CN114602485A - Preparation method of hydrotreating catalyst - Google Patents
Preparation method of hydrotreating catalyst Download PDFInfo
- Publication number
- CN114602485A CN114602485A CN202011396878.3A CN202011396878A CN114602485A CN 114602485 A CN114602485 A CN 114602485A CN 202011396878 A CN202011396878 A CN 202011396878A CN 114602485 A CN114602485 A CN 114602485A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- roasting
- drying
- hours
- boehmite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 99
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 38
- 239000002699 waste material Substances 0.000 claims abstract description 36
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- 238000001035 drying Methods 0.000 claims abstract description 25
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 19
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 18
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims abstract description 18
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 18
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims abstract description 17
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 17
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 16
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 15
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 230000004913 activation Effects 0.000 claims abstract description 13
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
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- 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
- -1 VIB group metals Chemical class 0.000 description 2
- IOGARICUVYSYGI-UHFFFAOYSA-K azanium (4-oxo-1,3,2-dioxalumetan-2-yl) carbonate Chemical compound [NH4+].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O IOGARICUVYSYGI-UHFFFAOYSA-K 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
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- 238000006477 desulfuration reaction Methods 0.000 description 2
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- 238000010438 heat treatment Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 2
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- 229910003296 Ni-Mo Inorganic materials 0.000 description 1
- 229910018104 Ni-P Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910018536 Ni—P Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 238000012512 characterization method Methods 0.000 description 1
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- 235000006408 oxalic acid Nutrition 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—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
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- 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
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
- B01J35/64—Pore diameter
- B01J35/651—50-500 nm
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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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—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
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/205—Metal content
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of a hydrotreating catalyst, which comprises the following steps: (1) crushing a molybdenum-nickel heavy oil hydrogenation catalyst poisoned by vanadium to a certain particle size, preferably adding pseudo-boehmite and/or kaolin into crushed waste catalyst powder, uniformly mixing, and then roasting to obtain a material A; (2) mixing the material A, ammonium bicarbonate and water, carrying out hydrothermal activation treatment on the mixed material, carrying out solid-liquid separation on the treated material, and drying the solid material to obtain a material B; (3) uniformly mixing the material B with the pseudo-boehmite, adding a peptizer with a proper concentration into the mixed material, kneading and molding, and drying and roasting the molded product; (4) and (4) placing the alumina carrier roasted in the step (3) in a phosphoric acid solution for aging treatment, drying and roasting the aged material to obtain the alumina carrier, and then loading a hydrogenation active component to obtain the hydrogenation catalyst. The hydrotreating catalyst prepared by the method has higher hydrodemetallization and hydrodesulfurization activity.
Description
Technical Field
The invention relates to the field of catalyst preparation, in particular to a preparation method of a hydrotreating catalyst.
Background
The shortage and deterioration of global petroleum resources lead to the continuous improvement of the proportion of heavy crude oil and high-sulfur crude oil in the crude oil market, and simultaneously, the market demand for clean oil products is also rapidly increased along with the rapid development of economy and the increasingly strict environmental protection regulations in China. Therefore, the lightening and upgrading of heavy oil are important tasks which are urgently needed to be solved at present. The residual oil hydrotreating technology is an effective means for solving the problems. Heavy oil residues contain a large amount of sulfur, most of which is present in asphaltenes, and are difficult to remove. Hydrodesulfurization has been regarded as an important process in petroleum refining and synthetic ammonia production using petroleum as a raw material.
CN1107102C discloses a hydrodemetallization and hydrodesulfurization catalyst and a preparation method thereof, wherein a pore-expanding method is adopted by adding carbon black and the acidity of a carrier is adjusted by adding boron. The carrier obtained by the method has a double-peak structure, the first peak is concentrated at about 10nm, the second peak is a pore channel left after the carbon black is burnt out and is concentrated at about 200-500nm, most of the pore channels left by the carbon black are ink bottle openings, the pore channel is not beneficial to the separation of residual oil asphaltene micelles, and the hydrodesulfurization rate is low.
CN104646009A discloses a poor-quality heavy oil hydrodesulfurization catalyst and a preparation method thereof. The catalyst takes alumina as a carrier and VIII group and VIB elements, particularly Ni-Mo as active components, and is prepared by treating formed and roasted carrier particles with an acid solution with continuously increased concentration.
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 increasingly stringent requirements 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.
