CN111821992B - Preparation method of high-activity hydrodemetallization catalyst - Google Patents
Preparation method of high-activity hydrodemetallization catalyst Download PDFInfo
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- CN111821992B CN111821992B CN201910311688.8A CN201910311688A CN111821992B CN 111821992 B CN111821992 B CN 111821992B CN 201910311688 A CN201910311688 A CN 201910311688A CN 111821992 B CN111821992 B CN 111821992B
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- catalyst
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- ammonium bicarbonate
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- 239000003054 catalyst Substances 0.000 title claims abstract description 74
- 230000000694 effects Effects 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 62
- 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 38
- 238000001035 drying Methods 0.000 claims abstract description 33
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- 239000000243 solution Substances 0.000 claims abstract description 19
- 239000007864 aqueous solution Substances 0.000 claims abstract description 17
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 16
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- KKTCWAXMXADOBB-UHFFFAOYSA-N azanium;hydrogen carbonate;hydrate Chemical compound [NH4+].O.OC([O-])=O KKTCWAXMXADOBB-UHFFFAOYSA-N 0.000 claims abstract 2
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/90—Regeneration or reactivation
- B01J23/94—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the iron group metals or copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/394—Metal dispersion value, e.g. percentage or fraction
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1077—Vacuum residues
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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- 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
- C10G2300/205—Metal content
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/205—Metal content
- C10G2300/206—Asphaltenes
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
- C10G2300/701—Use of spent catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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Abstract
The invention discloses a preparation method of a high-activity hydrodemetallization catalyst, which comprises the following steps: (1) immersing the treated waste hydrotreating catalyst into an ammonium bicarbonate water solution for heat treatment, drying the material, then immersing the material in a polyethylene glycol solution, and drying to obtain a pretreated material A; (2) immersing alumina powder into an ammonium bicarbonate aqueous solution for sealing heat treatment, drying the heat-treated material, and immersing the material in an immersion liquid containing a hydrogenation active component I to obtain a pretreated material B; (3) kneading and molding pseudo-boehmite, the pretreatment material A and the pretreatment material B, and drying and roasting the molded product to obtain a carrier; (4) impregnating the carrier with an impregnation liquid containing a hydrogenation active component II, and drying and roasting the carrier to obtain the hydrogenation demetallization catalyst. The method utilizes the waste catalyst to prepare the hydrodemetallization catalyst, reduces the production cost and pollution, and has higher hydrodemetallization activity and stronger asphaltene conversion capacity.
Description
Technical Field
The invention relates to the field of catalyst preparation, in particular to a preparation method of a high-activity hydrodemetallization catalyst.
Background
With the deterioration and heaviness of crude oil, the efficient conversion of heavy oil and the improvement of the yield of light oil products become an important trend in the development of oil refining technology. The residue fixed bed hydrogenation technology is an effective means for realizing the high-efficiency conversion of heavy oil. By adopting the technical route, the impurities such as metal, sulfur, nitrogen, carbon residue and the like in the residual oil can be effectively removed, high-quality feed is provided for catalytic cracking, and the strict environmental protection regulation requirements are met while the yield of light oil products is increased. During the processing of heavy oil, the metal compounds in the heavy oil are decomposed, and metal impurities are deposited on the inner surface and the outer surface of the catalyst to block the pore channels, so that the catalyst is even poisoned and deactivated.
In the using process of the catalyst, the catalyst becomes waste due to the loss of the original activity, and the waste catalyst rich in metal is not used, so that resources are wasted and the environment is polluted. Recently, environmental regulations have become more stringent for the disposal of spent catalysts. The waste catalyst is treated by several methods, such as landfill treatment, metal recovery, regeneration or recycling, and is used as a raw material to generate other useful products to solve the problem of the waste catalyst.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method of a high-activity hydrodemetallization catalyst. The method utilizes the waste catalyst to prepare the hydrodemetallization catalyst, reduces the production cost and environmental pollution, and the hydrodemetallization catalyst has higher hydrodemetallization activity and stronger asphaltene conversion capability.
