.
Example 4
The same as in example 1, except that the propylene oxide concentration in step (1) was 7.5%, the solution amount was 430 g, and the hydrothermal treatment was conducted at 95℃for 1.5 hours and then at 155℃for 16.5 hours. The concentration of molybdenum oxide in the active component impregnating solution I in the step (2) is 8.5g/100mL, the concentration of nickel oxide in the active component impregnating solution I is 2.3g/100mL, the solution dosage is 27mL, the concentration of molybdenum oxide in the active component impregnating solution II is 6.5g/100mL, the concentration of nickel oxide in the active component impregnating solution II is 1.5g/100mL, and the hydrogenation protective agent Cat-4 is prepared, wherein the catalyst properties are shown in Table 1.
Comparative example 1
A comparative hydrogenation protecting agent Cat-5 was prepared as in example 1 except that the propylene oxide solution was changed to an aqueous ammonia solution of the same mass concentration in step (1), and the catalyst properties were shown in Table 1.
Comparative example 2
The comparative hydrogenation protecting agent Cat-6 was prepared by the same procedure as in example 1 except that the propylene oxide solution was changed to the ethylene oxide solution having the same concentration in step (1), and the scanning electron microscope images of the outer surface of the prepared alumina carrier were shown in FIG. 3 and FIG. 4, and the catalyst properties were shown in Table 1.
Comparative example 3
Comparative hydrogenation protecting agent Cat-7 was prepared as in example 1 except that the propylene oxide concentration in step (1) was 1%, and the catalyst properties are shown in Table 1.
Comparative example 4
The comparative hydrogenation protecting agent Cat-8 was prepared as in example 1 except that the hydrothermal treatment in step (1) was one-step hydrothermal treatment at 90℃for 22 hours, and the catalyst properties are shown in Table 1.
TABLE 1 hydrogenation protectant Properties
Example 5
The hydrogenation protection catalysts Cat-1, cat-2, cat-3, cat-4 and comparative examples prepared by the invention are respectively filled into fixed bed hydrogenation reactors, and the treated raw materials (see Table 2) are tested as follows: the reaction temperature is 385 ℃, the hydrogen-oil volume ratio is 785, the liquid hourly space velocity is 1.0h -1, the hydrogen partial pressure is 15.5MPa, the continuous operation is carried out for 2000 hours, and the impurity removal property is shown in Table 3.
TABLE 2 oil Properties of raw materials
Table 3 evaluation results of catalysts
As can be seen from the results in Table 3, compared with the comparative hydrogenation protecting agent, the hydrogenation protecting catalyst prepared by the method of the invention has higher Ca, fe, ni, V removal rate and good stability.
Claims (10)
1. The preparation method of the hydrogenation protective agent is characterized by comprising the following steps: (1) Immersing an alumina carrier precursor into an epoxypropane aqueous solution for sealing heat treatment, carrying out solid-liquid separation on the treated material, and drying and roasting the solid material to obtain an alumina carrier; (2) Sequentially impregnating the alumina carrier in the step (1) with a low-concentration hydrogenation active component impregnating solution and a high-concentration hydrogenation active component impregnating solution, and drying and roasting the impregnated material to obtain the hydrogenation protective agent.
2. The method according to claim 1, characterized in that: the alumina carrier precursor in the step (1) is gamma-phase alumina, the particle diameter is 2-8.0mm, the specific surface area is 120-260m 2/g, the pore volume is 0.5-1.0mL/g, the pore volume of the pores with the pore diameter smaller than 10nm accounts for less than 30% of the total pore volume, and the pore volume of the pores with the pore diameter of 10-30nm accounts for 40% -60% of the total pore volume.
3. The method according to claim 1, characterized in that: the mass percentage concentration of the epoxypropane aqueous solution in the step (1) is 2.5-12%, preferably 4-8%.
4. The method according to claim 1, characterized in that: the mass ratio of the dosage of the epoxypropane aqueous solution to the alumina carrier precursor in the step (1) is 3:1-10:1, preferably 4:1-8:1.
5. The method according to claim 1, characterized in that: the sealing heat treatment in the step (1) is carried out in a closed container, and the sealing heat treatment is as follows: sealing and heat treating at 60-100deg.C for 1-4 hr, and then at 110-180deg.C for 14-20 hr.
6. The method according to claim 1, characterized in that: the drying temperature in the step (1) is 100-160 ℃, and the drying time is 2-8 hours; the roasting temperature is 750-950 ℃, the roasting time is 4-6 hours, and the roasting is carried out in an oxygen-containing atmosphere.
7. The method according to claim 1, characterized in that: the alumina carrier obtained in the step (1) comprises main alumina and flaky alumina grains which grow on the outer surface of the main alumina in situ, wherein the flaky alumina grains have a parallelepiped structure, and the grain size is 100-400nm; the flaky alumina grains are piled up on the outer surface of the main body alumina to form pore channels of 40-300 nm; the coverage rate of the flaky alumina grains on the outer surface of the main body alumina is 85% -100%, wherein the coverage rate refers to the percentage of the surface occupied by the flaky alumina grains on the outer surface of the main body alumina to the outer surface of the main body alumina.
8. The method according to claim 1, characterized in that: the low-concentration hydrogenation active component impregnating solution and the high-concentration hydrogenation active component impregnating solution in the step (2) adopt active metal components which are VIB group metals and/or VIII group metals, wherein the VIB group metals are preferably Mo and/or W, and the VIII group metals are preferably Co and/or Ni; the content of the VIB group metal in the low-concentration hydrogenation active component impregnating solution is 6.5-15.0 g/100mL in terms of metal oxide, the content of the VIII group metal is 1.5-6.0 g/100mL in terms of metal oxide, and the dosage of the low-concentration hydrogenation active component impregnating solution is 70-90% of the saturated water absorption capacity of the alumina carrier; the content of the VIB group metal in the high-concentration hydrogenation active component impregnating solution is 4.5-8.5 g/100mL calculated by metal oxide, the content of the VIII group metal is 1.2-3.5g/100mL calculated by metal oxide, and the dosage of the high-concentration hydrogenation active component impregnating solution is 25-35% of the saturated water absorption capacity of the alumina carrier; the sum of the dosage of the low-concentration hydrogenation active component impregnating solution and the high-concentration hydrogenation active component impregnating solution is the saturated water absorption capacity of the alumina carrier.
9. The method according to claim 1, characterized in that: the drying temperature in the step (2) is 100-160 ℃, and the drying time is 2-8 hours; the roasting temperature is 450-550 ℃ and the roasting time is 4-6 hours.
10. The hydrogenation protective agent prepared by the method according to any one of claims 1-9 is suitable for the hydrotreating process of heavy residual oil.
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