CN102441440A discloses a method for preparing a hydrotreating catalyst from a spent catalyst. Grinding the waste hydrotreating catalyst, adding alumina, a binder, an acid solution or an alkaline solution and other raw materials into the ground powder, kneading, molding, drying and roasting the molded sample to obtain the new hydrotreating catalyst. Although the method utilizes the waste catalyst to prepare the new hydrotreating catalyst, the pore volume of the catalyst needs to be further improved.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method of a hydrotreating catalyst. The method activates the deactivated waste catalyst to remove the deposited vanadium metal in the waste catalyst, so that the activated material has higher pore volume and specific surface area, and prepares the hydrotreating catalyst by taking the activated waste catalyst as part of raw materials, the added activated waste catalyst material can effectively adjust the pore structure of the hydrotreating catalyst, the content of macropores is improved, and the prepared hydrotreating catalyst has higher hydrodemetallization and hydrodesulfurization activity.
The preparation method of the hydrotreating catalyst comprises the following steps:
(1) crushing a molybdenum-nickel heavy oil hydrogenation catalyst poisoned by vanadium to a certain particle size, preferably adding pseudo-boehmite and/or kaolin into crushed waste catalyst powder, uniformly mixing, and then roasting to obtain a material A;
(2) mixing the material A, ammonium bicarbonate and water, carrying out hydrothermal activation treatment on the mixed material, carrying out solid-liquid separation on the treated material, and drying the solid material to obtain a material B;
(3) uniformly mixing the material B with the pseudo-boehmite, adding a peptizer with a proper concentration into the mixed material, kneading and molding, and drying and roasting the molded product;
(4) and (4) placing the alumina carrier roasted in the step (3) in a phosphoric acid solution for aging treatment, drying and roasting the aged material to obtain the alumina carrier, and then loading a hydrogenation active component to obtain the hydrogenation catalyst.
In the method, the molybdenum-nickel heavy oil hydrogenation catalyst poisoned by vanadium in the step (1) generally refers to a catalyst which is inactivated or can not meet the reaction requirement due to deposition of heavy metals such as vanadium, iron and the like and carbon deposit in the hydrogenation treatment processes such as hydrodemetallization, hydrodesulfurization, denitrification and the like of wax oil and residual oil; based on the weight of the catalyst, the content of vanadium is 5-30 percent by oxide, the active component of the catalyst is 3-20 percent by oxide, and the content of nickel is 2-15 percent by oxide.
In the method of the present invention, the molybdenum-nickel heavy oil poisoned by vanadium in the step (1) is hydro-pulverized to have a mesh number of more than 80 mesh, preferably more than 200 mesh, and more preferably 400-800 mesh. According to the invention, the pseudo-boehmite and/or the kaolin are preferably added into the crushed waste catalyst powder and uniformly mixed, and the mass ratio of the waste catalyst to the pseudo-boehmite and/or the kaolin is 1:1-3: 1.
In the method, the roasting temperature in the step (1) is 700-950 ℃, and the roasting time is 6-12 hours.
In the method, the mass ratio of the ammonium bicarbonate in the step (2) to the material A is 4:1-8:1, and the mass ratio of the water consumption to the total mass of the ammonium bicarbonate and the waste catalyst is 2:1-4: 1; the material A, the ammonium bicarbonate and the water can be added and mixed in any order, for example, the water can be added into the mixture of the material A and the ammonium bicarbonate, or the material A can be immersed into the aqueous solution of the ammonium bicarbonate.
In the method of the present invention, the conditions of the hydrothermal activation treatment in step (2) are as follows: the temperature is 120-160 ℃, and the treatment time is 4-8 hours. The hydrothermal activation treatment is generally carried out in a closed pressure-resistant vessel such as an autoclave.
In the method, the drying temperature in the step (2) is 60-160 ℃, and the drying time is 4-8 hours.
In the method, the mass ratio of the material B in the step (3) to the pseudo-boehmite is 20:100-50: 100.
In the method, the kneading molding in the step (3) is carried out by adopting a conventional method in the field, and an extrusion aid can be added according to needs in the molding process, wherein the extrusion aid is sesbania powder. The peptizing agent is one or more of hydrochloric acid, nitric acid, sulfuric acid, acetic acid or oxalic acid, the concentration of the peptizing agent is 0.1wt% -3wt%, the drying temperature is 100-160 ℃, the drying time is 6-10 hours, the roasting temperature is 400-550 ℃, and the roasting time is 4-8 hours.
In the method, the mass concentration of the phosphoric acid solution in the step (4) is 10-30%, the solution is used for completely immersing the solid material, the aging is carried out at the temperature of 30-60 ℃, and the aging time is 3-6 hours.
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 600-800 ℃, and the roasting time is 4-8 hours.