The preparation method of the high-activity hydrodemetallization catalyst comprises the following steps:
(1) the waste hydrotreating catalyst is crushed and then roasted. Immersing the treated material into an ammonium bicarbonate aqueous solution for sealing heat treatment, drying the treated material, then soaking the treated material in a polyethylene glycol solution, filtering and drying to obtain a pretreated material A;
(2) immersing alumina powder into an ammonium bicarbonate aqueous solution for sealing heat treatment, drying the heat-treated material, and immersing the material in an immersion liquid containing a hydrogenation active component I to obtain a pretreated material B;
(3) kneading and molding pseudo-boehmite, the pretreatment material A and the pretreatment material B, and drying and roasting molded objects to obtain carriers;
(4) and (3) impregnating the carrier with an impregnating solution containing a hydrogenation active component II, and then drying and roasting to obtain the hydrogenation demetallization catalyst.
In the method of the present invention, the spent hydrotreating catalyst in step (1) refers to a hydrotreating catalyst such as hydrodesulfurization, denitrification, etc. of distillate oil and residual oil which has not achieved the reaction requirement or has not been completely deactivated due to gradation. The hydrotreating catalyst contains hydrogenation active metal, the active metal is one or more of VIB and VIII group metals, and the waste hydrotreating catalyst contains sulfide and alumina of the active metal, and also contains other oxides such as titanium oxide, silicon oxide, boron oxide, molecular sieves and the like, and impurities such as carbon deposition, heavy metals and the like. The active metal content on the spent hydroprocessing catalyst is typically from 1wt% to 40wt% of the catalyst weight and the metal impurities are typically from 0.1wt% to 30 wt%. The shape is generally cylindrical, spherical or multi-lobed. The waste hydrotreating catalyst is crushed to be more than 200 meshes, and preferably 400-800 meshes. The roasting temperature is 700-950 ℃, and the roasting time is 6-12 hours.
In the method, the dosage of the ammonium bicarbonate aqueous solution in the step (1) is at least used for immersing and roasting the waste hydrotreating catalyst, and the mass percentage concentration of the ammonium bicarbonate aqueous solution is 15-25%.
In the method, the sealing heat treatment temperature in the step (1) is 120-180 ℃, preferably 120-160 ℃, and the treatment time is 4-8 hours.
In the method of the present invention, the drying conditions in step (1) are as follows: the drying temperature is 100-160 ℃, and the drying time is 6-10 hours.
According to the method, the pretreated material A in the step (1) is of a mutually staggered columnar structure, the length of the columnar structure is 0.5-2 mu m, and the diameter of the columnar structure is 50-200 nm.
In the method of the invention, the alumina powder in the step (2) is gamma-alumina powder which is prepared according to the prior art or is commercially available. The preparation method is generally a pseudo-boehmite roasting method, wherein the roasting temperature is 450-600 ℃, and the roasting time is 4-8 hours. The dosage of the ammonium bicarbonate aqueous solution is that at least alumina powder is immersed, and the mass concentration of the ammonium bicarbonate aqueous solution is 15-25%. The sealing heat treatment temperature is 120-160 ℃, and the treatment time is 4-8 hours. The drying conditions were as follows: the drying temperature is 100-160 ℃, and the drying time is 6-10 hours.
In the method, the pretreatment material B in the step (2) is a cluster structure formed by disordered and staggered rod-shaped alumina, the outer diameter of the rod-shaped alumina cluster is 5-20 mu m, wherein the rod-shaped alumina accounts for more than 85% of the rod-shaped alumina cluster, preferably more than 90%, the rest is spherical or ellipsoidal alumina, the length of a single rod-shaped alumina is 1-5 mu m, and the diameter is 100-300 nm.
In the method, the mass ratio of the pretreatment material A, the pretreatment material B and the pseudo-boehmite in the step (3) is 1:10:30-1:2: 15.