In the method, the hydrogenation active metal component in the step (4) is VIB group and/or VIII group metals, the VIB group metals are selected from one or more of W, Mo, the VIII group metals are selected from one or more of Co and Ni, when in loading, an active component impregnation liquid is used in a volume impregnation or supersaturation impregnation mode, then the active component is loaded on an alumina carrier through drying and roasting, the active component impregnation liquid can be an acid solution, an alkali solution or an aqueous solution containing the hydrogenation active component, the VIB group metals content in the impregnation liquid is 7-20g/100mL calculated by metal oxides, and the VIII group metals content is 1-10g/100mL calculated by metal oxides. The drying temperature is 80-160 ℃, the drying time is 6-10 hours, and the roasting is 4-8 hours at the temperature of 450-550 ℃.
Compared with the prior art, the invention has the following advantages:
(1) according to the method, the waste catalyst poisoned by vanadium is subjected to hydrothermal activation treatment, vanadium pentoxide and molybdenum oxide in the waste catalyst are respectively converted into ammonium metavanadate and ammonium molybdate to be dissolved in the solution during activation, the process of removing aluminum in advance and precipitating vanadium in the conventional method is not needed, the raw material of the waste catalyst is directly treated in one step, and the specific surface area and the pore volume of the waste catalyst are well recovered due to the dissolution and migration of metal oxides in the waste catalyst.
(2) When the waste catalyst is subjected to hydrothermal treatment in an ammonium bicarbonate solution, under the closed and weakly alkaline hydrothermal condition, one step of partial alumina in the waste catalyst is subjected to crystallization reaction, crystal grains grow up, a part of alumina reacts with ammonium bicarbonate to form aluminum ammonium carbonate, and the macroporous content of the final alumina carrier is increased due to the increase of the size of the alumina crystal grains. On the other hand, the formed ammonium aluminum carbonate can effectively adjust the accumulation state of alumina crystal grains, improve the content of macropores and play a good role in reaming the generated gas during roasting.
(3) Preferably, pseudo-boehmite and/or kaolin are added into the waste catalyst powder, the pseudo-boehmite and/or the kaolin are correspondingly converted into gamma-alumina and metakaolin during roasting, the gamma-alumina and/or the metakaolin can form long rod-shaped particles through hydrothermal crystallization and directional growth during hydrothermal treatment, the long rod-shaped particles can improve the content of macropores in an alumina carrier, meanwhile, metal substances such as molybdenum, vanadium and the like dissolved in the waste catalyst can be adsorbed by the gamma-alumina and the metakaolin after the hydrothermal treatment, and can be used as an active metal component of a hydrogenation catalyst to improve the catalytic activity of the final catalyst.
(4) When the alumina carrier is aged in a phosphoric acid solution, metal nickel and vanadium in the waste catalyst are redispersed in the alumina carrier and are secondarily utilized as hydrogenation active components; on the other hand, due to the aging effect of phosphoric acid, micro particles in the pore channels of the alumina carrier are dissolved, the content of macropores of the carrier is improved, and meanwhile, the connectivity of the pore channels is enhanced.
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. Wt% in the present invention represents a mass fraction.
The BET method: application N2Physical adsorption-desorptionThe pore structures of the carriers of the examples and comparative examples were characterized by the following specific operations: adopting ASAP-2420 type N2And 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 carriers 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 dilatometer and degassed for 30 minutes while maintaining the vacuum conditions given by the instrument, and charged with mercury. The dilatometer was then placed in the autoclave and vented. And then carrying out a voltage boosting and reducing test. The mercury contact angle is 130 degrees, and the mercury interfacial tension is 0.485N.cm-1The distribution ratio of the pore diameter of 100nm or more is measured by mercury intrusion method.
XRF characterization: the components of the sample, the target material Rh, the light path atmosphere were analyzed by using a Japanese ZSX100e X-ray fluorescence spectrometer: and (4) vacuum conditions.
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.
Percent V + Ni removal rate = (raw material oil metal V + Ni content-product metal V + Ni content)/raw material oil metal V + Ni content is multiplied by 100 percent
Percent desulfurization rate = (raw material oil sulfur content-product sulfur content)/raw material oil sulfur content x100 percent
The waste catalyst used in the examples is the waste catalyst (containing MoO) of fixed bed residue oil hydrogenation industrial device3：7.1%，NiO：9.7%，V2O5：25.9%，Al2O3: 42.5, C: 13.3%), extracted to remove oil on the surface of the catalyst and dried.