In the method of the invention, the kneading molding in the step (3) is carried out by adopting a conventional method in the field, and in the molding process, conventional molding aids, such as one or more of peptizing agents, extrusion aids and the like, can be added according to the needs. The peptizing agent is one or more of hydrochloric acid, nitric acid, sulfuric acid, acetic acid, oxalic acid and the like; the extrusion aid is sesbania powder. The drying temperature is 100-160 ℃, and the drying time is 6-10 hours; the roasting temperature is 600-750 ℃, and the roasting time is 4-6 hours; the calcination is carried out in an oxygen-containing atmosphere, preferably an air atmosphere.
In the method, the content of Co in the dipping solution containing the hydrogenation active component I is 2.0-4.5g/100mL calculated by oxide, the content of W is 0.5-1.0g/100mL calculated by metal oxide, and the using amount of the solution is the saturated water absorption capacity of the material after hydrothermal treatment; the content of Mo in the dipping solution containing the hydrogenation active component II is 8-15g/100mL calculated by oxide, and the content of Ni is 2.5-4.0g/100mL calculated by metal oxide.
In the method, the drying temperature in the step (4) is 100-160 ℃, and the drying time is 6-10 hours; the roasting temperature is 400-550 ℃, and the roasting time is 4-6 hours; the calcination is carried out in an oxygen-containing atmosphere, preferably an air atmosphere.
Compared with the prior art, the invention has the following advantages:
(1) the invention takes the waste hydrogenation catalyst as the raw material, obtains the mutually staggered columnar structure through the simple pretreatment process, forms larger through pore channels by forming with pseudo-boehmite and dispersing in a carrier, and the pore channels are mutually communicated, thereby being beneficial to the mass transfer and the diffusion of macromolecular reactants, having higher metal-containing capability, further concentrating active metal in the waste catalyst by the columnar structure, simultaneously exposing more surfaces by the columnar structure, increasing more active sites by further loading active components, ensuring that the catalyst has higher activity, simultaneously ensuring that the catalyst has good stability, and prolonging the operation period of the device.
(2) In the invention, part of alumina powder with a rod-like cluster structure is added and doped into an alumina carrier, and the rod-like cluster structure is integrally dispersed in the carrier to form a larger through pore channel, thus being beneficial to the mass transfer and diffusion of macromolecular reactants; in addition, active metal W, Co is introduced into the rod-shaped alumina cluster structure in advance, and active metals Mo and Ni are introduced during later impregnation, so that a multi-component composite component structure of W, Co, Mo and Ni is formed at the rod-shaped alumina cluster structure, and the composite component is organically combined with the pore channel of the carrier, so that the hydrodemetallization activity and the asphaltene conversion capability of the catalyst are improved.
(3) The method is simple, and the alumina raw material is replaced by partial waste catalyst, so that the waste is changed into valuable, the production cost is reduced, and the environmental pollution is reduced.
Drawings
FIG. 1 SEM images of pretreated materials A-I.
FIG. 2 SEM images of pretreated materials B-I.
Detailed Description
The technical solutions and effects of the present invention are further described below with reference to the following examples, but the present invention is not limited to the following examples. Wherein, in the present invention, wt% represents a mass fraction.
The BET method: application N 2 Physical adsorption-desorption characterization of the pore structures of the carriers of the examples and the comparative examples, the specific operations are as follows: adopting ASAP-2420 type N 2 And the physical adsorption-desorption instrument is used for characterizing the pore structure of the sample. A small amount of samples are taken to be treated for 3 to 4 hours in vacuum at the temperature of 300 ℃, and finally, the product is placed under the condition of liquid nitrogen low temperature (-200 ℃) to be subjected to nitrogen absorption-desorption test. Wherein the specific surface area is obtained according to a BET equation, and the distribution rate of the pore volume and the pore diameter below 30nm is obtained according to a BJH model.