Example 1
(1) Taking the waste catalyst powder crushed to be more than 600 meshes, and roasting at 820 ℃ for 7 hours to obtain a material A;
(2) weighing 100 g of the material A and 630 g of ammonium bicarbonate in the step (1), adding 2000 g of distilled water, stirring for 20 minutes, transferring the mixed material into a high-pressure kettle, heating to 135 ℃, carrying out hydrothermal activation treatment for 6 hours, carrying out liquid-solid separation on the material after the hydrothermal treatment, and drying a filter cake for 6 hours at 120 ℃ to obtain a material B;
(3) weighing 100 g of pseudoboehmite (produced by Zibojiarun chemical Co., Ltd.), 33 g of the material B in the step (2) and 1.5 g of sesbania powder, uniformly mixing the materials, adding a proper amount of aqueous solution in which 3 g of acetic acid is dissolved, kneading, extruding into strips, forming, drying the formed product at 140 ℃ for 6 hours, and roasting at 450 ℃ for 6 hours to obtain a carrier C;
(4) weighing 50 g of the carrier C in the step (3), placing the carrier in 60ml of 20% phosphoric acid solution at 40 ℃, heating and refluxing for 4.5 hours, carrying out liquid-solid separation on the heated material, drying the solid material at 120 ℃ for 7 hours, and then roasting at 700 ℃ for 6 hours to obtain a D alumina carrier;
(5) weighing 30 g of the D alumina carrier, placing the D alumina carrier in a spray-dip rolling pot, spray-dipping the D alumina carrier in a Mo-Ni-P solution with the molybdenum oxide concentration of 13.5g/100ml and the nickel oxide concentration of 3.6g/100ml in a saturated dipping mode, drying the dipped catalyst at 120 ℃, and roasting at 450 ℃ for 5 hours to obtain the catalyst Cat-1, wherein the properties of the catalyst are shown in Table 1.
Example 2
In the same way as example 1, except that pseudo-boehmite was added to the waste catalyst powder, the mass ratio of the waste catalyst to the pseudo-boehmite was 1:1, the calcination temperature was 730 ℃, the ammonium bicarbonate addition amount was 510 g, the hydrothermal activation treatment temperature was 145 ℃, the treatment time was 7 hours, the material B addition amount was 42 g, the phosphoric acid mass concentration was 24%, the aging temperature was 50 ℃, and the aging time was 4 hours, the catalyst Cat-2 was obtained, and the catalyst properties are shown in table 1.
Example 3
In the same manner as in example 1, except that kaolin was added to the waste catalyst powder in a mass ratio of 3:1, the calcination temperature was 910 ℃, the amount of ammonium bicarbonate added was 440 g, the hydrothermal activation treatment temperature was 125 ℃, the treatment time was 8 hours, the amount of material B added was 22 g, the mass concentration of phosphoric acid was 13%, the aging temperature was 55 ℃, and the aging time was 3.5 hours, catalyst Cat-3 was obtained, and the properties of the catalyst are shown in table 1.
Example 4
Similar to example 1, except that the waste catalyst powder was added with pseudo-boehmite and kaolin, the mass ratio of the waste catalyst, pseudo-boehmite and kaolin was 4:1:1, the ammonium bicarbonate addition was 780 g, the hydrothermal activation treatment temperature was 155 ℃, the treatment time was 5 hours, the material B addition was 27 g, the phosphoric acid mass concentration was 29%, the aging temperature was 35 ℃, and the aging time was 5.5 hours, a catalyst Cat-4 was prepared, and the catalyst properties are shown in Table 1.
Comparative example 1
A comparative catalyst, Cat-5, was prepared as in example 2 except that the ammonium bicarbonate was replaced with the same amount of ammonium carbonate, and the catalyst properties are shown in Table 1.
Comparative example 2
A comparative catalyst, Cat-6, was prepared as in example 2, except that the phosphoric acid solution had not been aged, and the catalyst properties are shown in Table 1.
Comparative example 3
Comparative catalyst Cat-7 was prepared as in example 2 except that the spent catalyst was not subjected to hydrothermal activation, and the catalyst properties are shown in Table 1.