Mercury pressing method: the pore diameter distribution of the samples of the examples and the comparative examples is characterized by applying a mercury porosimeter, and the specific operation is as follows: and characterizing the distribution of sample holes by using an American microphone AutoPore9500 full-automatic mercury porosimeter. The samples were dried, weighed into an dilatometer, degassed for 30 minutes while maintaining the vacuum conditions given by the instrument, and filled with mercury. The dilatometer was then placed in the autoclave and vented. Then, the voltage boosting and reducing tests are carried out. The mercury contact angle is 130 degrees, and the mercury interfacial tension is 0.485N.cm -1 The distribution ratio of the pore diameter of 100nm or more is measured by mercury intrusion method.
The scanning electron microscope is used for representing the microstructure of a sample, and the specific operation is as follows: and a JSM-7500F scanning electron microscope is adopted to represent the microstructure of the sample, the accelerating voltage is 5kV, the accelerating current is 20 muA, and the working distance is 8 mm.
The method adopts NB/SH/T0704-.
The sulfur content in the oil product is determined by adopting an SH/T0689-.
The content of carbon residue in the oil product is determined by adopting an SH/T0266-92 standard method.
And the contents of Ni and V in the oil product are determined by adopting a GB/T34099-2017 standard method.
The waste catalyst used in the examples is the waste catalyst (containing MoO) of fixed bed residue oil hydrogenation industrial device 3 ：5%，NiO：8.3%，V 2 O 5 ：17.8%，Fe 2 O 3 ：1.6%，Al 2 O 3 : 52.4, C: 14.9%), extracted to remove oil on the surface of the catalyst and dried.
Preparation of pretreated Material A:
taking the waste catalyst crushed to more than 230 meshes, roasting at 750 ℃ for 8 hours, weighing 100 g of the waste catalyst, placing the waste catalyst into 400 g of ammonium bicarbonate aqueous solution with the mass concentration of 24%, transferring the mixed material into a high-pressure kettle, sealing, heating at 130 ℃ for 8 hours, and drying the powder at 110 ℃ for 6 hours to obtain a pretreated material A-I, wherein a scanning electron microscope image of the A-I is shown in figure 1.
Taking waste catalyst crushed to more than 230 meshes, roasting at 900 ℃ for 8 hours, weighing 100 g of the waste catalyst, placing the waste catalyst into 600 g of ammonium bicarbonate aqueous solution with the mass concentration of 20%, transferring the mixed material into a high-pressure kettle, sealing, heating at 155 ℃ for 6 hours, and drying the powder at 110 ℃ for 6 hours to obtain the pretreated material A-II.
Preparation of pretreated Material B:
weighing 200 g of alumina powder, placing the alumina powder into 1000 g of ammonium bicarbonate aqueous solution with the mass concentration of 22.5wt%, sealing the alumina powder in a closed high-pressure kettle, carrying out heat treatment at 155 ℃ for 4 hours, filtering and washing the alumina powder, drying the alumina powder at 110 ℃ for 6 hours, weighing 50 g of the dried material, soaking the dried material in a soaking solution I with the tungsten oxide concentration of 2.8g/100mL and the cobalt oxide concentration of 0.81g/100mL, and drying the soaked material at 120 ℃ for 6 hours to obtain a pretreated material B-I, wherein a scanning electron microscope image of the B-I is shown in figure 1.
Weighing 200 g of alumina powder, placing the alumina powder into 1400 g of ammonium bicarbonate aqueous solution with the mass concentration of 24.0wt%, sealing the alumina powder in a sealed high-pressure kettle, carrying out heat treatment at 140 ℃ for 6 hours, filtering and washing the alumina powder, drying the material at 110 ℃ for 6 hours, weighing 50 g of the dried material, soaking the material by using a soaking solution I with the tungsten oxide concentration of 3.1g/100mL and the cobalt oxide concentration of 0.75g/100mL, and drying the soaked material at 120 ℃ for 6 hours to obtain a pretreated material B-II.
Example 1
Weighing 150 g of pseudo-boehmite, 6.7 g of the pretreatment material A-I, 6.7 g of the pretreatment material B-I33 g and 2.5 g of sesbania powder, uniformly mixing the materials physically, adding a proper amount of aqueous solution dissolved with 3g of acetic acid, kneading, extruding into strips, forming, drying the formed product at 140 ℃ for 6 hours, and roasting the dried product in air at 750 ℃ for 5 hours to prepare the alumina carrier.
Weighing 50 g of the alumina carrier, adding 100mL of Mo-Ni-P impregnation liquid II (the concentration of molybdenum oxide in the impregnation liquid is 9.3g/100mL, and the concentration of nickel oxide is 3.43g/100 mL), impregnating for 2 hours, filtering out excessive solution, drying at 120 ℃, and roasting at 450 ℃ for 5 hours to obtain the demetallization catalyst Cat-1, wherein the properties of the catalyst are shown in Table 1.
Example 2
In the same manner as in example 1, except that the addition amount of the pretreatment material A-I was changed to 8.1 g of A-II, the addition amount of the pretreatment material B-I was changed to 29 g of B-II, the concentration of molybdenum oxide in the impregnation solution II was 9.1g/100mL, and the concentration of nickel oxide was 3.3g/100mL, the demetallization catalyst Cat-2 of the present invention was prepared, and the properties of the catalyst are shown in Table 1.
Example 3
Similar to example 1, except that the amounts of the pretreatment materials A to I added were 5.5 g, the amounts of the pretreatment materials B to I added were 45 g, the concentration of molybdenum oxide in the impregnation solution II was 8.9g/100mL, and the concentration of nickel oxide was 3.1g/100mL, the demetallization catalyst Cat-3 of the present invention was obtained, and the properties of the catalyst are shown in Table 1.
Example 4
The same as example 1, except that the amount of the pretreatment materials A-I added was 9.5 g, the amount of the pretreatment materials B-I was changed to B-II added was 22 g, the concentration of molybdenum oxide in the impregnation solution II was 9.4g/100mL, and the concentration of nickel oxide was 3.2g/100mL, to obtain the demetallization catalyst Cat-4 of the present invention, the properties of which are shown in Table 1.
Comparative example 1
Comparative demetallization catalyst Cat-5 was prepared as in example 1 except that the pretreatment feed A-I was treated at a treatment temperature of 100 ℃ in water treatment, and the catalyst properties are shown in Table 1.
Comparative example 2
Similar to example 1, except that the pretreated material B-I was not impregnated with the active metal W, Co, the same active metal was loaded on the surface of alumina in an impregnation manner to obtain a comparative demetallization catalyst Cat-6, and the catalyst properties are shown in Table 1.
Comparative example 3
A comparative demetallization catalyst Cat-7 was prepared as in example 1 except that pretreatment materials B-I were not added to the catalyst and the catalyst properties are shown in Table 1.
TABLE 1 catalyst Properties
Evaluation of catalytic performance:
the hydrodemetallization catalyst (Cat-1-Cat-7) prepared above was evaluated for catalytic performance by the following method:
the vacuum residue listed in Table 2 was used as a raw material, and the catalytic performance of Cat-1-Cat-7 was evaluated on a fixed bed residue hydrogenation reactor, the catalyst was a 2-3 mm long strip, and the reaction conditions were as follows: the reaction temperature is 387 ℃, the hydrogen partial pressure is 15.7MPa, and the liquid hour volume space velocity is 1.0 hour -1 The volume ratio of hydrogen to oil is 758, the content of each impurity in the produced oil is measured after 1500 hours of reaction, the impurity removal rate is calculated, and the evaluation result is shown in table 3.
TABLE 2 Properties of the feed oils
TABLE 3 comparison of catalyst hydrogenation performance
It can be seen from the data in table 3 that the catalyst prepared by the process of the present invention has higher hydrodemetallization activity and asphaltene hydroconversion compared to the comparative catalyst.