TABLE 1 catalyst Properties
| Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| Catalyst and process for preparing same | Cat-1 | Cat-2 | Cat-3 | Cat-4 | Cat-5 | Cat-6 | Cat-7 |
| Specific surface area, m2/g | 193 | 221 | 201 | 212 | 167 | 235 | 141 |
| Pore volume, mL/g | 0.88 | 0.93 | 0.90 | 0.91 | 0.79 | 0.89 | 0.71 |
| Hole is divided intoV% of cloth | |||||||
| 10-30nm | 57 | 62 | 55 | 58 | 42 | 47 | 38 |
| 100-200nm | 18 | 29 | 25 | 27 | 13 | 19 | 10 |
| MoO3，wt% | 13.7 | 13.8 | 13.6 | 13.7 | 13.8 | 13.7 | 13.8 |
| NiO，wt% | 3.9 | 3.8 | 3.7 | 3.7 | 3.9 | 3.8 | 3.8 |
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 385 ℃, the hydrogen partial pressure is 15.3MPa, and the liquid hourly space velocity is 0.4 h-1The volume ratio of hydrogen to oil was 1000, the content of each impurity in the produced oil was measured after 1500 hours of reaction, the impurity removal rate was calculated, and the evaluation results are shown in table 3.
TABLE 2 Properties of the feed oils
| Item | |
| Density (20 ℃ C.), g/cm3 | 0.97 |
| S，wt% | 4.2 |
| N，wt% | 0.31 |
| Ni，µg/g | 23.8 |
| V，µg/g | 82.5 |
| CCR，wt% | 14.6 |
TABLE 3 comparison of catalyst hydrogenation performance
| Catalyst numbering | Cat-1 | Cat-2 | Cat-3 | Cat-4 | Cat-5 | Cat-6 | Cat-7 |
| The relative demetallization rate of the alloy is higher,% | 100 | 117 | 113 | 115 | 73 | 89 | 67 |
| relative desulfurization rate% | 100 | 103 | 119 | 108 | 82 | 91 | 80 |
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 simultaneously higher hydrodesulfurization activity than the comparative catalyst.
Claims (10)
1. A preparation method of a hydrotreating catalyst is characterized by comprising the following steps: (1) crushing a molybdenum-nickel heavy oil hydrogenation catalyst poisoned by vanadium to a certain particle size, preferably adding pseudo-boehmite and/or kaolin into crushed waste catalyst powder, uniformly mixing, and then roasting to obtain a material A; (2) mixing the material A, ammonium bicarbonate and water, carrying out hydrothermal activation treatment on the mixed material, carrying out solid-liquid separation on the treated material, and drying the solid material to obtain a material B; (3) uniformly mixing the material B with pseudo-boehmite, adding a peptizer with a proper concentration into the mixed material, kneading and molding, and drying and roasting the molded product; (4) and (4) placing the alumina carrier roasted in the step (3) in a phosphoric acid solution for aging treatment, drying and roasting the aged material to obtain the alumina carrier, and then loading a hydrogenation active component to obtain the hydrogenation catalyst.
2. The method of claim 1, wherein: the molybdenum-nickel heavy oil hydrogenation catalyst poisoned by vanadium in the step (1) refers to a catalyst which is inactivated or can not meet the reaction requirement due to deposition of heavy metal and carbon deposit in the hydrotreating process of wax oil and residual oil; based on the weight of the catalyst, the content of vanadium is 5-30 percent by oxide, the active component of the catalyst is 3-20 percent by oxide, and the content of nickel is 2-15 percent by oxide.
3. The method of claim 1, wherein: the molybdenum-nickel heavy oil subjected to vanadium poisoning in the step (1) is subjected to hydro-pulverization until the mesh number is more than 80 meshes, preferably more than 200 meshes, and more preferably 400-800 meshes.
4. The method of claim 1, wherein: the mass ratio of the waste catalyst in the step (1) to the pseudoboehmite and/or the kaolin is 1:1-3: 1.
5. The method of claim 1, wherein: the roasting temperature in the step (1) is 700-950 ℃, and the roasting time is 6-12 hours.
6. The method of claim 1, wherein: the mass ratio of the ammonium bicarbonate to the material A in the step (2) is 4:1-8:1, and the mass ratio of the water consumption to the total mass of the ammonium bicarbonate and the waste catalyst is 2:1-4: 1.
7. The method of claim 1, wherein: the conditions of the hydrothermal activation treatment in the step (2) are as follows: the temperature is 120-160 ℃, and the treatment time is 4-8 hours.
8. The method of claim 1, wherein: the drying temperature in the step (2) is 60-160 ℃, and the drying time is 4-8 hours.
9. The method of claim 1, wherein: the mass ratio of the material B in the step (3) to the pseudo-boehmite is 20:100-50: 100.
10. The method of claim 1, wherein: the mass concentration of the phosphoric acid solution in the step (4) is 10-30%, the solution is used for completely immersing the solid material, and the aging is carried out at the temperature of 30-60 ℃ for 3-6 hours.
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