Claims (7)
1. A preparation method of a high-activity hydrodemetallization catalyst is characterized by comprising the following steps: (1) crushing the waste hydrotreating catalyst, roasting, soaking the treated material in ammonium bicarbonate water solution, sealing, heat treating, filtering, drying, soaking in polyethylene glycol solution, filtering, and drying to obtain pretreated material A; (2) immersing alumina powder into an ammonium bicarbonate aqueous solution for sealing heat treatment, drying the heat-treated material, and immersing the material in an immersion liquid containing a hydrogenation active component I to obtain a pretreated material B; (3) kneading and molding pseudo-boehmite, the pretreatment material A and the pretreatment material B, and drying and roasting molded objects to obtain carriers; (4) impregnating the carrier with impregnation liquid containing a hydrogenation active component II, and then drying and roasting to prepare the high-activity hydrogenation demetallization catalyst; wherein the hydrogenation active component I is W, Co, and the hydrogenation active component II is Mo and Ni; the sealing heat treatment temperature in the step (1) is 120-180 ℃, and the treatment time is 4-8 hours; the pretreatment material A in the step (1) is of a mutually staggered columnar structure, the length of the columnar structure is 0.5-2 mu m, and the diameter of the columnar structure is 50-200 nm; the sealing heat treatment temperature in the step (2) is 120-160 ℃, and the treatment time is 4-8 hours; the pretreatment material B in the step (2) is a cluster structure formed by disordered and staggered rod-shaped alumina, the outer diameter of the rod-shaped alumina cluster is 5-20 mu m, rod-shaped alumina accounts for more than 85% of the rod-shaped alumina cluster, the rest is spherical or ellipsoidal alumina, the length of a single rod-shaped alumina is 1-5 mu m, and the diameter is 100-300 nm.
2. The method of claim 1, wherein: the waste hydrotreating catalyst in the step (1) comprises active metal sulfide and an alumina carrier; the active metal content on the spent hydroprocessing catalyst is 1wt% to 40wt% of the weight of the catalyst.
3. The method of claim 1, wherein: the roasting temperature in the step (1) is 700-950 ℃, and the roasting time is 6-12 hours.
4. The method of claim 1, wherein: the dosage of the ammonium bicarbonate aqueous solution in the step (1) is at least to immerse the waste hydrotreating catalyst after roasting treatment, and the mass percentage concentration of the ammonium bicarbonate aqueous solution is 15-25%.
5. The method of claim 1, wherein: the amount of the ammonium bicarbonate aqueous solution in the step (2) is that at least alumina powder is immersed, and the mass concentration of the ammonium bicarbonate aqueous solution is 15-25%.
6. The method of claim 1, wherein: the mass ratio of the pretreatment material A, the pretreatment material B and the pseudo-boehmite in the step (3) is 1:10:30-1:2: 15.
7. The method of claim 1, wherein: the content of Co in the dipping solution containing the hydrogenation active component I in the step (2) is 2.0-4.5g/100mL calculated by oxide, the content of W is 0.5-1.0g/100mL calculated by metal oxide, and the using amount of the solution is the saturated water absorption amount of the material after hydrothermal treatment; the content of Mo in the dipping solution containing the hydrogenation active component II in the step (4) is 8-15g/100mL calculated by oxide, and the content of Ni is 2.5-4.0g/100mL calculated by metal oxide.
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| CN115957770B (en) * | 2021-10-08 | 2024-06-28 | 中国石油化工股份有限公司 | Preparation method of boiling bed residual oil hydrogenation catalyst |
| CN115957827B (en) * | 2021-10-08 | 2024-08-06 | 中国石油化工股份有限公司 | Activation regeneration method of ebullated bed residuum hydrogenation catalyst |
| CN115945199B (en) * | 2021-10-09 | 2024-06-28 | 中国石油化工股份有限公司 | Activation method of metal deposition deactivated catalyst and carbon-containing hydrogenation catalyst |
| CN116037141B (en) * | 2021-10-28 | 2024-08-06 | 中国石油化工股份有限公司 | Regeneration method of deactivated catalyst |
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